Effect of Rh(III) and Ru(II) complexes in the polymerization of vinyl monomers initiated by charge transfer mechanism

The initiation of polymerization of vinyl monomers such as methyl methacrylate (MMA) and methyl acrylate (MA) by a charge transfer complex formed between n-butylamine(nBA) and carbon tetrachloride (CCl₄) in dimethylsulfoxide (DMSO) at 30°C is slow. The effect of the dimethylsulfoxide complexes of Rh(III) and Ru(II) on the polymerization of MMA and MA in the presence of nBA, and CCl₄ in DMSO has been studied. The rate of polymerization and percent conversion of the MMA and MA at 30°C are evaluated at the critical concentration of the metal complexes. At the critical range of the metal complex concentrations, both R_p, and percent conversion of MMA and MA were found to be highest. However, above and below the critical concentrations, R_p and percent conversion of the monomers were found to decrease. A suitable mechanism for the polymerization has been proposed.     

Chain transfer by addition–substitution–fragmentation mechanism. I. End–functional polymers by a single-step free radical transfer reaction: Use of a new allylic linear peroxyketal

A new chain transfer agent, ethyl 2-[1-(1-n-butoxyethylperoxy) ethyl] propenoate (EBEPEP) was used in the free radical polymerization of methyl methacrylate (MMA), styrene (St), and butyl acrylate (BA) to produce end-functional polymers by a radical addition–substitution–fragmentation mechanism. The chain transfer constants (C_tr) for EBEPEP in the three monomers polymerization at 60°C were determined from measurements of the degrees of polymerization. The C_tr were determined to be 0.086, 0.91, and 0.63 in MMA, St, and BA, respectively. EBEPEP behaves nearly as an “azeotropic” transfer agent for styrene at 60°C. The activation energy, E_atr, for the chain transfer reaction of EBEPEP with PMMA radicals was determined to be 29.5 kJ/mol. Thermal stability of peroxyketal EBEPEP in the polymerization medium was estimated from the DSC measurements of the activation energy, E_ath = 133.5 kJ/mol, and the rate constants, k_th, of the thermolysis to various temperature. © 1994 John Wiley & Sons, Inc.     

Photopolymerization of methyl methacrylate and some other vinyl monomers with the use of a pyridine–bromine charge-transfer complex as photoinitiator

Polymerization of MMA was carried out under visible light (440 nm) with the use of pyridine–bromine (Py–Br₂) charge-transfer (CT) complex as the photoinitiator. Initiator exponent and intensity exponent were 0.5 and 0.43, respectively, and the monomer exponent was found to be dependent on the nature of the solvent or diluent used. The Polymerization was inhibited in the presence of hydroquinone, but oxygen had very little inhibitory effect. An average value of k_p²/k_t for this polymerization system was 1.19 × 10^?2, and the activation energy of photopolymerization was 4.95 kcal/mole. Kinetic data and other evidence indicate that the overall polymerization takes place by a radical mechanism. With Py–Br₂ complex as the photoinitiator, the order of polymerizability at 40°C was found to be MMA, EMA ? Sty, MA.     

Alternating terpolymerization of three non-homopolymerizable monomers

The free-radical terpolymerization of maleic anhydride (MSA), isobutyl vinyl ether (VIBE) and anethol (ANE) at 60°C is described. These three monomers do not homopolymerize under the conditions used. Binary copolymers are only obtained from MSA and one of the two investigated donor monomers, whereas the binary copolymerization of VIBE with ANE is not possible. In all terpolymers from these three non-homopolymerizable monomers the MSA content amounts to about 50 mol-%; VIBE is about twice as reactive as ANE. The terpolymerization can formally also be described under the assumption that two binary complexes (MSA/ANE (I) and MSA/VIBE (II)) are copolymerized. For this case the reactivity ratios r_I = 0,9 and r_II = 1,7 are obtained.     

Studies of methyl methacrylate–glycidyl methacrylate copolymers: Copolymerization to low molecular weights and modification by ring-opening reaction of epoxy side groups

The copolymerization of methyl methacrylate (MMA) with glycidyl methacrylate (GMA) at 60°C with 2,2′-azobisisobutyronitrile (AIBN) as radical initiator and in the presence of thiophenol (TP) as chain-transfer agent has been investigated. Monomer reactivity ratios for MMA and GMA are found to be r₁ (MMA) = 0.80 ± 0.015 and r₂ (GMA) = 0.70 ± 0.015, from which Q and e values are calculated to be 0.68 and ?0.36 for GMA. The initial rate of copolymerization R_p at 60°C with AIBN (0.02 mole/l.) and TP (0.1, 0.01 mole/l.) were found to increase nonlinearly with increasing GMA concentration in the monomer feed. Homopolymerizations of MMA and GMA monomers were studied in the presence and in the absence of thiophenol. The values of δ (= k_t^1/2/k_p) for MMA and GMA were determined to be 10.25 and 3.00 (mole-sec/l.)^1/2, respectively. Using the values r₁ (MMA), r₂ (GMA), δ₁ (MMA), δ₂ (GMA), and R_p, the cross-termination constants ? for MMA–GMA monomers were determined (average value ? = 0.42). The increase in R_p values with increasing GMA content has been attributed to the cross-termination of MMA–GMA radicals. The transfer constant of TP has also been determined for GMA and found to be 1.00. A MMA–GMA copolymer of low molecular weight, containing 2.01% of oxirane oxygen, was modified by opening of the oxirane ring of GMA by reaction with diethanolamine (DEA). The reaction was carried out at 70 ± 1°C, the copolymer content of epoxy groups and the amine being assumed to be in the molar ratio of 1:4. Addition of a hydrogen-bond acceptor like nitrobenzene decreases, while addition of a hydrogen-bond donor like phenol increases the rate of epoxy ring opening with DEA. This indicates that a hydrogen-bonded intermediate is involved in this reaction and that it weakens the epoxy ring and enhances the rate of its opening with DEA. From the studies of the conversion rates, existence of a “nonspecific” side reaction has been shown which involves the reaction of the terminal epoxy groups of the copolymer and the hydroxyl groups of DEA or formed in the reaction with DEA (involves a chain coupling). DEA can be trifunctional in this reaction. This has been further confirmed from the increase of number-average molecular weights M?_n of the copolymers resulting from this coupling and the nitrogen content in the copolymers after modification with DEA.     

Hydrophilic and hydrophobic copolymer systems based on acrylic derivatives of pyrrolidone and pyrrolidine

This article deals with the synthesis of hydrophilic methacrylic monomers derived from ethyl pyrrolidone [2‐ethyl‐(2‐pyrrolidone) methacrylate (EPM)] and ethyl pyrrolidine [2‐ethyl‐(2‐pyrrolidine) methacrylate (EPyM)] and their respective homopolymers. For the determination of their reactivity in radical copolymerization reactions, both monomers were copolymerized with methyl methacrylate (MMA), the reactivity ratios being calculated by the application of linear and nonlinear mathematical methods. EPM and MMA had ratios of r_EPM = 1.11 and r_MMA = 0.76, and this indicated that EPM with MMA had a higher reactivity in radical copolymerization processes than vinyl pyrrolidone (VP; r_VP = 0.005 and r_MMA = 4.7). EPyM and MMA had reactivity ratios of r_EPyM = 1.31 and r_MMA = 0.92, and this implied, as for the EPM–MMA copolymers, a tendency to form random or Bernoullian copolymers. The glass‐transition temperatures of the prepared copolymers were determined by differential scanning calorimetry (DSC) and were found to adjust to the Fox equation. Total‐conversion copolymers were prepared, and their behavior in aqueous media was found to be dependent on the copolymer composition. The swelling kinetics of the copolymers followed water transport mechanism case II, which is the most desirable kinetic behavior for a swelling controlled‐release material. Finally, the different states of water in the hydrogels—nonfreezing water, freezing bound water, and unbound freezing water—were determined by DSC and found to be dependent on the hydrophilic and hydrophobic units of the copolymers. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 395–407, 2003     

Controlled/living polymerization of MMA promoted by heterogeneous initiation system (EPN‐X–CuX–bpy)

The polymerization of methyl methacrylate (MMA) promoted by heterogeneous initiation system (ethyl‐2‐halopropionate (EPN‐X)–CuX–2,2′‐bipyridyl (bpy), where X = Br or Cl) is studied in detail. The results show that ethyl‐2‐bromopropionate (EPN‐Br) is an efficient initiator as expected, and that CuCl–bpy, instead of CuBr–bpy, is a better catalyst for the controlled polymerization of MMA. The solvents with a high value of dielectric constant (ε) will lead to fast initiation and narrow molecular weight distribution (MWD). As a result, the controlled, living polymerization of MMA with EPN‐Br–CuCl–bpy can be got in ethyl acetate (EAc) at 100°C and in acetonitrile at 80°C. All results suggest that the initiation reaction is a controlling step in the controlled polymerization of MMA. The relationship between the UV spectra of CuCl–bpy and the performances of the polymerization in EAc or acetonitrile suggest that the formation of bis‐bpy complex, [Cubpy₂]X⁻, will lead to fast initiation and good control of the polymerization. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1255–1263, 1999     

Copolymerization of vinyl monomers with Gd(OCOCCl3)3-(i-Bu)3Al-Et2AlCl

The polymerization of polar monomers such as methyl methacrylate (MMA), methyl acrylate (MA), methacrylonitrile (MAN), and acrylonitrile (AN) was carried out with gadolinium-based Ziegler–Natta catalysts [Gd(OCOCCl₃)₃-(i-Bu)₃Al-Et₂AlCl] in hexane at 50°C under N₂ to elucidate the effect of the monomer's HOMO(highest occupied moleculor orbital) and LUMO (lowest unoccupied molecular orbital) levels on the polymerizability. In the case of homopolymerization, all monomers were found to polymerize and the order of relative polymerizability was as follows: MM > MA > MAN > AN. On the other hand, the result of copolymerization of St with MMA shows that the values of the monomer reactivity ratios are r₁ = 0.06 and r₂ = 1.98 for St(M₁)/MMA(M₂). The monomer reactivity ratios of styrene (St), p-methoxystyrene (PMOS), p-methylstyrene (PMS), and p-chlorostyrene (PCS) evaluated as r₁ = 0.55 and r₂ = 1.07 for St(M₁)/PMOS(M₂), r₁ = 0.38 and r₂ = 0.51 for St(M₁)/PMS(M₂), and r₁ = 0.72 and r₂ = 1.25 for St(M₁)/PCS(M₂) were compared with those for St(M₁)/MMA(M₂). The copolymerization behavior is apparently different from the titanium-based Ziegler—Natta catalyst, regarding a larger monomer reactivity ratio of PCS. The lower LUMO level of PCS and MMA may enhance a back-donation process from the metal catalyst, therefore resulting in high polymerizability. These results are discussed on the basis of the energy level of the gadolinium catalyst and the HOMO and LUMO levels of the monomers. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 2591–2597, 1997     

Complex‐radical terpolymerization of acceptor–donor–acceptor systems: Maleic anhydride (n‐butyl methacrylate)–styrene–acrylonitrile

Some features of radical ternary copolymerization of maleic anhydride (MA)–styrene (St)–acrylonitrile (AN) and n‐butyl methacrylate (BMA)–St–AN acceptor–donor–acceptor monomer systems have been revealed. The terpolymer compositions and kinetics of copolymerizations were studied in the initial and high conversion stages. The considerable divergence in the copolymer compositions was observed when a strong acceptor MA monomer was substituted with BMA having comparatively low acceptor character in the ternary system studied. Obtained results show that terpolymerization proceeded mainly through “complex” mechanism in the state of near binary copolymerization of St…MA (or BMA) and AN…St complexes only in the chosen ratios of complexed monomers. The terpolymers synthesized have high thermal stabilities (295–325 °C), which is explained by possible intermolecular fragmentation of AN‐units through cyclization and crosslinking reactions during thermotreatment in the isothermal heating conditions. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2652–2662, 2000     

Ferrocene-containing polymers. II. Radiation-induced copolymerizations of ferrocenylmethyl methacrylate with styrene,methyl methacrylate,and ethyl acrylate

Ferrocenylmethyl methacrylate (FMMA) was copolymerized with styrene (St), methyl methacrylate (MMA), and ethyl acrylate (EA) in benzene solution at 25°C by γ radiation. The reactions proceeded by a free radical mechanism, and monomer reactivity ratios were derived by the Tidwell–Mortimer method for St(M₁)–FMMA(M₂), r₁ = 0.35 and r₂ = 0.46; for MMA(M₁–FMMA)(M₂), r₁ = 0.85 and r₂ = 1.36; for EA(M₁)–FMMA(M₂), r₁ = 0.36 and r₂ = 3.03. The Q and e values of FMMA determined from copolymerization with St were 0.97 and 0.55, respectively. Terpolymerization of a MMA–FMMA–EA system based on the Alfrey–Goldfinger equations was studied. This is a typical terpolymerization system in which reactivities of the monomers obey the Q–e scheme. Comparing the results obtained here with those previously reported for other monomers, we concluded that FMMA is one of the most highly reactive monomers among alkyl methacrylates.     

Stereocontrol during the free‐radical polymerization of methacrylates with Lewis acids

The free‐radical polymerizations of methyl methacrylate (MMA), ethyl methacrylate, isopropyl methacrylate, and 2‐methoxyethyl methacrylate were carried out in the presence of various Lewis acids. The MMA polymerization in the presence of scandium trifluoromethanesulfonate [Sc(OTf)₃] in toluene or CHCl₃ produced a polymer with a higher isotacticity and heterotacticity than that produced in the absence of Sc(OTf)₃. Similar effects were observed during the polymerization of the other monomers. ScCl₃, Yb(OTf)₃, Er(OTf)₃, HfCl₄, HfBr₄, and In(OTf)₃ also increased the isotacticity and heterotacticity of the polymers. The effects of the Lewis acids were greater in a solvent with a lower polarity and were negligible in tetrahydrofuran and N,N‐dimethylformamide. Sc(OTf)₃ was also found to accelerate the polymerization of MMA. On the basis of an NMR analysis of a mixture of Sc(OTf)₃, MMA, and poly(methyl methacrylate), the monomer–Sc(OTf)₃ interaction seems to be involved in the stereochemical mechanism of the polymerization. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1463–1471, 2001     

Grafting onto Wool. XV. Graft Copolymerization of MA and MM A by Use of Mn(acac)3 as Initiator

Graft copolymerization of acceptor monomers MA and MMA onto Himachali wool fiber in an aqueous medium was studied by using Mn(acac)s as initiator. Nitric acid was found to catalyze the graft copolymerization. Percentage of grafting and percent efficiency have been determined as functions of the concentration of chelate, nitric acid, monomer, time, and temperature, Under optimum conditions, MMA produced a maximum grafting of 82.5% while MA afforded maximum grafting to the extent of 27.5%. Relative reactivities of MA and MMA toward grafting have been compared with those of EA, BA, and VAc reported earlier from this laboratory. Different vinyl monomers were found to follow the following reactivity order toward grafting onto wool fiber in the presence of Mn(acac)₃: MMA > EA > BA > MA > VAc. An attempt has been made to explain the observed reactivity pattern shown by different vinyl monomers in graft copolymerization reactions.     

Simple and effective one‐pot synthesis of (meth)acrylic block copolymers through atom transfer radical polymerization

The synthesis of di‐ and triblock copolymers using atom transfer radical polymerization (ATRP) of n‐butyl acrylate (BA) and methyl methacrylate (MMA) is reported. In particular, synthetic procedures that allow for an easy and convenient synthesis of such block copolymers were developed by using CuBr and CuCl salts complexed with linear amines. Polymerizations were successfully conducted where the monomers were added to the reactor in a sequential manner. Poor cross‐propagation between poly(n‐butyl acrylate) (PBA) macroinitiators and MMA was minimized, and therefore control of molecular weights and distributions was realized, by using halogen exchange—a technique involving the addition of CuCl to the MMA during the chain extension of the PBA macroinitiator. High molecular weight (M_n ∼ 90,000) and low polydispersity (M_w /M_n < 1.35) ABA triblock copolymers were also prepared and their structure and properties in bulk have been preliminary characterized indicating the potential of ATRP for the production of all‐acrylic thermoplastic elastomers. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2023–2031, 2000     

ESR single-crystal study of radical and radical-pair formation in some γ-irradiated vinyl monomers

Single crystals of methyl methacrylate (MMA), methyl acrylate (MA), and acrolein (A) have been prepared by a low-temperature technique. After irradiation with γ-rays at 77°K the paramagnetic species were identified by ESR spectroscopy. MMA gave a seven-line single spectrum from radicals formed by hydrogen addition. The hyperfine coupling constants are slightly anisotropic with a mean value of 22 G. Radical pairs were observed as ΔM_s = 1 and ΔM_s = 2 transitions; the hyperfine coupling was 11 G. From the strongly anisotropic dipolar interaction, upper limits for the distances between the pair components were calculated to be 5.45 Å and 6.3 Å. MA gave a five-line main spectrum with the same hyperfine coupling values and two radical pairs, one with a distance 5.9 Å between the components. In a there was also a strongly anisotropic interaction. The hyperfine coupling of the ΔM_s = 2 transition was 9.8 G. The number of radical pairs compared to the total number of radicals increases only slightly with the radiation dose. This makes it likely that pair formation occurs in the spurs and blobs formed by the γ-radiation. At an increased temperature the radical pairs disappeared; the spectrum of MMA changed to that characteristic of propagating polymer radicals.     

A new tetradentate ligand for atom transfer radical polymerization

The properties of a ligand, including molecular structure and substituents, strongly affect the catalyst activity and control of the polymerization in atom transfer radical polymerization (ATRP). A new tetradentate ligand, N,N′‐bis(pyridin‐2‐ylmethyl‐3‐hexoxo‐3‐oxopropyl)ethane‐1,2‐diamine (BPED) was synthesized and examined as the ligand of copper halide for ATRP of styrene (St), methyl acrylate (MA), and methyl methacrylate (MMA), and compared with other analogous linear tetrdendate ligands. The BPED ligand was found to significantly promote the activation reaction: the CuBr/BPED complex reacted with the initiators so fast that a large amount of Cu(II)Br₂/BPED was produced and thus the polymerizations were slow for all the monomers. The reaction of CuCl/BPED with the initiator was also fast, but by reducing the catalyst concentration or adding CuCl₂, the activation reaction could be slowed to establish the equilibrium of ATRP for a well‐controlled living polymerization of MA. CuCl/BPED was found very active for the polymerization of MA. For example, 10 mol% of the catalyst relatively to the initiator was sufficient to mediate a living polymerization of MA. The CuCl/BPED, however, could not catalyze a living polymerization of MMA because the resulting CuCl₂/BPED could not deactivate the growing radicals. The effects of the ligand structures on the catalysis of ATRP are also discussed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3553–3562, 2004     

Preparation of composite polyacrylate latex particles with in situ‐formed methylsilsesquioxane cores

Composite polyacrylate latex particles were prepared through a simple method by dissolving organosilicon monomer methyltrimethoxysilane in a monomer mixture of acrylic monomers methyl methacrylate (MMA), n‐butyl acrylate (n‐BA), and acrylic acid (AA). With the addition of water needed for hydrolysis, methyltrimethoxylsilane hydrolyzed under catalysis by AA and further condensed to form polymeric methylsilsesquioxane (MSQ). The monomer mixture containing in situ‐formed MSQ was then subjected to emulsification and emulsion polymerization. Transmission electron microscopy (TEM) images showed that the obtained latex particles had a core–shell structure. Differences between the X‐ray photoelectron spectroscopy (XPS) results of the contents of silicon atoms on surfaces of films formed at temperatures above and below glass transition temperatures (T_gs) of polyacrylate evidenced that the cores were made up of MSQ and the shells were made up of polyacrylate. The static water contact angle measurements indicated that the incorporation of MSQ can result in composite latex with higher hydrophobicity. Copyright © 2009 John Wiley & Sons, Ltd.     

Grafting of polymer matrix to exfoliated montmorillonite nanoplatelets in nanocomposite film cast from soap‐free emulsion polymerized latex and its fortified mechanical properties

Poly(methyl acrylate‐co‐methyl methacrylate) [P(MA‐co‐MMA)] nanocomposite film containing 1 wt % of montmorillonite (MMT) exhibited unusual higher ductility, higher strain recovery ratio after creep, and higher modulus and strength compared to neat P(MA‐co‐MMA) as they were cast from their individual latices fabricated by soap‐free emulsion polymerization. The fortified mechanical properties were attributed to the MgO components of exfoliated MMT nanoplatelets being grafted by P(MA‐co‐MMA) chains as verified by FTIR and XPS spectroscopies, which to the best of our knowledge is the first time in the literature providing the direct evidence for the polymer chains grafting onto the exfoliated MMT. TEM investigation of the stretched nanocomposite film revealed that the microcracks in the nanocomposite film appeared mainly in the bulk region of polymer matrix, implying that the interfacial strength between P(MA‐co‐MMA) and its grafted MMT nanoplatelets was higher than the cohesion strength of P(MA‐co‐MMA). © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5891–5897, 2009     

Solubility and diffusivity of methylmethacrylate and butylacrylate monomers in a MMA–BA copolymer

Mutual diffusion coefficients and sorption isotherms of methyl methacrylate (MMA) and butyl acrylate (BA) monomers in methyl methacrylate‐butyl acrylate copolymer (MMA‐BA) have been measured by gravimetric sorption. MMA is found to have higher solubility and diffusion rates in the copolymer than BA. Sorption data for MMA were interpreted using classical Flory‐Huggins thermodynamic theory with a constant interaction parameter (χ). A modified version of this theory has been applied to correlate the sorption data of BA, which exhibit a temperature and concentration‐dependent χ parameter. For MMA, the isotherm data reveal enhanced polymer‐solvent interactions with increasing temperature, while for BA the data indicate a drive toward phase separation with increasing temperature. Despite the difference in thermodynamic behavior, both monomers are found to exhibit Fickian diffusion and the diffusivity data are correlated reasonably well with the Vrentas‐Duda free volume theory. Some deviation between the free‐volume correlation and the experimental data is observed at the lowest temperature and BA concentration examined. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1996–2006, 2007     

Modeling the free radical polymerization of acrylates

Acrylates have gained importance because of their ease of conversion to high‐molecular‐weight polymers and their broad industrial use. Methyl methacrylate (MMA) is a well‐known monomer for free radical polymerization, but its α‐methyl substituent restricts the chemical modification of the monomer and therefore the properties of the resulting polymer. The presence of a heteroatom in the methyl group is known to increase the polymerizability of MMA. Methyl α‐hydroxymethylacrylate (MHMA), methyl α‐methoxymethylacrylate (MC₁MA), methyl α‐acetoxymethylacrylate (MAcMA) show even better conversions to high‐molecular‐weight polymers than MMA. In contrast, the polymerization rate is known to decrease as the methyl group is replaced by ethyl in ethyl α‐hydroxymethylacrylate (EHMA) and t‐butyl in t‐butyl α‐hydroxymethylacrylate (TBHMA). In this study, quantum mechanical tools (B3LYP/6‐31G*) have been used in order to understand the mechanistic behavior of the free radical polymerization reactions of acrylates. The polymerization rates of MMA, MHMA, MC₁MA, MAcMA, EHMA, TBHMA, MC₁AN (α‐methoxymethyl acrylonitrile), and MC₁AA (α‐methoxymethyl acrylic acid) have been evaluated and rationalized. Simple monomers such as allyl alcohol (AA) and allyl chloride (AC) have also been modeled for comparative purposes. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

Synthesis and polymerization of new di‐octadecyl ester derivatives of α‐hydroxymethyl acrylate: A structure‐property correlation for their copolymers with methyl methacrylate

New ether dimer (ED‐Od) and diester (ODE) derivatives of α‐hydroxymethylacrylate, each having two octadecyl side chains, were synthesized and (co)polymerized to evaluate the effects of differences in the structures of the monomers on final (co)polymer properties, particularly glass transition temperature. The free radical polymerizations of both monomers yielded high‐molecular weight polymers. Cyclopolymer formation of ED‐Od was confirmed by ¹³C NMR analysis and the cyclization efficiency (0.95 or greater) was found to be as high as the cyclization efficiencies of the cyclopolymerizations of ether dimers of various alkyl α‐hydroxymethylacrylates synthesized previously. Copolymers of both ED‐Od and ODE with methyl methacrylate (MMA) showed significant T_g decreases over PMMA due to octadecyl side groups causing “internal” plasticization. Comparison of the T_g's of the copolymers of octadecyl methacrylate, ED‐Od and ODE with MMA revealed that the impacts of these monomers on depression of T_g's are identical. That is, the magnitude of decrease in T_g's was quantitatively related to the number of the octadecyl side groups in the copolymers rather than their placement on the same or randomly incorporated repeat units. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7785–7793, 2008