Polymerization of o‐quinodimethanes. IV. Radical polymerization of 1‐cyano‐o‐quinodimethane in the presence of TEMPO

The radical polymerization behavior of 1‐cyano‐o‐quinodimethane generated by thermal isomerization of 1‐cyanobenzocyclobutene in the presence of 2,2,6,6‐tetramethylpiperidine‐N‐oxide (TEMPO) and the block copolymerization of the obtained polymer with styrene are described. The radical polymerization of 1‐cyanobenzocyclobutene was carried out in a sealed tube at temperatures ranging from 100 to 150 °C for 24 h in the presence of di‐tert‐butyl peroxide (DTBP) as a radical initiator and two equivalents of TEMPO as a trapping agent of the propagation end radical to obtain hexane‐insoluble polymer above 130 °C. Polymerization at 150 °C with 5 mol % of DTBP in the presence of TEMPO resulted in the polymer having a number‐average molecular weight (M_n ) of 2900 in 63% yield. The structure of the obtained polymer was confirmed as the ring‐opened polymer having a TEMPO unit at the terminal end by ¹H NMR, ¹³C NMR, and IR analyses. Then, block copolymerization of the obtained polymer with styrene was carried out at 140 °C for 72 h to give the corresponding block copolymer in 82% yield, in which the unimodal GPC curve was shifted to a higher molecular weight region. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3434–3439, 2000     

Synthesis,characterization, thermal properties,and antimicrobial activity of 4‐chloro‐3‐methyl phenyl methacrylate/8‐quinolinyl methacrylate copolymers

4‐Chloro‐3‐methyl phenyl methacrylate (CMPM) and 8‐quinolinyl methacrylate (8‐QMA) were synthesized through the reaction of 4‐chloro‐3‐methyl phenol and 8‐hydroxy quinoline, respectively, with methacryloyl chloride. The homopolymers and copolymers were prepared by free‐radical polymerization with azobisisobutyronitrile as the initiator at 70 °C. Copolymers of CMPM and 8‐QMA of different compositions were prepared. The monomers were characterized with IR spectroscopy and ¹H NMR techniques. The copolymers were characterized with IR spectroscopy. UV spectroscopy was used to obtain the compositions of the copolymers. The monomer reactivity ratios were calculated with the Fineman–Ross method. The molecular weights and polydispersity values of the copolymers were determined with gel permeation chromatography. The thermal stability of the polymers was evaluated with thermogravimetric analysis under a nitrogen atmosphere. The homopolymers and copolymers were tested for their antimicrobial activity againstbacteria, fungi, and yeast. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 157–167, 2005     

Novel miktofunctional initiator for the preparation of an ABC‐type miktoarm star polymer via a combination of controlled polymerization techniques

An ABC‐type miktoarm star polymer was prepared with a core‐out method via a combination of ring‐opening polymerization (ROP), stable free‐radical polymerization (SFRP), and atom transfer radical polymerization (ATRP). First, ROP of ϵ‐caprolactone was carried out with a miktofunctional initiator, 2‐(2‐bromo‐2‐methyl‐propionyloxymethyl)‐3‐hydroxy‐2‐methyl‐propionic acid 2‐phenyl‐2‐(2,2,6,6‐tetramethyl‐piperidin‐1‐yl oxy)‐ethyl ester, at 110 °C. Second, previously obtained poly(ϵ‐caprolactone) (PCL) was used as a macroinitiator for SFRP of styrene at 125 °C. As a third step, this PCL–polystyrene (PSt) precursor with a bromine functionality in the core was used as a macroinitiator for ATRP of tert‐butyl acrylate in the presence of Cu(I)Br and pentamethyldiethylenetriamine at 100 °C. This produced an ABC‐type miktoarm star polymer [PCL–PSt–poly(tert‐butyl acrylate)] with a controlled molecular weight and a moderate polydispersity (weight‐average molecular weight/number‐average molecular weight < 1.37). The obtained polymers were characterized with gel permeation chromatography and ¹H NMR. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4228–4236, 2004     

Photocurable and thermally stable polymers based on 1,4‐pentadien‐3‐one‐1‐p‐hydroxyphenyl‐5‐p‐phenyl methacrylate: Copolymerization with ethyl acrylate

1,4‐Pentadien‐3‐one‐1,5‐bis(p‐hydroxyphenyl) (PBHP) was prepared by reacting p‐hydroxybenzaldehyde and acetone in the presence of an acid catalyst. 1,4‐Pentadiene‐3‐one‐1‐p‐hydroxyphenyl‐5‐p‐phenyl methacrylate (PHPPMA) monomer was prepared by reacting PBHP dissolved in ethyl methyl ketone (EMK) with methacryloyl chloride in the presence of triethylamine. A free‐radical solution polymerization technique was used for synthesizing homo‐ and copolymers of different feed compositions of PHPPMA and ethyl acrylate (EA) in EMK as a solvent with benzoyl peroxide as a free‐radical initiator at 70 ± 1 °C. All the polymers were characterized with IR and ¹H NMR techniques. The compositions of the copolymers were determined with the ¹H NMR technique. The copolymer reactivity ratios were evolved with Kelen–Tudos (EA = 1.25 and PHPPMA = 0.09) and extended Kelen–Tudos (EA = 1.30 and PHPPMA = 0.09) methods. Q (0.48) and e (1.68) values for the new monomer (PHPPMA) were calculated with the Alfrey–Price method. UV absorption spectra for poly(PHPPMA) showed two absorption bands at 302 and 315 nm. The photocrosslinking properties of the polymer samples were examined with the solvent method. Thermal analyses of the polymers were performed with the thermogravimetric‐differential thermogravimetric technique. First, the decomposition temperatures started for poly(PHPPMA), copoly(EA‐PHPPMA) (62:38), and copoly(EA‐PHPPMA) (41:59) were at 350, 410, and 417 °C, respectively. A gel permeation chromatographic method was used for determining the polymer molecular weights (weight‐average molecular weight: 2.67 × 10⁴ and number‐average molecular weight: 1.41 × 10⁴) and polydispersity index (1.89). The solubility of the monomer and the copolymers occurred at 30 °C with solvents having different polarities. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1632–1640, 2003     

Self‐assembly of star‐shaped polystyrene‐block‐polypeptide copolymers synthesized by the combination of atom transfer radical polymerization and ring‐opening living polymerization of α‐amino acid‐N‐carboxyanhydrides

The self‐assembling nature and phase‐transition behavior of a novel class of triarm, star‐shaped polymer–peptide block copolymers synthesized by the combination of atom transfer radical polymerization and living ring‐opening polymerization of α‐amino acid‐N‐carboxyanhydride are demonstrated. The two‐step synthesis strategy adopted here allows incorporating polypeptides into the usual synthetic polymers via an amido–amidate nickelacycle intermediate, which is used as the macroinitiator for the growth of poly(γ‐benzyl‐L ‐glutamate). The characterization data are reported from analyses using gel permeation chromatography and infrared, ¹H NMR, and ¹³C NMR spectroscopy. This synthetic scheme grants a facile way to prepare a wide range of polymer–peptide architectures with perfect microstructure control, preventing the formation of homopolypeptide contaminants. Studies regarding the supramolecular organization and phase‐transition behavior of this class of polymer‐block‐polypeptide copolymers have been accomplished with X‐ray diffraction, infrared spectroscopy, and thermal analyses. The conformational change of the peptide segment in the block copolymer has been investigated with variable‐temperature infrared spectroscopy. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2774–2783, 2006     

Polymerization of o‐quinodimethanes. III. Polymerization of o‐quinodimethanes bearing electron‐withdrawing groups formed in situ by thermal ring‐opening isomerization of corresponding benzocyclobutenes

The substituent effect on the radical polymerization of o‐quinodimethanes, generated by thermal isomerization of benzocyclobutenes, was investigated. Polymerizations of three benzocyclobutenes bearing electron‐withdrawing groups were studied, namely 1‐cyanobenzocyclobutene (1), 1‐chlorobenzocyclobutene (2), and 1‐bromobenzocyclobutene (3). While radical polymerizations of 2 and 3 did not afford any polymer, radical polymerization of 1 afforded n‐hexane‐insoluble polymer(M_n = 5000) in moderate yields at temperatures above 120°C. The structure of the obtained polymer was confirmed to be a ring‐opened polymer(4) by IR, ¹H‐, and ¹³C‐NMR. The yield of the polymer increased with an increase in the initiator concentration. The polymer yield reported in this paper is higher than those of benzocyclobutenes bearing electron‐donating groups, reported previously by the authors. The semi‐empirical molecular orbital calculation supported the contribution of ring‐opening polymerization of spiro‐compounds, rejecting the possibility of 1,4‐polymerization. Lastly, radical copolymerizations of 1 with various comonomers were also performed to obtain the corresponding copolymers. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1555–1563, 1999     

One‐ and two‐dimensional NMR characterization of N‐vinyl‐2‐pyrrolidone/methyl acrylate copolymers

N‐vinyl‐2‐pyrrolidone/methyl acrylate (V/M) copolymers were prepared by free‐radical bulk polymerization using benzoyl peroxide as an initiator. The copolymer composition of these copolymers was calculated from ¹H NMR spectra. The radical reactivity ratios for N‐vinyl‐2‐pyrrolidone (V) and methyl acrylate (M) were r_V = 0.09, r_M = 0.44. These reactivity ratios for the copolymerization of V and M were determined using the Kelen–Tudos and nonlinear least‐squares error‐in‐variable methods. The ¹³C{¹H} and ¹H NMR spectra of these copolymers overlapped and were complex. The complete spectral assignment of the ¹³C and ¹H NMR spectra were done with distortionless enhancement by polarization transfer and two dimensional ¹³C‐¹H heteronuclear single quantum correlation spectroscopic experiments. The two‐dimensional ¹H‐¹H homonuclear total correlation spectroscopic NMR spectrum showed the various bond interactions, thus inferring the possible structure of the copolymers. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2225–2236, 2002     

One‐ and two‐dimensional NMR characterization of N‐vinyl‐2‐pyrrolidone/methyl acrylate copolymers

N‐vinyl‐2‐pyrrolidone/methyl acrylate (V/M) copolymers were prepared by free‐radical bulk polymerization using benzoyl peroxide as an initiator. The copolymer composition of these copolymers was calculated from ¹H NMR spectra. The radical reactivity ratios for N‐vinyl‐2‐pyrrolidone (V) and methyl acrylate (M) were r_V = 0.09, r_M = 0.44. These reactivity ratios for the copolymerization of V and M were determined using the Kelen–Tudos and nonlinear least‐squares error‐in‐variable methods. The ¹³C{¹H} and ¹H NMR spectra of these copolymers overlapped and were complex. The complete spectral assignment of the ¹³C and ¹H NMR spectra were done with distortionless enhancement by polarization transfer and two dimensional ¹³C‐¹H heteronuclear single quantum correlation spectroscopic experiments. The two‐dimensional ¹H‐¹H homonuclear total correlation spectroscopic NMR spectrum showed the various bond interactions, thus inferring the possible structure of the copolymers. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2225–2236, 2002     

Controlled/living free‐radical copolymerization of 4‐(azidocarbonyl) phenyl methacrylate with methyl acrylate under 60Co γ‐ray irradiation

A new vinyl acyl azide monomer, 4‐(azidocarbonyl) phenyl methacrylate, has been synthesized and characterized by NMR and FTIR spectroscopy. The thermal stability of the new monomer has been investigated with FTIR and thermal gravimetry/differential thermal analysis (TG/DTA), and the monomer has been demonstrated to be stable below 50 °C in the solid state. The copolymerizations of the new monomer with methyl acrylate have been carried out at room temperature under ⁶⁰Co γ‐ray irradiation in the presence of benzyl 1H‐imidazole‐1‐carbodithioate. The results show that the polymerizations bear all the characteristics of controlled/living free‐radical polymerizations, such as the molecular weight increasing linearly with the monomer conversion, the molecular weight distribution being narrow (<1.20), and a linear relationship existing between ln([M]₀/[M]) and the polymerization time. The data from ¹H NMR and FTIR confirm that no change in the acyl azide groups has occurred in the polymerization process and that acyl azide copolymers have been obtained. The thermal stability of the polymers has also been investigated with TG/DTA and FTIR. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2609–2616, 2007     

Preparation and characterization of biodegradable poly(trimethylenecarbonate‐ε‐caprolactone)‐block‐poly(p‐dioxanone) copolymers

A series of poly(trimethylenecarbonate‐ε‐caprolactone)‐block‐poly(p‐dioxanone) copolymers were prepared with varying feed rations by using two step polymerization reactions. Poly(trimethylenecarbonate)(ε‐caprolactone) random copolymer was synthesized with stannous‐2‐ethylhexanoate and followed by adding p‐dioxanone monomer as the other block. The ring opening polymerization was carried out at high temperature and long reaction time to get high molecular weight polymers. The monofilament fibers were obtained using conventional melting spun methods. The copolymers were identified by ¹H and ¹³C NMR spectroscopy and gel permeation chromatography (GPC). The physicochemical properties, such as viscosity, molecular weight, melting point, glass transition temperature, and crystallinity, were studied. The hydrolytic degradation of copolymers was studied in a phosphate buffer solution, pH = 7.2, 37 °C, and a biological absorbable test was performed in rats. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2790–2799, 2005     

Synthesis,characterization, and thermal properties of a novel pentaerythritol‐initiated star‐shaped poly(p‐dioxanone)

A novel star‐shaped poly(p‐dioxanone) was synthesized by the ring‐opening polymerization of p‐dioxanone initiated by pentaerythritol with stannous octoate as a catalyst in bulk. The effect of the molar ratio of the monomer to the initiator on the polymerization was studied. The polymers were characterized with ¹H NMR and ¹³C NMR spectroscopy. The thermal properties of the polymers were investigated with differential scanning calorimetry and thermogravimetric analysis. The novel star‐shaped poly(p‐dioxanone) has a potential use in biomedical materials. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1245–1251, 2006     

New copolymers of a tautomerizable β‐ketonitrile monomer: Synthesis,characterization and solution tautomerism

The monomer 2‐methyl‐3‐oxo‐5‐phenyl‐4‐pentenonitrile (MOP) was prepared by reaction of ethyl cinnamate and propionitrile in alkaline mixture. This monomer exhibits three possible tautomeric forms. The tautomeric equilibria of MOP and its copolymers with styrene in different solvents were analyzed by ¹H NMR spectroscopy. The bulk and solution radical copolymerization initiated with azobisisobutyronitrile was carried out at 60 °C. The products were characterized by ¹H NMR, ¹³C NMR, HSQC NMR, HMBC NMR, and FTIR spectroscopies. The weight‐average molecular weight and polydispersity index were analyzed with size exclusion chromatography. The monomer reactivity ratios were obtained with the Fineman‐Ross method, obtaining a value of r₁r₂ = 0.286. MOP copolymer composition as well as the nature of the solvent significantly affected the tautomeric equilibrium. Regression analysis of the copolymer composition with solvatochromic parameters showed a good linear correlation, as quantitatively expressed by means of the linear solvation energy relationship using the empirical set of Kamlet‐Taft solvent parameters. This behavior could be attributed to polymer–polymer or polymer‐solvent interactions prevalent in solvents of different polarity, which are responsible for changes in macromolecular chain conformations, as confirmed by FTIR and viscometric studies. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Polymerization of methyl methacrylate by 2‐pyrrolidinone and n‐dodecyl mercaptan

The bulk polymerization of methyl methacrylate initiated with 2‐pyrrolidinone and n‐dodecyl mercaptan (R‐SH) has been explored. This polymerization system showed “living” characteristics; for example, the molecular weight of the resulting polymers increased with reaction time by gel permeation chromatographic analysis. Also, the polymer was characterized by Fourier transform infrared spectroscopy, ¹H NMR, and ¹³C NMR techniques. The polymer end with the iniferter structures was found. By the initial‐rate method, the polymerization rate depended on [2‐pyrrolidinone]^1.0 and [R‐SH]⁰. Combining the structure analysis and the polymerization‐rate expression, a possible mechanism was proposed. n‐Dodecyl mercaptan served dual roles—as a catalyst at low conversion and as a chain‐transfer agent at high conversion. Finally, the thermal properties were studied, and the glass‐transition temperature and thermal‐degradation temperature were, respectively, 25 and 80–100 °C higher than that of the azobisisobutyronitrile system. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3692–3702, 2002     

Synthesis and enzymatic degradation of 2‐methylene‐1,3‐dioxepane and methyl acrylate copolymers

Copolymers of 2‐methylene‐1,3‐dioxepane (MDO) and methyl acrylate (MA) containing ester units both in the backbone and as pendant groups were synthesized by free‐radical copolymerization. The influence of reaction conditions such as the polymerization time, temperature, initiator concentration, and comonomer feed ratio on the yield, molecular weight, and copolymer composition was investigated. The structure of the copolymers was confirmed by ¹H NMR, ¹³C NMR, and IR spectroscopy. Differential scanning calorimetry indicated that the copolymers had a random structure. An NMR study showed that hydrogen transfer occurred during the copolymerization. The reactivity ratios of the comonomers were r_MDO = 0.0235 and r_MA = 26.535. The enzymatic degradation of the copolymers obtained was carried out in the presence of proteinase K or a crude enzyme extracted from earthworms. The experimental results showed that the higher ester molar percentage in the backbone caused a faster degradation rate. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2898–2904, 2003     

A practical route for the preparation of poly(4‐hydroxystyrene), a useful photoresist material

The synthesis and characterization of poly(4‐hydroxystyrene) (PHS) and poly(4‐vinylphenol) (PVPh) by the polymer modification route are reported. Polystyrene prepared by free‐radical and anionic polymerization was acetylated quantitatively to poly(4‐acetylstyrene) (ACPS) with acetyl chloride and anhydrous aluminum trichloride in carbon disulfide. The acetylation worked equally well in a mixture of 1,2‐dichloroethane (DCE) and nitrobenzene containing largely DCE. The extent of the acetylation was estimated by ¹H NMR. The oxidation of ACPS was carried out with various oxidizing agents and reaction conditions. The peracetic acid oxidation in chloroform resulted in quantitative oxidation to poly(4‐acetoxystyrene) (APS) as estimated by ¹H NMR spectroscopy. The treatment of APS with hydrazine hydrate in dioxane resulted in the formation of PVPh. Deacetylation occurred with equal versatility in a mixture of aqueous sodium hydroxide and tetrahydrofuran. All the polymers were characterized via gel permeation chromatography, IR, UV, ¹H NMR, and ¹³C NMR spectroscopic techniques. This is the first report on the synthesis of ACPS, APS, and PHS of reasonably narrow molecular weight distributions or otherwise by the polymer modification route. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 453–461, 2000     

Synthesis of head‐to‐tail polyurethanes from nonsymmetric diisocyanate and ethylene glycol with organotin catalysts

An ordered head‐to‐tail (HT) polyurethane was successfully prepared by the polyaddition reaction of p‐isocyanatobenzyl isocyanate with ethylene glycol with dibutyltin dilaurate as a catalyst. Furthermore, the HT regularity of polyurethane was improved to 83% with 1,1,3,3‐tetraphenyl‐1,3‐dichlorodistannoxane. The polymerization was conducted in N,N‐dimethylformamide at 30 °C with both monomers mixed at once. The microstructure of the polymer was investigated by ¹H and ¹³C NMR spectroscopy, and the polymer obtained by the polyaddition reaction had the expected HT linkages. The constitutional regularity of the polymers influenced the thermal properties and crystallinity. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 416–429, 2001     

Synthesis of poly(D,L‐lactic acid‐alt‐glycolic acid) from D,L‐3‐methylglycolide

D ,L ‐3‐Methylglycolide (MG) was synthesized via two step reactions with a good yield (42%). It was successfully polymerized in bulk with stannous octoate as a catalyst at 110 °C. The effects of the polymerization time and catalyst concentration on the molecular weight and monomer conversion were studied. Poly(D ,L ‐lactic acid‐co‐glycolic acid) (D ,L ‐PLGA50; 50/50 mol/mol) copolymers were successfully synthesized from the homopolymerization of MG with high polymerization rates and high monomer conversions under moderate polymerization conditions. ¹H NMR spectroscopy indicated that the bulk ring‐opening polymerization of MG conformed to the coordination–insertion mechanism. ¹³C NMR spectra of D ,L ‐PLGA50 copolymers obtained under different experimental conditions revealed that the copolymers had alternating structures of lactyl and glycolyl. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4179–4184, 2000     

Polymer electrolyte membranes based on p‐toluenesulfonic acid doped poly(1‐vinyl‐1,2,4‐triazole): Synthesis,thermal and proton conductivity properties

Throughout this work, the synthesis, thermal as well as proton conducting properties of acid doped heterocyclic polymer were studied under anhydrous conditions. In this context, poly(1‐vinyl‐1,2,4‐triazole), PVTri was produced by free radical polymerization of 1‐vinyl‐1,2,4‐triazole with a high yield. The structure of the homopolymer was proved by FTIR and solid state ¹³C CP‐MAS NMR spectroscopy. The polymer was doped with p‐toluenesulfonic acid at various molar ratios, x = 0.5, 1, 1.5, 2, with respect to polymer repeating unit. The proton transfer from p‐toluenesulfonic acid to the triazole rings was proved with FTIR spectroscopy. Thermogravimetry analysis showed that the samples are thermally stable up to ～250 °C. Differential scanning calorimetry results illustrated that the materials are homogeneous and the dopant strongly affects the glass transition temperature of the host polymer. Cyclic voltammetry results showed that the electrochemical stability domain extends over 3 V. The proton conductivity of these materials increased with dopant concentration and the temperature. Charge transport relaxation times were derived via complex electrical modulus formalism (M*). The temperature dependence of conductivity relaxation times showed that the proton conductivity occurs via structure diffusion. In the anhydrous state, the proton conductivity of PVTri1PTSA and PVTri2PTSA was measured as 8 × 10^?4 S/cm at 150 °C and 0.012 S/cm at 110 °C, respectively. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1016–1021, 2010     

Acid chloride‐functionalized hyperbranched polyester for facile and quantitative chain‐end modification: One‐pot synthesis and structure characterization

Carboxylic acid chloride end‐functionalized all‐aromatic hyperbranched polyesters were prepared from the bulk polycondensation of the AB₂ monomer 5‐(trimethylsiloxy)isophthaloyl dichloride. The acid chloride end functionality of the hyperbranched polyester was modified in situ with methanol and yielded methyl ester ends in a one‐pot process. Chain‐end functionalization and esterification were quantitative according to both potentiometric titration and ¹H NMR analysis. The signals of ¹H and ¹³C NMR spectra of the esterified hyperbranched polyester were fully assigned from model compounds of the focal, linear, dendritic, and terminal units. The degree of branching and molecular weight averages measured by ¹H and ¹³C NMR spectroscopy and multidetector size exclusion chromatography increased systematically with increasing polymerization temperatures between 80 and 200 °C. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2855–2867, 2002     

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