Effects of Operating Conditions on the Copolymerization of Castor Oil Maleate–Styrene by Suspension Polymerization

This work studies the synthesis of copolymers (MACO‐St) of castor oil maleate (MACO) and styrene (St) initiated using benzoyl peroxide (BPO) as free radical initiator through suspension polymerization. The study investigates the effects of temperature (100–140 °C), the molar ratio between styrene and MACO (2:1–4:1), BPO concentration (0.10–0.20 wt%), and water concentration (50–100 wt%) on the molecular weight distribution, thermal stability, viscosity, and biodegradability of the copolymers. Suspension polymerization allows the production of a broad range of number average molecular weight (3465–18 995 g mol^?1) and molecular weight distributions with dispersions (?) ranging from 1.8 to 4.4. The reaction presents high yields of castor oil into copolymers (>90%), which displays thermal stability up to 200 °C and are highly biodegradable according to the International Organization of Standardization reference.     

Cationic polymerization of L,L‐lactide

Cationic bulk polymerization of L ,L‐ lactide (LA) initiated by trifluromethanesulfonic acid [triflic acid (TfA)] has been studied. At temperatures 120–160 °C, polymerization proceeded to high conversion (>90% within ～8 h) giving polymers with M_n ～ 2 × 10⁴ and relatively high dispersity. Thermogravimetric analysis of resulting polylactide (PLA) indicated that its thermal stability was considerably higher than the thermal stability of linear PLA of comparable molecular weight obtained with ROH/Sn(Oct)₂ initiating system. Also hydrolytic stability of cationically prepared PLA was significantly higher than hydrolytic stability of linear PLA. Because thermal or hydrolytic degradation of PLA starting from end‐groups is considerably faster than random chain scission, both thermal and hydrolytic stability depend on molecular weight of the polymer. High thermal and hydrolytic stability, in spite of moderate molecular weight of cationically prepared PLA, indicate that the fraction of end‐groups is considerably lower than in linear PLA of comparable molecular weight. According to proposed mechanism of cationic LA polymerization growing macromolecules are fitted with terminal ? OH and ? C(O)OSO₂CF₃ end‐groups. The presence of those groups allows efficient end‐to‐end cyclization. Cyclic nature of resulting PLA explains its higher thermal and hydrolytic stability as compared with linear PLA. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2650–2658, 2010     

Ring‐opening polymerization of lactones using binaphthyl‐diyl hydrogen phosphate as organocatalyst and resulting monosaccharide functionalization of polylactones

Binaphthyl‐diyl hydrogen phosphate has been assessed for the first time as a catalyst for the ring‐opening polymerization of ε‐caprolactone (CL) and δ‐valerolactone (VL). In the presence of benzyl alcohol as coinitiator at 40–60 °C, the polymerization is quantitative and controlled both in terms of dispersity and of number‐average molecular weight corresponding to the monomer/initiator ratio. The use of a selectively protected D ‐glucose derivative bearing the primary C6 hydroxyl group as initiator leads to the quantitative end‐functionalization of the polyesters in rather short reaction times (ca. 10 min at 60 °C for δ‐VL) with dispersities around 1.08–1.10. Methyl‐α‐D ‐glucopyranoside has been used as a carbohydrate polyol initiator in bulk. The initiation efficiency is partial, leading to hydrophilic carbohydrates functionalized polylactones in a one‐step procedure. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Core‐stabilized polymeric micelle as potential drug carrier: increased solubilization of taxol

Poly(ethylene glycol‐b‐lactide) possessing a methoxy group at the poly(ethylene glycol) (PEG) chain end and a polymerizable methacryloyl group at the poly(lactic acid) (PLA) chain end (MeO–PEG/PLA–methacryloyl) was prepared by an anionic ring‐opening polymerization of ethylene oxide and DL ‐lactide in tandem manner initiated with a potassium 2‐methoxyethanolate, followed by end‐capping with an excess of methacrylic anhydride. The molecular weight of the obtained polymer was controlled by the initial monomer/initiator ratio, which was confirmed by the combination of gel permeation chromatography and nuclear magnetic resonance analyses. The functionality of the methacryloyl–PLA end was almost quantitative. The MeO–PEG/PLA–methacryloyl (38/35; these numbers in parentheses denote the molecular weights of PEG and PLA segments divided by 100, respectively) formed a core–shell type spherical micelle in aqueous media obtained by a dialysis technique, the cumulant diameter of which was ca. 30 nm with very low polydispersity factor. The methacryloyl group adjacent to the PLA was polymerized in the PLA core of the micelle. The polymerization proceeded thermally with radical initiator and photochemically with photo‐initiator to produce core‐polymerized nanoparticles, which was found by spectroscopic and light‐scattering techniques. Taxol‐incorporated micelles were prepared to entrap Taxol into MeO–PEG/PLA–methyacryloyl block copolymer micelles by the oil/water emulsion method. Copyright © 1999 John Wiley & Sons, Ltd.     

Ring-opening polymerization of 1,5-dioxepan-2-one initiated by a cyclic tin–alkoxide initiator in different solvents

Ring-opening polymerization of 1,5-dioxepan-2-one initiated by 1,1,6,6-tetra-n-butyl-1,6-distanna-2,5,7,10-tetraoxacyclodecane was carried out in chloroform, dichloromethane, or 1,2-dichloroethane. Effects of reaction temperature, solvent, and monomer-to-initiator ratio were investigated. Polymerization kinetics showed a first-order dependence on the monomer for polymerization in chloroform and dichloromethane at 40°C. The kinetic order with respect to the initiator were a first order when dichloromethane was used as the solvent, the order in initiator changed, depending on the initiator concentration when chloroform was used. A maximum in molecular weight was observed at 40°C when chloroform was used as the solvent. The change of solvent did not markedly alter the polymerization rate or the molecular weight of the polymers prepared, as expected from the coordination insertion mechanism. Depolymerization of the polymers formed was observed when the reaction was allowed to continue after complete monomer conversion in chloroform as reaction medium at 40°C. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3407–3417, 1999     

A novel scheme of heterogeneous polymerization of ethylene

The heterogeneous polymerization of ethylene initiated by radiation in tert-butyl alcohol was studied. The polymerization was carried out in a 100-ml reactor at 25–100°C and pressures of 200–300 kg/cm² in the presence of 50 ml of tert-butyl alcohol containing 7 wt-% water. The amounts of polymerized monomer, the average molecular weight of polymer formed, and the molecular weight distribution of polymer were measured at various stages of reaction and at various temperatures. The molecular weight distribution was found to be very much dependent on the reaction time and temperature. For the polymer formed at 50–60°C in the very early stages of reaction, the molecular weight distribution is unimodal, and in the intermediate stage a shoulder appears at a molecular weight higher than the first peak which increases as the polymerization proceeds; eventually a bimodal curve is formed. The bimodal distribution curves were analyzed to determine the fractions and average molecular weights of the each peak. On the basis of these data for the molecular weight distribution and kinetic behavior, a new scheme for the heterogeneous polymerization is proposed which indicates that the polymerization proceeds via propagating radicals in two different physical states, namely, loose and rigid states.     

Biodegradable Composites of Poly(lactic acid) with Cellulose Fibers Polymerized by Aluminum Triflate

Biodegradable polymer composites consisting of poly(lactic acid) (PLA) and cellulose fibers (CF) were prepared by our newly developed method. L-Lactic acid (LA) was reacted by ring-opening polymerization with aluminum triflate as a catalyst, glycerol as an initiator and CF as a filler, in simple plastic tubes at 100 °C for 6 hours. By this method, CF could be mixed with the polymer matrix easily and homogeneously. The molecular weight and molecular weight distribution of the PLA matrix were determined by gel permeation chromatography (GPC). The M_n of the composite samples decreased from 6200 to 2800 with increasing CF content. The molecular weight distribution of composites was around 2.5 regardless of the CF content. Biodegradation of samples was determined by measuring the results from the Microbial Oxidative Degradation Analyzer (MODA) and the weight loss in compost. Biodegradation of composite samples of PLA with CF increases with increasing CF content as measured by the MODA. Apparent density of composite samples was calculated by using the weight and sizes of column shape specimens. The density of the composite samples was a bit lower than that of PLA pure samples without CF. Mechanical properties such as the elastic modulus and strength were investigated by compression tests using column shape specimens. For the sample with filter paper as CF, the strength of composite samples increases with increasing CF content.     

Ring opening polymerization and copolymerization of L‐lactide and ɛ‐caprolactone by bis‐ligated magnesium complexes

Seven magnesium complexes ( 1–7 ) were synthesized by reaction of new ( L ³ ‐H – L ⁵ ‐H ) and previously reported ketoimine pro‐ligands with dibutyl magnesium and were isolated in 59–70% yields. Complexes 1–7 were characterized fully and consisted of bis‐ligated homoleptic ketoiminates coordinated in distorted octahedral geometry around the magnesium centers. The complexes were investigated for their ability to initiate the ring opening polymerization (ROP) of l ‐lactide (L‐LA) to poly‐lactic acid (PLA) and ?‐caprolactone (?CL) to poly‐caprolactone in the presence of 4‐fluorophenol co‐catalyst. For L‐LA polymerization, complexes containing ligand electron‐donating groups ( 1–5 ) achieved >90% conversion in 2 h at 100 °C, while the presence of CF₃ groups in 6 and 7 slowed or resulted in no PLA detected. With ?CL, ROP initiated with 1–7 resulted in lower percentage conversion with similar electronic effects. Moderate molecular weight PLA polymeric material (14.3–21.3 kDa) with low polydispersity index values (1.23–1.56) was obtained, and ROP appeared to be living in nature. Copolymerization of L‐LA and ?CL yielded block copolymers only from the sequential polymerization of ?CL followed by L‐LA and not the reverse sequence of monomers or the simultaneous presence of both monomers. Polymers and copolymers were characterized with NMR, gel permeation chromatography, and differential scanning calorimetry. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 48–59     

Polymers of carbonic acid. XXVII. Macrocyclic polymerization of trimethylene carbonate

2,2-Dibutyl-2-stanna-1,3-dioxepane (DSDOP) was used as cyclic initiator for the polymerization of trimethylene carbonate (TMC). The polymerizations were either conducted in concentrated chlorobenzene solution at 50 and 80°C or in bulk at 60 and 120°C. With monomer/initiator ratios ≤100 the conversion was complete within 2 h at 80°C and within 12 h at 50°C. Variation of the reaction time revealed that the rapid polymerization is followed by a relatively rapid (backbiting) degradation even at 80°C. The polymerizations in bulk at 60°C were somewhat slower than those at 80°C in solution, but the influence of degradation reactions was less pronounced. With optimized reaction time the number average molecular weight (M_n) roughly parallels the monomer/initiator ratio and M_n's up to 100,000 were obtained. In contrast to a classical living polymerization broader polydispersities (1.5–1.7) were found. In the case of 5,5-dimethyltrimethylene carbonate rapid degradation and chain transfer reactions prevented the formation of high molecular weight polymers. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2179–2189, 1999     

Polymerization of vinyl chloride by alkyllithium compounds

The polymerization of vinyl chloride initiated by alkyllithium compounds was investigated. The effect of temperature, initiator concentration, and monomer concentration on the conversion and the properties of the resulting polymers were studied. The optimum temperature in the investigated range (between ?20°C and +20°C) was +5°C. The conversion is directly proportional to the concentration of both the initiator and the monomer. The molecular weight is inversely proportional to the initiator concentration and directly proportional to the monomer concentration. Under optimum conditions the molecular weight of the polymers is as high as 140,000. These results differ by an order from hitherto published data on the nonradical polymerization of vinyl chloride. The proportion of isotactic and syndiotactic structures resulting from the presence of tert-butyllithium does not differ from that obtained by radical polymerization, but the occurrence of anomalous structures is reduced to a minimum. The stability of the macromolecules is higher. A mechanism of the polymerization is suggested.     

Ring-opening polymerization of L-lactide and preparation of its microsphere in supercritical fluids

The ring-opening polymerization of L-lactide initiated by stannous octoate was carried out in supercritical chlorodifluoromethane (scR22) at various reaction conditions (time and temperature) and reactant concentrations (initiator, monomer, and solvent). The monomer conversion increased to ca. 70% on increasing the reaction time to 1 h. The molecular weight of the poly(L-lactide) (PLLA) product also increased to ca. 160,000 g x mol(-1) over the same period. Increasing reaction temperature from 90 to 130 degrees C resulted in increased monomer conversion and PLLA molecular weight. A series of polymerizations conducted at various 1-dodecanol and stannous octoate concentrations suggested that stannous octoate does not act as an initiator by itself, and that the tin-alkoxide formed from 1-dodecanol and stannous octoate serves as the initiating species in scR22. While enhancements of the monomer conversion and PLLA molecular weight were observed with increasing monomer concentration, the chlorodifluoromethane concentration had the opposite on both. After the polymerization, PLLA microspheres were prepared in situ by using a continuous supercritical antisolvent process without residual organic solvent and monomer to yield highly purified microspheres for environmental and biomedical applications.     

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     

Polymers from 1,2-Disubstituted Ethylenic Monomers. IX. Radical High Polymerization of Methyl-tert-butyl Fumarate

Methyl-tert-butyl fumarate (MtBF) was found to homopolymerize in bulk in the presence of 2,2′-azobisisobutyronitrile (AIBN) at 50–80°C to give a high molecular weight polymer. From IR, ¹H-NMR and ¹³C-NMR spectra, this polymer was assumed to consist of alternating methoxycarbonylmethylene and tert-butoxycarbonylmethylene units, indicating that it was produced from MtBF through an ordinary vinylene polymerization mechanism. Consideration of a molecular model suggested that this polymer had a less flexible rodlike structure with the diameter of about 13.5 Å. The thermal properties of this polymer were also evaluated. Moreover, the bulk polymerization of MtBF initiated by AIBN was investigated kinetically at 60°C. The overall activation energy for this polymerization was determined to be 83.5 kJ/mol. The reaction orders with respect to the monomer and initiator concentrations were obtained as 2.0 and 0.33, respectively.     

Reverse atom transfer radical polymerization of methyl methacrylate initiated by p‐chlorobenzenediazonium tetrafluoroborate

The controlled polymerization of methyl methacrylate (MMA) in bulk was initiated with p‐chlorobenzenediazonium tetrafluoroborate ( 1 ) and Cu(II) or Cu(I)/Cu(II)/N,N,N′,N″,N″‐pentamethyldietylene triamine (PMDETA) complex system at various temperatures (20, 60, and 90 °C). The proposed polymerization mechanism is based on the Meerwein‐type arylation reaction followed by a reverse atom transfer radical polymerization. In this mechanism, aryl radicals formed by the reaction with 1 and Cu(I) and/or PMDETA initiated the polymerization of MMA. The polymerization is controlled up to a molecular weight of 46,000 at 90 °C. Chain extension was carried out to confirm the controlled manner of the polymerization system. In all polymerization systems, the polydispersity index and initiator efficiency ranged from 1.10–1.57 to 0.10–0.21, respectively. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2019–2025, 2003     

Synthesis,characterization, and thermal stability of poly (lactic acid)/zinc oxide pillared organic saponite nanocomposites via ring‐opening polymerization of d,l‐lactide

Poly (lactic acid) (PLA) was synthesized using d , l ‐lactide monomer and zinc oxide (ZnO) pillared organic saponite as the green catalyst, through ring‐opening polymerization. The effects of stoichiometry of catalyst and polymerization conditions on molecular weight of PLA were evaluated by orthogonal experiment. The optimum polymerization parameters were: 0.5 wt% ZnO pillared organic saponite and reaction conditions of 170°C for 20 hr. Fourier transform infrared spectroscopy and ¹H nuclear magnetic resonance spectroscopy confirmed the PLA structure. Gel permeation chromatography showed that the average molecular weight of PLA was 48,442 g/mol, and its polydispersity index was 1.875. Differential scanning calorimetry, X‐ray diffraction, and polarized optical microscopy showed that ZnO pillared organic saponite improved the crystallinity of PLA. Thermal gravimetric analysis showed improved thermal stability of PLA because of ZnO pillared organic saponite. Thermal decomposition kinetics of PLA/ZnO pillared organic saponite nanocomposites was also studied. The activation energies (E_a) for thermal degradation of PLA and PLA/ZnO pillared organic saponite nanocomposites were evaluated by the Kissinger and Ozawa methods, which demonstrated that ZnO pillared organic saponite enhanced E_a of thermal degradation of PLA and significantly improved its thermal stability. Copyright © 2015 John Wiley & Sons, Ltd.     

Dispersion copolymerization of poly(oxyethylene) macromonomers and styrene

The kinetics of dispersion copolymerization of methacryloyl-terminated poly(oxyethylene) (PEO-MA) and p-vinylbenzyl-terminated (PEO-St) polyoxyethylene macromonomers and styrene (St), initiated by a water- and/or oil-soluble initiator, was investigated using conventional gravimetric and NMR methods at 60°C. The batch copolymerizations in the water/ethanol continuous phase were conducted to high conversion. The rate of polymerization was described by the curve with a maximum at very low conversion. The initial rate of polymerization and the number-average molecular weight were found to decrease with increasing [PEO-MA], and the decrease was more pronounced in the range of a high macromonomer concentration. The rate per particle (at ca. 20% conversion) was found to be proportional to the −1.55th, the particle size to the −0.92nd, and the number of particles (at final conversion) to the 3.2nd power of [PEO-MA], respectively. At the beginning of polymerization the continuous phase is the main reaction locus. As the polymerization advances, the reaction locus is shifted from the continuous phase to the polymer particles. The transform of the reaction loci from the continuous phase to the polymer particles increases the rate of polymerization and the polymer molecular weights. The increase of the weight ratio PEO-MA/St favors the formation of monodisperse polymer particles, the colloidal stability of dispersion, and the formation of a larger number of polymer particles. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3131–3139, 1997     

Analysis of DSC curve of dodecyl methacrylate polymerization by two-peak deconvolution method

Free radical polymerization of n-dodecyl methacrylate (DDMA) in bulk has been investigated by differential scanning calorimetry (DSC). Autoacceleration of reaction was observed at the temperatures 70, 80, and 90 °C, with 0.25, 0.5, and 1 wt% of initiator, and was absent at 100 °C. DSC curves obtained at the temperatures below 100 °C were characterized by two maxima. Two-peak deconvolution was used to separate DSC curve into two constitutive unimodal curves, i.e., to calculate the contribution of polydodecyl methacrylate formed before (first maximum) and after (second maximum) the onset of autoacceleration. The share of second maximum decreases as the polymerization temperature and initiator concentration are increased. As the organization of monomer is known to decrease with increasing temperature, it can be expected that the fraction of polymerized disordered phase of monomer (first maximum in DSC curve) is the highest at 90 °C. Our results confirm this prediction and are in good agreement with those observed from conversion versus time curves of DDMA polymerization.     

Olefin polymerization in liquid sulfur dioxide initiated by m-chloroperbenzoic acid. I. Homopolymerization of styrene and α-methylstyrene

Homopolymerizations of styrene (Sty) and α-methylstyrene (AMS) in liquid sulfur dioxide were carried out in the temperature range from ?10°C to ?78°C, using m-chloroperbenzoic acid as initiator. It is shown, through the effect of initiator concentration, temperature, and times of reaction on the conversion and molecular weight of the polymers, that AMS is more reactive than Sty because it requires a smaller amount of initiator for the same conversion to be reached, although the molecular weight of the resulting polymer is lower. A linear relationship has been observed for Sty between the degree of polymerization and the initiator concentration. Within the experimental conditions employed, the presence of polysulfones has been discarded by elemental analysis. The polymerization reactions are considered to be cationic in mechanism.     

Cuso4‐amine redox‐initiated radical polymerization of methyl methacrylate mediated by a CuCl2 complex: Homogeneous reverse ATRP

Kinetic results of CuSO₄/2,2'‐bipyridine(bPy)‐amine redox initiated radical polymerization of methyl methacrylate (MMA) at 70 to 90 °C in dimethylsulfoxide suggest that such initiation is characteristic of a slow rate and a low initiator efficiency, but tertiary amines exhibit a relatively higher rate. UV‐Vis spectroscopy confirms the alpha‐amino functionality of PMMA chains. CuCl₂/bPy successfully mediates the redox‐initiated radical polymerization of MMA with aliphatic tertiary amines in a fashion of slow‐initiated reverse atom transfer radical polymerization (ATRP), i.e. both the initiator efficiency of aliphatic tertiary amines and the average molecular weight of PMMA increase gradually, while the molecular weight distribution remains narrow but become broader with the conversions. As the PMMA chains contain alpha amino and omega C‐Cl moieties, UV‐induced benzophenone‐initiated radical polymerization and Cu^ICl/bPy‐catalyzed ATRP initiated from PMMA lead to block copolymers from terminal functionalities. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2562‐2578     

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