Preparation of high molecular weight poly(N‐vinylcarbazole) in high yield by low‐temperature precipitation polymerization of N‐vinylcarbazole

To produce high molecular weight poly(N‐vinylcarbazole) (PVCZ) with high conversion, N‐vinylcarbazole (VCZ) was heterogeneously polymerized in methanol at 30, 40 and 50 °C using a low temperature initiator, 2,2′‐azobis(2,4‐dimethylvaleronitrile) (ADMVN), and the effects of polymerization temperature and concentration of initiator and solvent on the polymerization behaviour and molecular parameters of PVCZ investigated. Globally, experimental results correspond to predicted ones. Low polymerization temperature using ADMVN and a heterogeneous system using methanol proved to be successful in obtaining poly(N‐vinylcarbazole) (PVCZ) of high molecular weight and high conversion with small temperature rise during polymerization, although free radical polymerization by azoinitiator was used. The polymerization rate of VCZ in methanol at 30 °C is proportional to the 0.88th power of ADMVN concentration. The molecular weight is higher and the molecular weight distribution is narrower with PVCZ polymerized at lower temperatures. For PVCZ produced in methanol at 30 °C using an ADMVN concentration of 0.0001 mol/mol of VCZ, a weight average molecular weight of 1 750 000 g mol⁻¹ is obtained, with a polydispersity index of 1.82 © 2000 Society of Chemical Industry     

Low‐temperature photoinitiation solution polymerization behavior of N‐vinylcarbazole in tetrahydrofuran

N‐Vinylcarbazole (VCZ) was solution‐polymerized in tetrahydrofuran (THF) at ?20, 0, and 20°C using the photoinitiation method; the effects of the amount of solvent, polymerization temperature, and photoinitiator concentration were investigated. On the whole, the experimental results corresponded to predicted ones. Low polymerization temperature using photoinitiation proved to be successful in obtaining poly(N‐vinylcarbazole) (PVCZ) of a high molecular weight with a smaller temperature rise during polymerization; nevertheless of free radical polymerization by 2,2′‐azobis(2,4‐dimethylvaleronitrile) (ADMVN). The photo‐solution polymerization rate of VCZ in THF was proportional to the 0.47 power of ADMVN concentration. The molecular weight was higher and the molecular weight distribution was narrower with PVCZ polymerized at lower temperatures. For PVCZ prepared in THF at ?20°C using a photoinitiator concentration of 0.00005 mol/mol of VCZ, a weight‐average molecular weight of 510,000 was obtained, with a polydispersity index of 1.73, and a degree of lightness converged to about 99%. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3667–3672, 2002     

Preparation of high‐molecular‐weight poly(N‐vinylcarbazole) by the photoinduced low‐temperature solution polymerization of N‐vinylcarbazole in 1,1,2,2‐tetrachloroethane

For the preparation of high‐molecular‐weight (HMW) poly(N‐vinylcarbazole) (PVCZ) with a narrow molecular weight distribution, N‐vinylcarbazole (VCZ) was solution‐polymerized in 1,1,2,2‐tetrachloroethane (TCE) at ?20, 0, and 20°C with photoinitiation. The effects of the polymerization temperature and the concentrations of the polymerization solvent and photoinitiator on the polymerization behavior and molecular parameters of PVCZ were investigated. A low polymerization temperature with photoirradiation was successful in obtaining HMW PVCZ with a smaller temperature rise during polymerization than that for thermal free‐radical polymerization by azobisisobutyronitrile (AIBN). The photo‐solution‐polymerization rate of VCZ in TCE was proportional to [AIBN]^0.45. The molecular weight was higher and the molecular weight distribution was narrower for PVCZ made at lower temperatures. For PVCZ prepared in TCE at ?20°C with a photoinitiator concentration of 0.00003 mol/mol of VCZ, a weight‐average molecular weight of 920,000 was obtained, with a polydispersity index of 1.46, and the degree of transparency converged to about 99%. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2391–2396, 2003     

Preparation of high molecular weight poly(vinyl alcohol) with high yield using low‐temperature solution polymerization of vinyl acetate

Vinyl acetate (VAc) was solution‐polymerized in tertiary butyl alcohol (TBA) and in dimethyl sulfoxide (DMSO) having low chain transfer constant at 30, 40, and 50°C, using a low temperature initiator, 2,2′‐azobis(2,4‐dimethylvaleronitrile) (ADMVN). The effects of polymerization temperature and initiator concentration were investigated in terms of polymerization behavior and molecular structures of poly(vinyl acetate) (PVAc) and corresponding poly(vinyl alcohol) (PVA) obtained by saponification with sodium hydroxide. The polymerization rates of VAc in TBA and in DMSO were proportional to the 0.49 and 0.72 powers of ADMVN concentration, respectively. For the same polymerization conditions, TBA was absolutely superior to DMSO in increasing the molecular weight of PVA. In contrast, TBA was inferior to DMSO in causing conversion to polymer, indicating that the initiation rate of VAc in TBA was lower than that in DMSO. These effects could be explained by a kinetic order of ADMVN concentration calculated using initial rate method and by an activation energy difference of polymerization obtained from the Arrhenius plot. Low‐temperature solution polymerization of VAc in TBA or DMSO by adopting ADMVN proved successful in obtaining PVA of high molecular weight (number–average degree of polymerization (P_n): 4100–6100) and of high yield (ultimate conversion of VAc into PVAc: 55–80%) with diminishing heat generated during polymerization. In the case of bulk polymerization of VAc at the same conditions, maximum P_n and conversion of 5200–6200 and 20–30% was obtained, respectively. The P_n and lightness were higher, and the degree of branching was lower with PVA prepared from PVAc polymerized at lower temperatures in TBA. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1003–1012, 2001     

Preparation of high‐molecular‐weight poly(vinyl alcohol) with high yield by solution polymerization of vinyl acetate in methanol using 4,4′‐azobis(4‐cyanovaleric acid)

Vinyl acetate (VAc) was solution‐polymerized at 40°C and 50°C using 4,4′‐azobis(4‐cyanovaleric acid) (ACVA) as an initiator and methanol as a solvent, and effects of polymerization temperature and initiator concentration were investigated in terms of conversion of VAc into poly (vinyl acetate) (PVAc), degree of branching (DB) for acetyl group of PVAc, and molecular weights of PVAc and resulting poly(vinyl alcohol) (PVA) obtained by saponifying with sodium hydroxide. Slower polymerization rate by adopting ACVA and lower viscosity by methanol proved to be efficient in obtaining linear high‐molecular‐weight (HMW) PVAc with high conversion and HMW PVA. PVA having maximum number–average degree of polymerization (P_n) of 4300 could be prepared by the saponification of PVAc having maximum P_n of 7900 polymerized using ACVA concentration of 2 × 10^?5 mol/mol of VAc at 40°C. Moreover, low DB of below 1 could be obtained in ACVA system, nevertheless of general polymerization temperatures of 40°C and 50°C. This suggests an easy way for producing HMW PVA with high yield by conventional solution polymerization without using special methods such as low‐temperature cooling or irradiation. © 2006 Wiley Periodicals, Inc. J Appl PolymSci 102: 4831–4834, 2006     

Effect of Low-Temperature Solution Polymerization Conditions of Acrylonitrile on the Molecular Characteristics of Polyacrylonitrile

Abstract

Acrylonitrile (AN) was solution-polymerized in dimethyl sulfoxide (DMSO) and tertiary butyl alcohol (TBA) at 30,40 and 50°C using a low temperature initiator, 2,2′-azobis(2,4-dimethylvaleronitrile) (ADMVN), and effects of polymerization conditions were investigated in terms of molecular structures of polyacrylonitrile (PAN). Low polymerization temperature by adopting ADMVN proved to be successful in obtaining PAN of high molecular weight with smaller temperature rise during polymerization. Through a polymerization of AN in DMSO at 30°C, PAN having weight-average molecular weight (M _w ) of 931,000 was obtained, whose polydispersity index of 1.89. For the same polymerization conditions, DMSO was slightly superior to TBA in increasing molecular weight of PAN. In addition, DMSO was superior to TBA in diminishing molecular structural defects such as enaminonitrile structure in PAN polymerized, indicating that differences in polymerization and termination rates due to a different polymerization mechanisms using two polymerization solvents. The M _w , linearity, molecular structural regularity, and whiteness were higher with PAN polymerized at lower temperatures.     

Preparation of ultrahigh molecular weight syndiotactic poly(vinyl alcohol) microfibrillar fibers by low‐temperature solution polymerization of vinyl pivalate in tertiary butyl alcohol and saponification

Vinyl pivalate (VPi) was solution polymerized in tertiary butyl alcohol (TBA) and in dimethyl sulfoxide (DMSO) with a low chain transfer constant using a low temperature initiator, 2,2′‐azobis(2,4‐ dimethylvaleronitrile) (ADMVN). The effects of polymerization temperature and initiator concentration were investigated in terms of polymerization behavior and molecular structures of poly(vinyl pivalate) (PVPi) and its saponification product poly(vinyl alcohol) (PVA). TBA was absolutely superior to DMSO in increasing the syndiotacticity and molecular weight of PVA. In contrast, TBA was inferior to DMSO in causing conversion to polymer, indicating that the initiation rate of VPi production in TBA was lower than that in DMSO. These effects could be explained by a kinetic order of ADMVN concentration, calculated by the initial rate method. Low‐temperature solution polymerization of VPi in TBA or DMSO by adopting ADMVN proved to be successful in obtaining PVA of ultrahigh molecular weight [maximum number‐average degree of polymerization (P_n): 13,500–17,000] and of high yield (ultimate conversion of VPi into PVPi: 55–83%). In the case of bulk polymerization of VPi at the same conditions, maximum P_n and conversion were 14,500–17,500 and 22–36%, respectively. The P_n and syndiotactic diad content were much higher and the degree of branching was lower with PVA prepared from PVPi polymerized at lower temperatures in TBA. Moreover, PVA from the TBA system was fibrous, with a high degree of orientation of the crystallites, indicating the syndiotactic nature of TBA polymerization. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1992–2003, 2002     

Preparation and Molecular Structure of Poly(Vinyl Alcohol) by Low Temperature Bulk Polymerization of Vinyl Acetate and Saponification

Abstract

Vinyl acetate (VAc) was bulk-polymerized at 30, 40 and 50°C using a low temperature initiator, 2,2′-azobis(2,4-dimethylvaleronitrile) (ADMVN), and effects of polymerization temperature and initiator concentration were investigated in terms of polymerization behavior and molecular structures of poly(vinyl acetate) (PVAc) and corresponding poly(vinyl alcohol) (PVA) obtained by saponifying it with sodium hydroxide. Low polymerization temperature and low conversion by adopting ADMVN proved to be successful in obtaining PVA of high molecular weight. PVAc having number-average degree of polymerization (P_n ) of 6,800–10,100 was obtained, whose degree of branching for acetyl group of 0.6–0.7 at 30°C, 0.8–1.1 at 40°C, and 1.0–1.9 at 50°C at conversion of below 40%. Saponifying so prepared PVAc yielded PVA having P_n of 3,100–6,200, and syndiotactic diad (S-diad) content of 51–53%. The whiteness, S-diad content, and crystal melting temperature were higher with PVA prepared from PVAc polymerized at lower temperatures.     

Bulk polymerization of vinyl pivalate using low-temperature azoinitiator and saponification for the preparation of poly(vinyl alcohol) microfibrils

Vinyl pivalate (VPi) was bulk-polymerized at 30, 40, and 50°C using a low temperature initiator, i. e. 2,2′-azobis(2,4-dimethylvaleronitrile) (ADMVN). The effects of polymerization temperature and initiator concentration were investigated in terms of polymerization behavior and molecular structures of poly(vinyl pivalate) (PVPi) and corresponding poly(vinyl alcohol) (PVA) microfibrillar fiber obtained by saponification in KOH/methanol/water. Low polymerization temperature using ADMVN proved to be successful in obtaining PVA of syndiotacticity-rich high molecular weight. PVPi had a number-average degree of polymerization (P_n) of 27 100–35 900, and a degree of branching for pivaloyl group of 0.8–1.0 at 30°C, 1.0–1.3 at 40°C, and 1.4–1.7 at 50°C at conversions below 40%. Saponification of PVPi yielded PVA having a P_n of 10  400–16  500, and syndiotactic diad (S-diad) content of 58.8–61.5%. It was found that all PVA specimens represented microfibrillar morphologies, with high crystallinity and orientation. The S-diad content and crystal melting temperature were higher with PVA prepared from PVPi polymerized at lower temperatures.     

Preparation of isotacticity‐rich poly(tert‐butyl vinyl ether) by the cationic polymerization of tert‐butyl vinyl ether with dimethyl[rac‐ethylenebis(indenyl)]zirconium and tri(pentafluorophenyl)borane

tert‐Butyl vinyl ether (tBVE) was polymerized with the catalyst dimethyl[rac‐ethylenebis(indenyl)] zirconium (ansa‐zirconocene) with tri(pentafluorophenyl) borane [B(C₆F₅)₃] as a cocatalyst. The effects of various polymerization conditions, such as the polymerization time, type of polymerization solvent, polymerization temperature, and catalyst concentration, on the conversion of tBVE into poly(tBVE), its molecular weight and molecular weight distribution, and its stereoregularity were investigated. The maximum conversion of tBVE into poly(tBVE) was over 90% at a polymerization temperature of ?30°C with an ansa‐zirconocene and B(C₆F₅)₃ concentration of 3.0 × 10^?7 mol/mol of tBVE, respectively. The number‐average molecular weights of poly(tBVE) ranged from approximately 14,000 to 20,000, with a lower polydispersity index (weight‐average molecular weight/number‐average molecular weight) ranging from 1.48 to 1.77, at all polymerization temperatures. The number‐average molecular weight of poly(tBVE) increased with decreases in the polymerization temperature and catalyst concentration. The mm triad sequence fraction of poly(tBVE) polymerized with ansa‐zirconocene/B(C₆F₅)₃ at ?30°C was much higher than that of poly(tBVE) polymerized with the B(C₆F₅)₃ catalyst at ?30°C, and this indicated that the ansa‐zirconocene/B(C₆F₅)₃ catalyst system affected the isospecific polymerization of tBVE. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis,characterization and biological activity of 3‐(1‐cyclohexyl)azetidinyl methacrylate monomer and its homopolymer

3‐(1‐Cyclohexyl)azetidiniyl methacrylate (CyAMA), a new methacrylate monomer, was synthesized by reaction of the sodium salt of 1‐cyclohexylazetidin‐3‐ol with methacryloyl chloride. The monomer was polymerized at 60 °C in 1,4‐dioxane solution using 2,2′‐ azobisisobutyronitrile (AIBN) as an initiator. CyAMA and poly(CyAMA) were characterized by FTIR and ¹H and ¹³C NMR spectroscopy. The activation energy of the initiation step of the polymerization was estimated from initial rates, and the number average molecular weight of the homopolymer was determined by gel permeation chromatography (GPC). The antibacterial and antifungal effects of the monomer and homopolymer were investigated on various bacteria and fungi. The thermal stability of poly(CyAMA) was investigated by TGA, and its glass transition temperature was determined by DSC as 93 °C. © 2000 Society of Chemical Industry     

Free radical kinetics of N‐methyl N‐vinyl acetamide polymerization at low conversions in aqueous media

N‐methyl N‐vinyl acetamide (NMNVA) monomer was polymerized at low conversions and its free radical kinetics were detailed using capillary dilatometry. The polymerizations were conducted isothermally, at 40°C using 2,2′‐azobis[2‐(2‐imidazolin‐2‐yl) propane dihydrochloride] (ABDH) as initiator. Monomer concentration and initiator concentration ranges were 1.10–1.70 mol · L⁻¹ and 1–4 mmol · L⁻¹, respectively. The aqueous polymerization media were kept at neutral pH. The rates of polymerization (R_p) and orders of reaction with respect to NMNVA and ABDH concentrations were evaluated and the kinetic expression was found to be ideal, with R_p ∝ [NMNVA]^1.07 [ABDH]^0.61. The polymers obtained were characterized by their viscosity numbers and correlation of viscosity average molecular weights was made with the amount of ABDH initiator. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 337–341, 2001     

Tert‐butyl peroxyacetate initiated semibatch polymerization of 1,1‐difluoroethylene in supercritical carbon dioxide

Due to its inertness and solubility in vinylidene fluoride, (VF2), supercritical carbon dioxide is used as a replacement solvent for producing polyvinylidene fluoride (PVDF). tert‐butyl peroxyacetate (TBPA) was evaluated for the first time as a free radical initiator for radical chain polymerization of VF2 producing PVDF without use of a dispersion agent in a semibatch reactor using supercritical carbon dioxide. Diethyl peroxydicarbonate (DEPDC) at 75°C has been evaluated in many publications as an initiator in batch and continuous reactors for polymerization of VF2 in supercritical carbon dioxide. The effects of monomer and initiator concentration, agitation, and reaction time upon average molecular weight and polydispersity were evaluated using TBPA as an initiator at 104°C and compared with DEPDC initiated polymerization. It was found that as agitation rate, monomer concentration, and reaction time increased, the average molecular weight of PVDF using TBPA as an initiator increased. Lower concentrations of TBPA were needed compared to DEPDC to produce comparable molecular weights of PVDF. Using TBPA as an initiator at the conditions investigated resulted in lower polydispersity at similar monomer concentrations compared to DEPDC. Average molecular weights using TBPA ranged from 49,900 g/mol to 1.3 million g/mol and polydispersity ranged from 1.3 to 5.4. POLYM. ENG. SCI., 56:435–440, 2016. © 2016 Society of Plastics Engineers     

Post‐extrusion solid‐state polymerization of fully drawn polyester yarns

Post‐extrusion solid‐state polymerization (SSP) of a commercial fully drawn filament yarn (FDY) of poly(ethylene terephthalate) was carried out at 220°C, 230°C, and 240°C for a duration of 30 min to 2 h under inert atmosphere. Molecular weight of the solid‐state polymerized polyester filaments was increased from 1.67 × 10⁴ gm/mol to a maximum of 2.61 × 10⁴ gm/mole for the sample subjected to 240°C for 2 h. The kinetics of the SSP in the highly oriented crystalline FDY polyester filaments was investigated using an empirical relation between initial molecular weight and time of SSP and was found to be greatly enhanced, compared to amorphous unoriented polyester chips. Though the free annealing (i.e., under no tension) of samples at high temperature during solid‐state polymerization had a detrimental effect on the orientation of the FDY yarn, the simultaneous increase in the molecular weight compensated the loss in mechanical properties to a great extent. Application of tension during SSP was found to improve the mechanical properties of the SSP yarn by a small value. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5113–5122, 2006     

Preparation of nanometer‐sized poly(methacrylic acid) particles in water‐in‐oil microemulsions

A water‐in‐oil microemulsion, water‐in‐cyclohexane stabilized by poly(ethylene glycol) tert‐octylphenyl, was developed to prepare poly(methacrylic acid) (PMAA) particles. Up to 100% conversion of the amphiphilic monomer, methacrylic acid (MAA), which could not be converted to the polymer efficiently in a dioctylsulfosuccinate sodium salt/toluene microemulsion, was achieved. The viscosity‐average molecular weight of the PMAA prepared was 1.45 × 10⁵ g/mol. The effects of some polymerization parameters, including the reaction temperature and the concentrations of the initiator and the monomer, on the polymerization of MAA were investigated. The results showed that the polymerization rate of MAA was slower than that of acrylamide in the microemulsions reported in the literature. The degree of conversion increased with the initiator concentration, reaction temperature, and monomer concentration. However, the stable microemulsions became turbid during the polymerization when the reaction temperature was at 70°C or at a high monomer concentration (40 wt %) The synthesized PMAA particles were spherical and had diameters in the range of ～50 nm. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2497–2503, 2006     

Surface grafting of polyacrylamide from polyethylene‐based copolymer film

Atom transfer radical polymerization (ATRP) was used to grow polyacrylamide from the surface of ethylene–acrylic acid copolymer (EAA) film. The surface functionalization constituted initiator immobilization and surface graft polymerization. All reaction steps were conducted at 24 ± 3°C; polymerization was done in aqueous solution. For initiator immobilization, the carboxylic acid groups on EAA film were converted to acid chloride groups; further reaction with ethanolamines gave hydroxyl groups onto which 2‐bromoisobutyryl bromide initiator was attached. ATR‐FTIR data indicated that 1.64 ± 0.09 times higher initiator density was achieved by using diethanolamine, relative to ethanolamine. Acrylamide monomer was polymerized from the initiator by ATRP to yield nondistorted, transparent films with polymerization times of up to 1 h. For films prepared using diethanolamine, 1 h polymerization time reduced the static water contact angle by more than 50°, significantly increasing the hydrophilicity of the film surface. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1589–1595, 2004     

ICAR ATRP of methyl methacrylate catalyzed by FeCl3·6H2O/succinic acid

In this work, methyl methacrylate (MMA) was polymerized by initiator for continuous activator regeneration (ICAR) atom transfer radical polymerization (ATRP) method to obtain low molecular weight living polymers. The ATRP initiator was ethyl 2‐bromoisobutyrate, the catalyst ligand complex system was FeCl₃·6H₂O/succinic acid, and the conventional radical initiator 2,2′‐azobisisobutyronitrile was used as a thermal radical initiator. Polymers with controlled molecular weight were obtained with ppm level of Fe catalyst complex at 90°C in N,N‐dimethylformamide. The polymer was characterized by nuclear magnetic resonance (NMR). The molecular weight and molecular weight distribution of the obtained poly (methyl methacrylate) were measured by gel permeation chromatography method. The kinetics results indicated that ICAR ATRP of MMA was a “living”/controlled polymerization, corresponding to a linear increase of molecular weights with the increasing of monomer conversion and a relatively narrow polydispersities index. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation of high molecular weight poly(vinyl pivalate) with high yield and high molecular weight poly(vinyl alcohol) by emulsion polymerization of vinyl pivalate and saponification

To prepare high molecular weight (HMW) poly(vinyl pivalate) (PVPi) with high yield and high linearity which is a promising precursor for syndiotactic poly (vinyl alcohol) (PVA), vinyl pivalate (VPi) was emulsion polymerized, using 2,2′‐azobis(2‐amidinopropane) dihydrochloride (AAPH) as an initiator and sodium dodecyl sulfate (SDS) as an emulsifier. The effect of the polymerization conditions on the conversion, molecular weight, and degree of branching was investigated. PVA with maximum number‐average degree of polymerization (P_n) of 6200 could be prepared by complete saponification of PVPi, with P_n of 13,300–16,700 obtained at polymerization temperature of 50°C, using SDS and AAPH concentration of 2.0 × 10^?3 mol/L of water and 1.0 × 10^?3 mol/L of water, respectively, and the maximum conversion was about 90%. From the emulsion polymerization of VPi, spherical PVPi with high yield was effectively prepared, which might be useful for the precursor of syndiotactic PVA micro‐ and nano‐spheres with various surface properties. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 410–414, 2007     

Controlled radical double ring‐opening polymerization of 2‐methylene‐1,4,6‐trioxaspiro[4,4]nonane

Controlled radical double ring‐opening polymerization of 2‐methylene‐1,4,6‐trioxaspiro[4,4]nonane (MTN) has been achieved with tert‐butyl perbenzoate (TBPB) as initiator in the presence of 2,2,6,6‐tetramethyl‐1‐piperidinyloxy free radical (TEMPO) at 125 °C. The molecular weight polydispersity of the polymers is obviously lower than that of polymers obtained by conventional procedures. As the [TEMPO]/[TBPB] molar ratio increased, the polydispersity decreased and a polydisperty as low as 1.2 was obtained at high TEMPO concentration. With the conversion of the monomer increasing, the molecular weight of the polymers turned higher and a linear relationship between the M_w and the monomer conversion was observed. The monomer conversion, however, did not exceed 30 %. © 2000 Society of Chemical Industry     

Initiator‐fragment incorporation radical polymerization of diallyl phthalate: Kinetics,formation of hyperbranched polymer,and iridescent porous film thereof

Diallyl phthalate (DAP) was polymerized in toluene using dimethyl 2,2′‐azobisisobutyrate (MAIB) of high concentrations (0.1–0.9 mol/L) as initiator. The polymerization of DAP of 1.50 mol/L with MAIB of 0.50 mol/L proceeded homogeneously at 80°C without gelation to give soluble polymers in a high yield of 93%. Kinetic results of the homogeneous polymerization at 80°C suggest significant contributions of the degradative chain transfer and the primary radical termination as shown by the rate equation, R_p = k [MAIB]^0.8[DAP]^1.0 (R_p = polymerization rate). The polymer formed in the polymerization of DAP (1.30 mol/L) with MAIB (0.50 mol/L) at 80°C for 8 h consisted of the DAP units with (17 mol %) and without (47 mol %) double bond and the methoxycarbonylpropyl group (36 mol %) as MAIB‐fragment. The large fraction of the incorporated initiator‐fragment as terminal group indicates that the polymer has a hyperbranched structure. The film cast from a solution of the hyperbranched poly(DAP) in tetrahydrofuran showed an iridescent color. The confocal scanning laser microscope image of the film revealed that the iridescent film contained the pores of about 1 μm arranged in an ordered array. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 408–415, 2006