Free‐radical polymerization of dioxolane and dioxane derivatives: Effect of fluorine substituents on the ring opening polymerization

Partially fluorinated and perfluorinated dioxolane and dioxane derivatives have been prepared to investigate the effect of fluorine substituents on their free‐radical polymerization products. The partially fluorinated monomer 2‐difluoromethylene‐1,3‐dioxolane (I) was readily polymerized with free‐radical initiators azobisisobutyronitrile or tri(n‐butyl)borane–air and yielded a vinyl addition product. However, the hydrocarbon analogue, 2‐methylene‐1,3‐dioxolane (II), produced as much as 50% ring opening product at 60 °C by free‐radical polymerization. 2‐Difluoromethylene‐4‐methyl‐1,3‐dioxolane (III) was synthesized and its free‐radical polymerization yielded ring opening products: 28% at 60 °C, decreasing to 7 and 4% at 0 °C and −78 °C, respectively. All the fluorine‐substituted, perfluoro‐2‐methylene‐4‐methyl‐1,3‐dioxolane (IV) produced only a vinyl addition product with perfluorobenzoylperoxide as an initiator. The six‐membered ring monomer, 2‐methylene‐1,3‐dioxane (V), caused more than 50% ring opening during free‐radical polymerization. However, the partially fluorinated analogue, 2‐difluoromethylene‐1,3‐dioxane (VI), produced only 22% ring opening product with free‐radical polymerization and the perfluorinated compound, perfluoro‐2‐methylene‐1,3‐dioxane (VII), yielded only the vinyl addition polymer. The ring opening reaction and the vinyl addition steps during the free‐radical polymerization of these monomers are competitive reactions. We discuss the reaction mechanism of the ring opening and vinyl addition polymerizations of these partially fluorinated and perfluorinated dioxolane and dioxane derivatives. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5180–5188, 2004     

Reversible addition–fragmentation chain transfer polymerization of glycidyl methacrylate with 2‐cyanoprop‐2‐yl 1‐dithionaphthalate as a chain‐transfer agent

A reversible addition–fragmentation chain transfer (RAFT) agent, 2‐cyanoprop‐2‐yl 1‐dithionaphthalate (CPDN), was synthesized and applied to the RAFT polymerization of glycidyl methacrylate (GMA). The polymerization was conducted both in bulk and in a solvent with 2,2′‐azobisisobutyronitrile (AIBN) as the initiator at various temperatures. The results for both types of polymerizations showed that GMA could be polymerized in a controlled way by RAFT polymerization with CPDN as a RAFT agent; the polymerization rate was first‐order with respect to the monomer concentration, and the molecular weight increased linearly with the monomer conversion up to 96.7% at 60 °C, up to 98.9% at 80 °C in bulk, and up to 64.3% at 60 °C in a benzene solution. The polymerization rate of GMA in bulk was obviously faster than that in a benzene solution. The molecular weights obtained from gel permeation chromatography were close to the theoretical values, and the polydispersities of the polymer were relatively low up to high conversions in all cases. It was confirmed by a chain‐extension reaction that the AIBN‐initiated polymerizations of GMA with CPDN as a RAFT agent were well controlled and were consistent with the RAFT mechanism. The epoxy group remained intact in the polymers after the RAFT polymerization of GMA, as indicated by the ¹H NMR spectrum. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2558–2565, 2004     

Cobalt complex bearing β‐ketoamine ligand: syntheses,structure, catalytic behavior for styrene and methyl methacrylate polymerization

Cobalt complex based on β‐ketoamine ligand [(Z)‐4‐((2,5‐dimethylphenylamino) (phenyl)methylene)‐3‐methyl‐1‐phenyl‐1H‐pyrazol‐5(4H)‐one] was successfully synthesized. The produced catalyst showed satisfactory activities in the cobalt‐mediated radical polymerization of styrene and methyl methacrylate with the common initiator of AIBN. The resulting polymerizations have the characteristics of living radical polymerization and displayed a nearly linear correlation between the number‐average molecular weight and monomer conversion. Low polydispersity was obtained for all polymerizations, and the polydispersity index decreased with the increase of conversion. These improvements facilitate the implementation of styrene and methacrylate cobalt‐mediated radical polymerization, and open the door to the scale‐up of the process. Copyright © 2014 John Wiley & Sons, Ltd.     

Radical ring‐opening polymerization of five‐membered cyclic vinyl sulfone using p‐toluenesulfonyl halides

Radical ring‐opening polymerizations of a five‐membered cyclic vinyl sulfone monomer, 2‐vinylthiolane‐1,1‐dioxide (VTDO), was carried out by using p‐toluenesulfonyl iodide (TosI) and bromide (TosBr) as radical initiators, and the corresponding ring‐opened polymer (PVTDO) was obtained. Both TosI and TosBr were found to work as the radical initiators for the polymerization of VTDO in bulk. The use of TosI gave PVTDOs with a broad, multimodal distribution of molecular weight in low yields. When 10 mol % of TosBr was employed, the isolated yield of PVTDO reached 49%, and the obtained PVTDO had a relatively narrow, monomodal molecular weight distribution of 1.8 with an M_n of 4100. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Use of germanium initiators in ring‐opening polymerization of L‐lactide

Three different, new germanium initiators were used for ring‐opening polymerization of L ‐lactide. Chlorobenzene and 120 °C was a usable polymerization system for solution polymerization, and the results from the polymerizations depended on the initiator structure and bulkiness around the insertion site. The average molecular weights as measured by size exclusion chromatography increased linearly with the monomer conversion, and the molecular weight dispersity was around 1.2 for initiators 1 and 2 , whereas it was around 1.4 for initiator 3 . The average molecular weight of poly(L ‐lactide) could be controlled with all three initiators by adding different ratios of monomer and initiator. The reaction rate for the solution polymerization was, however, overall extremely slow. With an initial monomer concentration of 1 M and a monomer‐to‐initiator ratio of 50, the conversion was 93% after 161 h for the fastest initiator. In bulk polymerization, 160 °C, the conversion was 90% after 10 h. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3074–3082, 2003     

Thermal polymerization of styrene in the presence of some ferrocene derivatives. II. Low concentrations of vinylferrocene and ethylferrocene

Styrene has been polymerized thermally at 60°C in the presence of low concentrations of vinylferrocene and in the presence and absence of 2,2′-azobisisobutyronitrile (AIBN). The polymerizations were studied in bulk and also in benzene solution. The thermal polymerization of styrene in the presence of ethylferrocene, but without added AIBN or solvent, was also examined. The bulk polymerizations exhibited high initial rates of polymerization followed by a decrease in rate. Initial rates of polymerization for bulk polymerizations in the absence of AIBN have been interpreted by means of a kinetic scheme involving propagation with styrene participating in a specific interaction with the ferrocene derivative and some kinetic parameters associated with this scheme have been evaluated. The decrease in the rate of polymerization is due to the formation of a retarder. The benzene solution polymerizations fitted a simple kinetic scheme and the transfer constant for vinylferrocene with respect to polystyryl radicals C_s, has been evaluated as 1.98 × 10^?3.     

Mapping the characteristics of the radical ring‐opening polymerization of a cyclic ketene acetal towards the creation of a functionalized polyester

Radical ring‐opening polymerization of cyclic ketene acetals is a means to achieve novel types of aliphatic polyesters. 2‐methylene‐1,3‐dioxe‐5‐pene is a seven‐membered cyclic ketene acetal containing an unsaturation in the 5‐position in the ring structure. The double bond functionality enables further reactions subsequent to polymerization. The monomer 2‐methylene‐1,3‐dioxe‐5‐pene was synthesized and polymerized in bulk by free radical polymerization at different temperatures, to determine the structure of the products and propose a reaction mechanism. The reaction mechanism is dependent on the reaction temperature. At higher temperatures, ring‐opening takes place to a great extent followed by a new cyclization process to form the stable five‐membered cyclic ester 3‐vinyl‐1,4‐butyrolactone as the main reaction product. Thereby, propagation is suppressed and only small amounts of other oligomeric products are formed. At lower temperatures, the cyclic ester formation is reduced and oligomeric products containing both ring‐opened and ring‐retained repeating units are produced at higher yield. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4587–4601, 2009     

Addition‐Fragmentation Chain Transfer to Polymer in the Free Radical Ring‐Opening Polymerization of an Eight‐membered Cyclic Allylic Sulfide Monomer

Summary: A detailed investigation of chain transfer to polymer during free radical ring‐opening polymerization of the eight‐membered disulfide monomer 2‐methyl‐7‐methylene‐1,5‐dithiacyclooctane (MDTO) is presented. It has been shown that extensive chain transfer to polymer occurs involving both poly(MDTO) radicals and cyanoisopropyl radicals. Significant decreases in molecular weight were observed when cyanoisopropyl radicals were generated in the presence of poly(MDTO) in the absence of monomer. The molecular weight distribution (MWD) obtained from polymerization of MDTO in the presence of pre‐added poly(MDTO) was markedly different from that obtained without pre‐added polymer. A kinetic model was constructed in an attempt to quantitatively describe the chain transfer to polymer process based on the addition fragmentation chain transfer mechanism. It was found however that the simulated MWDs were considerably broader than the experimental MWDs, which were similar to the Schulz‐Flory distribution.

Mechanism for chain transfer to polymer.     

Polyrotaxanes by free‐radical polymerization of acrylate and methacrylate monomers in the presence of a crown ether

Poly[(methyl acrylate)‐rotaxa‐(30‐crown‐10)] ( 5 ) and poly[(methyl methacrylate)‐rotaxa‐(30‐crown‐10)] ( 6 ) were synthesized by azobisisobutyronitrile‐initiated free‐radical bulk polymerizations of the respective monomers in the presence of 30‐crown‐10 ( 1 ; equimolar; 5 times the monomer mass). For 5 , 3.8 mass % (0.81 mol % with respect to the monomer) of the crown was incorporated versus 1.7 mass % (0.39 mol % with respect to the monomer) for 6 . Control reactions with 18‐crown‐6, which is to small to be threaded, showed that chain transfer to the crown ethers was detectable only for the acrylate but was relatively negligible and spectroscopically distinct. The threading yields were much higher with these systems than with polystyrene, most likely because of the greater compatibility of the crown ether with these polar monomers and polymers and the consequent ability to carry out the polymerizations homogeneously in the absence of added solvent; however, the threading process was still essentially statistical. Therefore, the polymerization of methacrylate monomers 8a – 8c based on tetraarylmethane moieties connected via diethyleneoxy or triethyleneoxy spacers was examined in the presence of 1 in the belief that the supramolecular semirotaxane monomer 9 formed statistically in situ could be captured more efficiently and produce higher threading yields, presumably of side‐chain polyrotaxanes, than the simple (meth)acrylate monomers. Azobisisobutyronitrile‐initiated polymerizations either neat or in toluene produced polyrotaxanes 10 with up to about 1.6 mass % and 2 mol % threaded crown ether, presumably trapped on the pendant stoppered side chains. Although primarily statistical in nature, the latter rotaxane syntheses afforded on a molar basis 3–7 times more efficient incorporation of 1 than styrene (0.33 mol %), methyl acrylate (0.81 mol %), or methyl methacrylate (0.39 mol %) monomers for the preparation of main‐chain polypseudorotaxanes and indeed even surpassed the 60‐crown‐20/polyacrylonitrile system (1.5 mol %). This was presumed to be due to the fact that the loss of the crown ether, once it was threaded onto the monomer to form 9 and the latter was polymerized, was either retarded (by the tetraphenylmethyl stopper in 10a ) or prevented completely [by tris(p‐t‐butylphenyl)phenylmethyl stoppers in 10b and 10c ]. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1978–1993, 2001     

Synthesis and copolymerization of new phosphorus‐containing acrylates

Two phosphorus‐containing acrylate monomers were synthesized from the reaction of ethyl α‐chloromethyl acrylate and t‐butyl α‐bromomethyl acrylate with triethyl phosphite. The selective hydrolysis of the ethyl ester monomer with trimethylsilyl bromide (TMSBr) gave a phosphonic acid monomer. The attempted bulk polymerizations of the monomers at 57–60 °C with 2,2′‐azobisisobutyronitrile (AIBN) were unsuccessful; however, the monomers were copolymerized with methyl methacrylate (MMA) in bulk at 60 °C with AIBN. The resulting copolymers produced chars on burning, showing potential as flame‐retardant materials. Additionally, α‐(chloromethyl)acryloyl chloride (CMAC) was reacted with diethyl (hydroxymethyl)phosphonate to obtain a new monomer with identical ester and ether moieties. This monomer was hydrolyzed with TMSBr, homopolymerized, and copolymerized with MMA. The thermal stabilities of the copolymers increased with increasing amounts of the phosphonate monomer in the copolymers. A new route to highly reactive phosphorus‐containing acrylate monomers was developed. A new derivative of CMAC with mixed ester and ether groups was synthesized by substitution, first with diethyl (hydroxymethyl)phosphonate and then with sodium acetate. This monomer showed the highest reactivity and gave a crosslinked polymer. The incorporation of an ester group increased the rate of polymerization. The relative reactivities of the synthesized monomers in photopolymerizations were determined and compared with those of the other phosphorous‐containing acrylate monomers. Changing the monomer structure allowed control of the polymerization reactivity so that new phosphorus‐containing polymers with desirable properties could be obtained. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2207–2217, 2003     

Kinetic comparison of isomeric oligo(ethylene oxide) (meth)acrylates: Aqueous polymerization of oligo(ethylene oxide) methyl ether methacrylate and methyl 2-(oligo(ethylene oxide) methyl ether)acrylate macromonomers

The photoinduced energy/electron transfer-reversible addition-fragmentation chain transfer (PET-RAFT) polymerizations of oligo(ethylene oxide) monomethyl ether methacrylate (OEOMA, also known as poly[ethylene glycol] methyl ether methacrylate, PEGMA) and isomeric methyl 2-(oligo(ethylene oxide) methyl ether)acrylate (2OEOAM) macromonomers with OEO average degree of polymerization of 22 or 45 were conducted in aqueous media to provide insight into the effect of monomer structure on grafting-through RAFT of 1,1-disubstituted acrylic macromonomers. The polymerizations of all four monomers reached nearly quantitative conversion. The longer macromonomers polymerized faster than the shorter ones within the same monomer class. The OEO side chain at the α (i.e., 2-) position of isomeric acrylates significantly slowed RAFT polymerization in comparison with OEO ester side chain of methacrylates.     

Skewered reactions in free‐radical crosslinking (co)polymerizations of liquid polybutadiene as internal olefinic multivinyl crosslinker

As an extension of our continuing studies concerned with the mechanistic discussion of network formation in the free‐radical crosslinking (co)polymerization of multivinyl monomers, this work refers to the skewered reactions in the crosslinking (co)polymerizations of liquid polybutadiene rubber (LBR) as an internal olefinic multivinyl monomer or crosslinker, especially focused on the competitive occurrence of both addition or skewered reaction to internal carbon–carbon (CC) double bonds and abstraction reaction of allylic hydrogens in LBR by growing polymer radical. Thus, LBR is regarded as an internal olefinic multiallyl monomer‐linked allyl groups (? CH?CH? CH₂? ) with methylene units (? CH₂? ). First, gelation in the polymerization of LBR was explored in detail, especially at elevated temperatures. The occurrence of intermolecular crosslinking was easier in the order LBR > LBR containing 20 mol % of 1,2‐structural units > liquid polyisoprene rubber. Then, we pursued the polymerization of LBR using dicumyl peroxide (DCPO) as typical organic peroxide used at elevated temperatures. The primary cumyloxy radical generated by the thermal decomposition of DCPO may add to CC double bond or abstract allylic hydrogen or undergo β‐scission to generate a secondary methyl radical. The initiation by the cumyloxy radical was omitted. The ratio of allylic hydrogen abstraction to β‐scission reaction was estimated; thus, only 39% of cumyloxy radical was used for the allylic hydrogen abstraction reaction. The addition of methyl radical to CC double bond was clearly observed. Finally, we pursued the intermolecular and intramolecular skewered reactions in free‐radical crosslinking LBR/vinyl pivalate copolymerizations. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Copolymerization of butyl vinyl ether and methyl methacrylate by combination of radical and radical promoted cationic mechanisms

Butyl vinyl ether (BVE) and methyl methacrylate (MMA) mixtures were polymerized by using free radical initiators in conjunction with a cationic initiator such as diphenyl iodonium salt. Polymerization mechanism involves free radical polymerization of MMA which is switched to cationic polymerization of BVE by addition of growing poly(MMA) radicals to BVE and subsequent oxidation of electron donating polymeric radicals to the corresponding cations by iodonium ions. Two representative bifunctional monomers, ethylene glycol divinyl ether (EGDVE) and ethylene glycol dimethacrylate (EGDMA) were also used together with MMA and BVE, respectively, in photo and thermal crosslinking polymerizations. Vinyl ether and methacrylate type monomers can successfully be copolymerized by this double-mode polymerization under photochemical conditions.     

Synthesis and polymerization of phosphorus‐containing acrylates

Novel phosphorus‐containing acrylate monomers were synthesized by two different routes. The first involved the reaction of ethyl α‐chloromethyl acrylate and t‐butyl α‐bromomethyl acrylate with diethylphosphonoacetic acid. The monomers were bulk‐ and solution‐polymerized at 56–64 °C with 2,2′‐azobisisobutyronitrile. The ethyl ester monomer showed a high crosslinking tendency under these conditions. The selective hydrolysis of the ethyl ester phosphonic ester compound was carried out with trimethylsilyl bromide, producing a phosphonic acid monomer. In the second route, ethyl α‐hydroxymethyl acrylate and t‐butyl α‐hydroxymethyl acrylate were reacted with diethylchlorophosphate. The bulk homopolymerization and copolymerization of these monomers with methyl methacrylate and 2,2′‐azobisisobutyronitrile gave soluble polymers. The attempted hydrolysis of the monomers was unsuccessful because of the loss of the diethylphosphate group. The relative reactivities of the monomers in the photopolymerizations were also compared. The ethyl α‐hydroxymethyl acrylate/diethylphosphonic acid monomer showed higher reactivity than the other monomers, which may explain the crosslinking during the polymerization of this monomer. The reactivities of other derivatives were similar, but the rates of polymerization were slow in comparison with those of methyl methacrylate. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3221–3231, 2002     

Reversible addition–fragmentation chain transfer polymerization of 2‐naphthyl acrylate with 2‐cyanoprop‐2‐yl 1‐dithionaphthalate as a chain‐transfer agent

The reversible addition–fragmentation chain transfer (RAFT) polymerizations of 2‐naphthyl acrylate (2NA) initiated by 2,2′‐azobisisobutyronitrile were investigated with 2‐cyanoprop‐2‐yl 1‐dithionaphthalate (CPDN) as a RAFT agent at various temperatures in a benzene solution. The results of the polymerizations showed that 2NA could be polymerized in a controlled way by RAFT polymerization with CPDN as a RAFT agent; the polymerization rate was first‐order with respect to the monomer concentration, and the molecular weight increased linearly with the monomer conversion. The polydispersities of the polymer were relatively low up to high conversions in all cases. The chain‐extension reactions of poly(2‐naphthyl acrylate) (P2NA) with methyl methacrylate and styrene successfully yielded poly(2‐naphthyl acrylate)‐b‐poly(methyl methacrylate) and poly(2‐naphthyl acrylate)‐b‐polystyrene block polymers, respectively, with narrow polydispersities. The P2NA obtained by RAFT polymerization had a strong ultraviolet absorption at 270 nm, and the molecular weights had no apparent effect on the ultraviolet absorption intensities; however, the fluorescence intensity of P2NA increased as the molecular weight increased and was higher than that of 2NA. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2632–2642, 2005     

Styrene miniemulsion polymerization initiated by 2,2′-azobisisobutyronitrile

The effects of various parameters on the dodecyl methacrylate (DMA) or stearyl methacrylate (SMA) containing styrene miniemulsion polymerizations were investigated. These parameters include the type of initiators [2,2′-azobisisobutyronitrile (AIBN) vs. sodium persulfate (SPS)], the size of the homogenized monomer droplets, the AIBN concentration, and the SDS concentration. A small quantity of a water-insoluble dye was also incorporated into the polymerization system to study the related particle nucleation mechanisms. The oil-soluble AIBN promotes nucleation in the monomer droplets, whereas homogeneous nucleation predominates in the reaction system with the water-soluble SPS. Homogeneous nucleation, however, cannot be ruled out in the DMA or SMA containing polymerizations with AIBN as the sole initiator. Increasing the level of AIBN or SDS enhances formation of particle nuclei via homogeneous nucleation. The reaction kinetics is primarily controlled by the competitive events of monomer droplet nucleation and homogeneous nucleation. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2537–2550, 1999     

Systematic Investigation of the Photopolymerization of Imidazolium-Based Ionic Liquid Styrene and Vinyl Monomers

The use of ionic liquids (ILs) as media in radical polymerizations has demonstrated the ability of these unique solvents to improve both reaction kinetics and polymer product properties. However, the bulk of these studies have examined the polymerization behavior of common organic monomers (e.g., methyl methacrylate, styrene) dissolved in conventional ILs. There is increasing interest in polymerized ILs (poly(ILs)), which are ionomers produced from the direct polymerization of styrene-, vinyl-, and acrylate-functionalized ILs. Here, the photopolymerization kinetics of IL monomers are investigated for systems in which styrene or vinyl functionalities are pendant from the imidazolium cation. Styrene-functionalized IL monomers typically polymerized rapidly (full conversion ≤1 min) in both neat compositions or when diluted with a nonpolymerizable IL, [C₂mim][Tf₂N]. However, monomer conversion in vinyl-functionalized IL monomers is much more dependent on the nature of the nonpolymerizable group. ATR-FTIR analysis and molecular simulations of these monomers and monomer mixtures identified the presence of multiple intermolecular interactions (e.g., π–π stacking, IL aggregation) that contribute to the polymerization behaviors of these systems. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 2364–2375     

Cationic polymerization of seven‐membered cyclic monothiocarbonate 1,3‐dioxepan‐2‐thione

The cationic ring‐opening polymerization of a seven‐membered cyclic monothiocarbonate, 1,3‐dioxepan‐2‐thione, produced a soluble polymer through the selective isomerization of thiocarbonyl to a carbonyl group {? [SC(C?O)O(CH₂)₄]_n? }. The molecular weights of the polymer could be controlled by the feed ratio of the monomer to the initiators or the conversion of the monomer during the polymerization, although some termination reactions occurred after the complete consumption of the monomer. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1014–1018, 2005     

Synthesis of nearly micron-sized particles by soap-free emulsion polymerization of methacrylic monomer using an oil-soluble initiator

Methacrylic monomer was used in soap-free emulsion polymerization in order to obtain a stable dispersion containing particles of the polymerized monomer. 2,2′-Azobis(2-methylpropionitrile) (AIBN) or 1,1′-azobis(1-acetoxy-1-phenylethane) (OT_AZO-15) were used as the radical initiator. Although particles with a size of about 1.0 μm were obtained when using methyl methacrylate as the monomer and AIBN as the initiator, the particles did not exhibit good dispersion stability. When OT_AZO-15, which has phenyl rings, was used as the initiator, the monomer phase solidified instead of forming particles in the aqueous phase. Benzyl methacrylate (BMA) monomer, which contains a phenyl ring, was polymerized using AIBN. Negatively charged particles with a size of 0.90 μm were formed. These particles exhibited good dispersion stability probably because of the pi electrons of the phenyl ring in the BMA monomer. The method in this study allows the synthesis of nearly micron-sized particles without surfactant, organic solvent, and electrolyte.     

Emulsion and controlled miniemulsion polymerization of the renewable monomer γ‐methyl‐α‐methylene‐γ‐butyrolactone

The kinetics of free‐radical emulsion polymerization of γ‐methyl‐α‐methylene‐γ‐butyrolactone (MeMBL), a renewable monomer related to methyl methacrylate, are presented in detail for the first time, and stable polymer latices are prepared. The effects of different reaction parameters on free‐radical emulsion polymerization of MeMBL are presented. Homogeneous nucleation is asserted to be the dominant path for particle formation. Miniemulsion copolymerization of MeMBL and styrene is also reported. In this case, the homogeneous nucleation process appears limited when using an oil soluble initiator. Both the RAFT miniemulsion polymerizations and RAFT bulk polymerizations are well controlled and narrow polydispersity copolymers are produced. Rate retardation is observed in the RAFT miniemulsion polymerizations compared with the free‐radical polymerization and RAFT bulk polymerizations and the possible causes of the retardation are discussed. The reactivity ratios of MeMBL and styrene in RAFT bulk copolymerization are also determined. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5929–5944, 2008