Effect of sparteine on the photopolymerization of methyl and ethyl methacrylates with bis(cyclopentadienyl)titanium dichloride in a water–methanol mixture

The photopolymerization of methyl methacrylate (MMA) with bis(cyclopentadienyl)titanium dichloride (Cp₂TiCl₂) in a H₂O‐MeOH [1 : 1 (v/v)] mixture was examined at 40°C in the presence of 2,2′‐bipyridyl (Bipy), 1,10‐phenanthlorine (Phen) or sparteine (Spr) as the chelating reagent. The presence of these chelating reagents retarded the photopolymerization. Poly(MMA)s formed in the presence of them were found to contain a considerable fraction of the benzene‐insoluble part, in contrast to the ones in the absence of them. Spr was the most effective for formation of the insoluble part. The benzene‐insoluble poly(MMA) was insoluble in usual organic solvents including acetone, tetrahydrofuran, ethyl acetate, and dimethyl sulfoxide, suggesting crosslinking. However, poly(MMA) reproduced by hydrolysis of the insoluble part followed by methylation was soluble in usual organic solvents, indicating no crosslinking between polymer main chains. The insoluble part was thermally more stable than the soluble part. Polymerization of ethyl methacrylate in the presence of Spr gave similar results. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 815–822, 2001     

Coevolution of the Activity and Thermostability of an ϵ-Keto Ester Reductase for Better Synthesis of an (R)-α-Lipoic Acid Precursor

In this work, we have identified a significantly improved variant (S131Y/Q252I) of the natural ϵ-keto ester reductase CpAR2 from Candida parapsilosis for efficiently manufacturing (R)-8-chloro-6-hydroxyoctanoic acid [(R)-ECHO] through co-evolution of activity and thermostability. The activity of the variant CpAR2_S131Y/Q252I towards the ϵ-keto ester ethyl 8-chloro-6-oxooctanoate was improved to 214 U mg⁻¹—from 120 U mg⁻¹ in the case of the wild-type enzyme (CpAR2_WT)—and the half-deactivating temperature (T₅₀, for 15 min incubation) was simultaneously increased by 2.3 °C in relation to that of CpAR2_WT. Consequently, only 2 g L⁻¹ of lyophilized E. coli cells harboring CpAR2_S131Y/Q252I and a glucose dehydrogenase (GDH) were required in order to achieve productivity similar to that obtained in our previous work, under optimized reaction conditions (530 g L⁻¹ d⁻¹). This result demonstrated a more economical and efficient process for the production of the key (R)-α-lipoic acid intermediate ethyl 8-chloro-6-oxooctanoate.     

Polymerization of methyl methacrylate with Ni(acac)2–methylaluminoxane catalyst

Polymerization of methyl methacrylate (MMA) with nickel(II) acetylacetonate [Ni(acac)₂] in combination with methylaluminoxane (MAO) was investigated. Ni(acac)₂ was found to be an effective catalyst for the polymerization of MMA. From a kinetic study of the polymerization of MMA with the Ni(acac)₂–MAO catalyst, the overall activation energy was estimated to be 15 kJmol⁻¹. The polymerization rate (R_p) was expressed as follows: R_p = k [MMA]^1.0[Ni(acac)₂–MAO]^0.6 (the MAO/Ni mole ratio was kept constant). The mechanism for the polymerization of vinyl monomers with the Ni(acac)₂–MAO catalyst is discussed. © 2000 Society of Chemical Industry     

Synthesis and characterization of poly(methyl methacrylate)‐grafted silica microparticles

A procedure to synthesize poly(methyl methacrylate)‐grafted silica microparticles was developed by using radical photopolymerization of methyl methacrylate (MMA) initiated from N,N‐diethyldithiocarbamate (DEDT) groups previously bound to the silica surface (grafting “from”). The functionalization of silica microparticles with DEDT groups was performed in two steps: introduction of chlorinated functions onto the surface of silica particles, and then nucleophilic substitution of chlorines by DEDT functions via a S_N2 mechanism. The study was performed with a Kieselgel® S silica which was initially chlorinated in surface, either by direct chlorination of silanols with thionyl chloride, or by using a condensation reaction between silanols and a chlorofunctional trialkoxysilane reagent, 4‐(chloromethyl)phenyltrimethoxysilane and chloromethyltriethoxysilane, respectively. Three types of DEDT‐functionalized silica microparticles were prepared with a good control of the reactions, and then characterized by solid‐state ¹³C and ²⁹Si CP/MAS NMR. Their ability to initiate MMA photopolymerization was studied. The kinetics of MMA photopolymerization was followed by HPLC and ¹H‐NMR. Whatever the silica used the grafting progresses very slowly. On the other hand, the conversion of MMA in PMMA grafts is depending on the structure of the DEDT‐functionalized Kieselgel® S used. Poly(methyl methacrylate)‐grafted silica microparticles bearing high length grafts ( about 100) were synthesized. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Photopolymerization of Methyl Methacrylate Sensitized by Tris(2,2′-bipyridine)iron(III)

The photopolymerization of methyl methacrylate (MMA) sensitized by tris(2,2′-bipyridine)iron(III ) complex, [Fe(bpy)₃]³⁺, was studied at 35°C in the presence of an electron donor, triethylamine (TEA) with UV radiation of wavelength 254nm. The initial rate of polymerization, R_p, shows a linear dependence on [MMA] with an exponential value of 1·18±0·04. R_p varies linearly with the square root of the photosensitizer concentration up to 2·00×10^-4moll^-1, and above this concentration, R_p decreases with the increase of photosensitizer concentration. The rate of polymerization is not affected by the concentration of the co-initiator, [TEA]. A suitable mechanism for the reaction is proposed to explain the kinetics of the reaction. © 1997 SCI.     

Atom transfer radical polymerization of methyl methacrylate initiated with a macroinitiator of poly(vinyl acetate)

Well‐defined poly(vinyl acetate‐b‐methyl methacrylate) block copolymers were successfully synthesized by the atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) in p‐xylene with CuBr as a catalyst, 2,2′‐bipyridine as a ligand, and trichloromethyl‐end‐grouped poly(vinyl acetate) (PVAc–CCl₃) as a macroinitiator that was prepared via the telomerization of vinyl acetate with chloroform as a telogen. The block copolymers were characterized with gel permeation chromatography, Fourier transform infrared, and ¹H‐NMR. The effects of the solvent and temperature on ATRP of MMA were studied. The control over a large range of molecular weights was investigated with a high [MMA]/[PVAc–CCl₃] ratio for potential industry applications. In addition, the mechanism of the polymerization was discussed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1089–1094, 2006     

Photo‐Induced atom transfer radical polymerization with nanosized α‐Fe2O3 as photoinitiator

Photo‐induced atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) was achieved in poly(ethylene glycol)‐400 with nanosized α‐Fe₂O₃ as photoinitiator. Well‐defined poly(methyl methacrylate) (PMMA) was synthesized in conjunction with ethyl 2‐bromoisobutyrate (EBiB) as ATRP initiator and FeCl₃·6H₂O/Triphenylphosphine (PPh₃) as complex catalyst. The photo‐induced polymerization of MMA proceeded in a controlled/living fashion. The polymerization followed first‐order kinetics. The obtained PMMA had moderately controlled number‐average molecular weights in accordance with the theoretical number‐average molecular weights, as well as narrow molecular weight distributions (M_w/M_n). In addition, the polymerization could be well controlled by periodic light‐on–off processes. The resulting PMMA was characterized by ¹H nuclear magnetic resonance and gel permeation chromatography. The brominated PMMA was used further as macroinitiator in the chain‐extension with MMA to verify the living nature of photo‐induced ATRP of MMA. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42389.     

Synthesis of hyperbranched polymers via a facile self-condensing vinyl polymerization system - Glycidyl methacrylate/Cp2TiCl2/Zn

A facile self-condensing vinyl polymerization (SCVP) system, the combination of glycidyl methacrylate, Cp₂TiCl₂ and Zn, has been firstly used to prepare novel hyperbranched polymers, consisting of vinyl polymers as the backbone, and cyclic ester polymers (poly(?-caprolactone) or poly(l-lactide)) as the side chains. The polymerizations are initiated by the epoxide radical ring-opening catalyzed by Cp₂Ti(III)Cl which is generated in situ via the reaction of Cp₂TiCl₂ with Zn. The key to success is that the polymerizations can proceed concurrently via two dissimilar chemistries possessing the opposite active initiating species, including ring-opening polymerization (ROP) and controlled/living radical polymerization (CRP). We have demonstrated that this facile one-step polymerization technique can be applied successfully to prepare highly branched polymers with a multiplicity of end reactive functionalities including Ti alkoxide, hydroxyl and vinyl functional groups.     

Photoinitiation of methyl methacrylate with a novel iron (III) oxalato complex

Summary The photopolymerization of methyl methacrylate (MMA) by the photoinitiator iron (III) tris (oxalato) ferrate(III) tetrahydrate, Fe[Fe(C₂O₄)₃] . 4H₂O (A) has been studied under UV radiation of 254 nm at 35°C in DMSO. The initial rate of polymerization, R_p is proportional to [MMA]^1.11±0.13. R_p also varies linearly with the square root of [A] up to 5.00 X 10^-4 mol l^-1 and above this concentration, R_p decreases with the increase of [A]. It is likely that at a higher concentration of the complex A, the termination of the polymer chain occurs through interaction between the molecules of the complex. A suitable mechanism has been proposed to explain the kinetics of the reaction.     

Catalytic Behavior of Bis(Pyrrolide-Imine) and Bis(Phenoxy-Imine) Titanium Complexes for the Copolymerization of Ethylene with Propylene, 1-Hexene,or Norbornene

This contribution reports the catalytic behavior of bis(pyrrolide-imine)Ti complexes 1 and 2 , [2-(RNCH)-C₄H₃N]₂TiCl₂ ( 1 , R = Ph; 2 , R = cyclohexyl), and bis(phenoxy-imine)Ti complex 3 , [2-(Ph-NCH)-3-t Bu-C₆H₃O]₂TiCl₂ for the copolymerization of ethylene with propylene, 1-hexene, or norbornene. An inspection of the X-ray structures of complexes 1–3 suggested that complexes 1 and 2 with pyrrolide-imine ligands would provide more space for olefin polymerization than complex 3 with phenoxy-imine ligands. In addition, DFT calculations also showed that active species derived from complexes 1 and 2 possess higher electrophilicity of the Ti center compared to that from complex 3 . Complexes 1 and 2 on activation with methylalumoxane (MAO) had higher affinity for propylene and 1-hexene and incorporated higher amounts of propylene ( 1 ; 30.5 mol%, 2 ; 23.4 mol%) and 1-hexene ( 1 ; 1.9 mol%, 2 ; 1.7 mol%) than complex 3 (propylene; 4.5 mol%, 1-hexene; 0.4 mol%). The incorporation levels of propylene and 1-hexene displayed by complexes 1 and 2 were lower than those for Cp₂TiCl₂ (propylene; 41.6 mol%, 1-hexene; 5.1 mol%) under identical conditions. In contrast, complexes 1 and 2 exhibited higher incorporation ability for norbornene and produced copolymers with much higher norbornene contents ( 1 ; 32.0 mol%, 2 ; 26.5 mol%) than Cp₂TiCl₂ (1.2 mol%) under the same conditions. Additionally, complex 3 also promoted higher norbornene incorporation (4.3 mol%) than Cp₂TiCl₂ and provided a copolymer with extremely narrow molecular weight distribution (M_w/M_n 1.14). A correlation exists between electrophilicity of the Ti center in active species and norbornene incorporation.     

Isotactic copolymerization of methyl methacrylate (MMA) with alkyl acrylates

Summary Copolymerization of methyl methacrylate(MMA) and alkyl acrylates [t-butyl(tBA) and 2-ethylhexyl(OA)] was realized from a short living pre-PMMA. The poly(MMA-co-tBA) and poly(MMA-co-OA) obtained with rac-Me₂Si(Ind)₂ZrMe₂ were characterized as random isotactic copolymers. Whereas, corresponding syndio-rich atactic random copolymers were obtained with Cp₂ZrMe₂.     

Solution properties of hyperbranched polymers and synthetic application for amphiphilic star‐hyperbranched copolymers by grafting from hyperbranched macroinitiator

Hyperbranched polystyrenes (PS) were prepared by living radical photopolymerization of N,N‐diethyldithiocarbamoylmethylstyrene (DTCS) as an inimer under UV irradiation. Branched PS with an average chain length between branching points of four styrene units was also prepared by living radical copolymerization of DTCS with styrene. The ratio of radius of gyration to hydrodynamic radius R_G/R_H for these hyperbranched polymers was in the range 0.82–0.89 in toluene. The translational diffusion coefficient D(C) showed a constant value in the range of 0–14 × 10^?3 g ml^?1 in toluene. It was found from these dilute solution properties that hyperbranched PSs formed a unimolecular structure even in a good solvent because of their compact nature. These hyperbranched PSs exhibited large amounts of photofunctional carbamate (DC) groups on their outside surfaces. Subsequently, we derived amphiphilic star‐hyperbranched copolymers by grafting from hyperbranched macroinitiator with 1‐vinyl‐2‐pyrrolidinone. These star‐hyperbranched copolymers were soluble in water and methanol. © 2001 Society of Chemical Industry     

Reactivity ratios and copolymer properties of 2‐(diisopropylamino)ethyl methacrylate with methyl methacrylate and styrene

Free radical copolymerization kinetics of 2‐(diisopropylamino)ethyl methacrylate (DPA) with styrene (ST) or methyl methacrylate (MMA) was investigated and the corresponding copolymers obtained were characterized. Polymerization was performed using tert‐butylperoxy‐2‐ethylhexanoate (0.01 mol dm^?3) as initiator, isothermally (70 °C) to low conversions (<10 wt%) in a wide range of copolymer compositions (10 mol% steps). The reactivity ratios of the monomers were calculated using linear Kelen–Tüd?s (KT) and nonlinear Tidwell–Mortimer (TM) methods. The reactivity ratios for MMA/DPA were found to be r₁ = 0.99 and r₂ = 1.00 (KT), r₁ = 0.99 and r₂ = 1.03 (TM); for the ST/DPA system r₁ = 2.74, r₂ = 0.54 (KT) and r₁ = 2.48, r₂ = 0.49 (TM). It can be concluded that copolymerization of MMA with DPA is ideal while copolymerization of ST with DPA has a small but noticeable tendency for block copolymer building. The probabilities for formations of dyad and triad monomer sequences dependent on monomer compositions were calculated from the obtained reactivity ratios. The molar mass distribution, thermal stability and glass transition temperatures of synthesized copolymers were determined. Hydrophobicity of copolymers depending on the composition was determined using contact angle measurements, decreasing from hydrophobic polystyrene and poly(methyl methacrylate) to hydrophilic DPA. Copolymerization reactivity ratios are crucial for the control of copolymer structural properties and conversion heterogeneity that greatly influence the applications of copolymers as rheology modifiers of lubricating oils or in drug delivery systems. © 2015 Society of Chemical Industry     

Fast transient fluorescence technique (FTRT) for studying dissolution of polymer glasses

The fast transient fluorescence technique (FTRT) was used for studying the swelling and dissolution of a glassy polymer formed by free‐radical polymerization of methyl methacrylate (MMA). Anthracene (An) was introduced during polymerization as a fluorescence probe to monitor swelling and dissolution. Swelling and dissolution processes of disc‐shaped poly(methyl methacrylate) (PMMA) glasses in a chloroform–heptane mixture were monitored by measuring the fluorescence lifetimes of An from its decay traces. A method is developed for low quenching efficiencies for measuring lifetimes, τ, of An, and it was observed that τ values decreased as the dissolution process proceeded. Desorption, D, and mutual diffusion, D_m, coefficients of An molecules were measured during dissolution of PMMA and found to be around 5.4 × 10⁻⁶ (cm²/s) and 2.2 × 10⁻⁵ (cm²/s), respectively. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 948–957, 1999     

The synthesis of poly(3‐hydroxybutyrate)‐g‐poly(methylmethacrylate) brush type graft copolymers by atom transfer radical polymerization method

Brush type of poly (3‐hydroxy butyrate), PHB, copolymer synthesis has been reported. Natural PHB was chlorinated by passing chlorine gas through PHB solution in CHCl₃/CCl₄ mixture (75/25 v/v) to prepare chlorinated PHB, PHB‐Cl, with the chlorine contents varying between 2.18 and 39.8 wt %. Toluene solution of PHB‐Cl was used in the atom transfer radical polymerization (ATRP) of methyl methacrylate, MMA, in the presence of cuprous bromide (CuBr)/2,2′‐bipyridine complex as catalyst, at 90°C. This “grafting from” technique led to obtain poly (3‐hydroxybutyrate)‐g‐poly(methylmethacrylate) (PHB‐g‐PMMA) brush type graft copolymers (cylindrical brush). The polymer brushes were fractionated by fractional precipitation methods and the γ values calculated from the ratio of the volume of nonsolvent to volume of solvent of brushes were ranged between 2.8 and 9.5 depending on the molecular weight, grafting density, and side chain length of the brushes, while the γ values of PHB, PHB‐Cl, and homo‐PMMA were 2.7–3.8, 0.3–2.4, and 3.0–3.9, respectively. The fractionated brushes were characterized by gel permeation chromatography, ¹H‐NMR spectrometry, thermogravimetric analysis (TGA), and differential scanning calorimetry techniques. PHB‐g‐PMMA brush type graft copolymers showed narrower molecular weight distribution (mostly in range between 1.3 and 2.2) than the PHB‐Cl macroinitiator (1.6–3.5). PHB contents in the brushes were calculated from their TGA thermograms and found to be in range between 22 and 42 mol %. The morphologies of PHB‐g‐PMMA brushes were also studied by scanning electron microscopy. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Structural estimation of particle arrays at air–water interface based on silica particles with well‐defined and highly grafted poly(methyl methacrylate)

Silica nanoparticles with well‐defined, highly grafted dense poly(methyl methacrylate) (MMA) were prepared by surface‐initiated activators regenerated by electron transfer for atom transfer radical polymerization (ARGET ATRP) of methyl methacrylate with an initiator‐fixed silica particle in the presence of air. Two different polymerizations of MMA were carried out under the same conditions using tris[2‐(dimethylamino)ethyl]amine (Me₆TREN) and N,N,N′,N′,N″‐pentamethyldiethylene‐triamine (PMDETA) as the ligand, respectively. In the CuCl₂/PMDETA system, polymerization appeared to be more controlled with a lower polydisperisty compared with the CuCl₂/Me₆TREN system. The monolayer of these particles was formed at the air–water interface using Langmuir‐Blodgett (LB) technique. Multilayers of the particles were fabricated by repetition of LB depositing. A surface pressure–area (π–A) measurement and SEM observation were used to characterize the particle arrays. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Methyl methacrylate based copolymers and terpolymers: Preparation,identification, and plasticizing capability for a poly(methyl methacrylate) used in aviation

In this study, we first synthesized transparent poly(methyl methacrylate–maleic anhydride) [P(MMA–MAH)] and poly(methyl methacrylate–maleic anhydride–N‐2‐methyl‐4‐nitrophenyl maleimide) [P(MMA–MAH–MI)] via free‐radical polymerization at different monomer ratios. The synthesized polymers were characterized by titration, viscometric, spectroscopy, and thermal analyses. Higher contents of maleic anhydride (MAH) resulted in increases in the viscosity, glass‐transition temperature (T_g), and transparency. The synthesized polymers were then blended with a commercial‐grade poly(methyl methacrylate) (PMMA) used in aviation in the presence of CHCl₃. According to the free volume theory, the incorporation of 5 wt % P(MMA–MAH)s or P(MMA–MAH–MI)s into the commercial PMMA resulted in a plasticizing impact on this thermoplastic, which was confirmed by the decrease in the T_g values of the blends with almost the same transparency as the initial PMMA. In fact, the higher the content of MAH was, the lower the T_g of the blends was. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46603.     

Determination of monomer reactivity ratios for copolymerizations of methacrylic acid with poly (ethylene glycol) monomethacrylate

Self-associating copolymers of methacrylic acid (MAA) with poly (ethylene glycol) monomethacrylate (PEGMA) were prepared by free radical copolymerization of MAA with PEGMA using dispersion polymerization in D₂O, or solution polymerization in a 50/50 ethanol–D₂O mixture. These copolymers have been studied as components of reversible hydrogels¹ and in medical applications.² In order to understand the relationship between the copolymer structure and its performance, it is important to determine the sequence distribution of the copolymer. The copolymer architecture is determined by the reactivity ratios and integrated instantaneous feed compositions. The reactivity ratios were determined using the first-order Markov method³ by running a series of reactions at various initial monomer ratios and determining the monomer incorporation into the copolymer as a function of time, via ¹H nuclear magnetic resonance. The reactivity ratios for dispersion copolymerizations of MAA with PEGMA in water were determined to be r₁ = 1.03 and r₂ = 1.02, whereas solution copolymerization in 50/50 EtOH–H₂O gave reactivity ratios of r₁ = 2.0 and r₂ = 3.6. These results show that the reactivity ratios and copolymer architecture are influenced by the solvent system. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1019–1025, 1998     

Synthesis of well‐defined comb‐like amphiphilic copolymers with protonizable units in the pendent chains: 1. Preparation of narrow polydispersity copolymers of methyl methacrylate and 2‐hydroxyethyl methacrylate by atom‐transfer radical polymerization

Well‐defined methyl methacrylate (MMA) and 2‐(trimethylsiloxy)ethyl methacrylate (Pro‐HEMA) copolymers were prepared by atom‐transfer radical polymerization(ATRP), using CuCl/2,2′‐bipyridine as catalytic system and p‐toluenesulfonyl chloride as initiator. ATRP process of MMA and Pro‐HEMA was monitored by ¹H NMR, and the kinetic curves of the MMA/Pro‐HEMA copolymerization were plotted in terms of the ¹H NMR data. At low content of Pro‐HEMA in the feed composition, the copolymerization can be well controlled with the molecular weight, polydispersity and the monomer distribution in the copolymer chain. With the increase of Pro‐HEMA content in the feed mixture, the composition of the final copolymer deviates from the composition of the feed mixture gradually, and gradient copolymers of MMA/Pro‐HEMA can be obtained. Through the hydrolysis process, well‐defined copolymers of MMA/HEMA were obtained from poly(MMA/Pro‐HEMA). Copyright © 2003 Society of Chemical Industry     

Analysis of nonideal kinetics in the polymerization of methyl methacrylate using some complex initiator systems based on a pyridine–sulfur dioxide charge transfer complex

The kinetic nonideality in the polymerization of methyl methacrylate was studied with the use of pyridine-sulfur dioxide charge transfer complex as the initiator under different conditions. The following systems were studied: (1) aqueous polymerization of methyl methacrylate (MMA) with the use of a pyridine-sulfur dioxide charge transfer complex as initiator, (2) photopolymerization of MMA initiated by the pyridine-sulfur dioxide complex in the presence of carbon tetrachloride, (3) photopolymerization of MMA in bulk and in a pyridine-diluted system with pyridine-sulfur dioxide alone and in combination with benzoyl peroxide as a photoinitiator. Polymerization in all these cases proceeded by radical mechanisms. The kinetic parameter /k_t for the aqueous system was 3.65 L mol⁻¹ s⁻¹, and for nonaqueous systems were 1.27 × 10⁻² to 1.40 × 10⁻² L mol⁻¹ s⁻¹. The monomer exponent and initiator exponent for ideal free radical polymerization systems are 1.0 and 0.5, respectively. In the system studied, the ideal kinetics were followed at specific concentration ranges of both monomer and initiator. At different concentration ranges, the systems behave nonideally. The kinetic nonidealities in monomer exponents, i.e., lower or higher than unity, were explained on the basis of (1) the rate-enhancing effect of different solvents, and (2) a radical generation step by in situ initiator monomer complexation reaction. The kinetic nonidealities in initiator exponent were analyzed and interpreted in terms of (1) primary radical termination, and (2) degradative initiator transfer with little reinitiator. Analysis of kinetic data shows that the degradative initiator transfer effect is more prominent in the present systems. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 585–595, 1998