Thermal polymerization of p-methyl styrene at high conversions and temperatures

An experimental investigation of the kinetics of the thermally initiated free radical polymerization of p-methyl styrene in bulk at temperatures of 120°, 140° and 160° in the conversion range, 0–96% is reported. Conversions were measured gravimetrically and by gas chromatography and molecular weight distributions and weight-average molecular weights by size exclusion chromatography (SEC) and low angle laser light scattering photometry (LALLSP). A kinetic model which accounts for diffusion-controlled termination and predicts conversion/time and molecular weight and long chain branching development for nonisothermal polymerizations has been developed. This model should find use in the design, simulation and optimization of poly(p-methyl styrene) reactors.     

Co(acac)2‐Mediated Radical Polymerization of Acrylonitrile: Control Over Molecular Weights and Copolymerization With Methyl Methacrylate

The cobalt‐mediated radical polymerization of acrylonitrile in DMSO using cobalt (II) acetylacetonate [Co(acac)₂] as mediator is studied. Both the evolution of molecular weight and conversion over time under various conditions are monitored. Molecular weights increase sharply at the beginning of the reaction and subsequently grow linearly with conversion. No branching of the polymer is observed by ¹³C NMR. By a careful design of the reaction parameters, number‐average molecular weights >1.2 · 10⁵ g · mol^?1 with a PDI around 2.4 together with conversions of up to 90% within 24 h are achieved. The copolymerization parameters of acrylonitrile with methyl methacrylate in DMSO at 30 °C are determined using the Kelen‐Tüdõs approach giving r_AN = 0.33, r_MMA = 0.71.

     

EMULSION COPOLYMERIZATION OF ACRYLONITRILE AND BUTADIENE. CALCULATION OF THE DETAILED MACROMOLECULAR STRUCTURE

A novel mathematical model is developed that predicts the detailed macromolecular structure of an acrylonitrile-butadiene rubber (NBR) produced in an industrial emulsion polymerization. The model consists of: (i) a basic module that calculates the monomer conversion and the copolymer composition; (ii) a particle size distribution module; and (iii) a macromolecular structure module that calculates the bivariate chain length distributions of the linear fraction and of each branched topology (characterized by the number of branching points per molecule). From the bivariate distributions, the univariate distributions of molecular weights, copolymer composition, and degrees of branching are obtained. The model was validated from global measurements of conversion, average molecular weights, average composition, and average degrees of branching.     

Free‐radical terpolymerization of n‐butyl acrylate/butyl methacrylate/d‐limonene

d ‐Limonene (Lim) is a renewable monoterpene derived from citrus fruit peels. We investigated it for use as part of a more sustainable polymer formulation. The bulk free‐radical terpolymerization of n‐butyl acrylate (BA)/butyl methacrylate (BMA)/Lim was carried out at 80°C with benzoyl peroxide as the initiator. The terpolymerization was studied at various initial BA/BMA/Lim molar ratios, and the products were characterized for conversion, terpolymer composition, molecular weight, and glass‐transition temperature. Lim was observed to undergo a significant degradative chain‐transfer reaction, which greatly influenced the polymerization kinetics. The rate of polymerization, final conversion, and polymer molecular weight were all significantly reduced because of the presence of Lim. Nonetheless, polymers with relatively high weight‐average molecular weights (20,000–120,000 Da) were produced. The terpolymer composition was well predicted with the reactivity ratios estimated for each of the three copolymer subsystems. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42821.     

Experimental study of the spontaneous thermal homopolymerization of methyl and n‐butyl acrylate

This article presents an experimental study of the spontaneous thermal homopolymerization of methyl acrylate (MA) and n‐butyl acrylate (nBA) in the absence of any known added initiators at 120 and 140°C in a batch reactor. The effects of the solvent type, oxygen level, and reaction temperature on the monomer conversion and polymer average molecular weights were investigated. Three solvents, dimethyl sulfoxide (DMSO; polar, aprotic), cyclohexanone (polar, aprotic), and xylene (nonpolar) were used. The spontaneous thermal polymerization of MA and nBA in DMSO resulted in a lower conversion and higher average molecular weights in comparison to polymerization in cyclohexanone and xylene under the same conditions. The highest final conversion of both monomers was obtained in cyclohexanone. The high polymerization rate in cyclohexanone was most likely due to an additional initiation mechanism where cyclohexanone complexed with the monomer to generate free radicals. Bubbling air through the mixture led to a higher monomer conversion during the early stage of the polymerization and a lower polymer average molecular weight in xylene and cyclohexanone; this indicated the existence of a distinct behavior between the air‐ and nitrogen‐purged systems. Matrix‐assisted laser desorption/ionization time‐of‐flight analysis of the polymer samples taken from nitrogen‐bubbled batches did not reveal fragments from initiating impurities. On the basis of the identified families of peaks, monomer self‐initiation is suggested as the principal mode of initiation in the spontaneous thermal polymerization of MA and nBA at temperatures above 100°C. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

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

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

GPC observations of branching effects in anionic polymerization of methyl methacrylate: A preliminary study

The anionic polymerization of methyl methacrylate was performed in tetrahydrofuran (THF) at ?78°C, using sec‐butyllithium/1,1‐diphenylethylene (DPE) as the initiation system. The effects of polymerization time and initiator concentration on the branching reaction were studied. High vacuum was used to prevent contamination during the polymerization. Gel permeation chromatography (GPC) was used to characterize the branching effect qualitatively. Experimental results indicated that the monomer conversion reached more than 98% in a polymerization time of 10 min. The branching reaction occurred after high monomer conversion, resulting in a tail of high molecular weight in the GPC trace. This branching effect, observed by GPC, increased with polymerization time. Rapid termination was thus probably required immediately after all of the monomer was consumed in the preparation of a well‐defined PMMA without a high‐molecular‐weight tail in this diphenylbutylllithium/THF/?78°C system. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Obvious complexity of the anionic polymerization of malolactonic acid esters

Summary The anionic polymerization and copolymerization of butyl and benzyl malolactonates initiated with potassium acetate/dibenzo-18-crown-6 or [222] complex have been studied at 40°C in bulk and in dichloromethane and tetrahydrofuran solutions. Kinetics and polymer molecular weights were followed by SEC. In bulk and for conversion below 30%, molecular weights are close to those calculated for a living process then the conversion increase leads to a significant discrepancy between theoretical and measured molecular weights. In solution, side reactions take place significantly and no evident relationship between molecular weight and initiator concentration can be established, even at low conversion. Same situation was observed in the case of block copolymers synthesis. At last, evidence for transfer reactions has been shown by using model reactions. Received: 11 September 1997/Revised version: 22 January 1998/Accepted: 23 January 1998     

A novel polymer chain growing mode and styrene copolymer prepared with low molecular weight copolymer of α‐methylstyrene and styrene as macroinitiator

A new polymer chain growth mode, having multiple potential chain propagation sites, initiated by oligomer of α‐methylstyrene (AMS) and styrene (St) (PAS) is presented in this article. The effects of PAS content, AMS fraction in PAS and reaction temperature on bulk polymerization of St have been investigated. It is demonstrated that the PAS performed as macroinitiator in the polymerization of St. The average molecular weights of products increase significantly with the evolution of the polymerization, which is different from conventional free radical polymerization. With 20 wt % macroinitiator, the molecular weights increase from 1.21 × 10⁵ to 3.00 × 10⁵ with the monomer conversion increasing from 15.3 to 83.0%. This unique feature is tentatively attributed to both the reversible polymerization–depolymerization of AMS segments at high temperature which could generate more than one propagation sites in a polymer chain and the combination termination of St free radical polymerization. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41460.     

Effect of some anions of some nickel salts on the aqueous polymerization of methyl methacrylate

The aqueous polymerization of methyl methacrylate in the absence and in the presence of some anions of nickel salts was carried out at temperatures of 40°C, 50°C, and 60°C using sodium bisulfite as initiator. The nitrate anion (NO) was found to have the highest catalytic effect and resulted in polymers having the least average molecular weights, while the sulfate anion (SO) was found to have the least catalytic effect and resulted in polymers having the highest average molecular weights. The apparent activation energy for the polymerization process was found to be 4.3, 3.6, 3.8, and 4.8 × 10⁴ J/mol in the absence and in the presence of Ni(NO₃)₂, NiCl₂, and NiSO₄ containing the same amount of nickel (0.00587 g). ¹³C-NMR spectra for the polymers obtained in the absence and in the presence of different nickel anions were found to result in nearly the same tacticity.     

Synthesis,characterization, and kinetic investigation of acrylic monomers derived from acetaminophen and ρ‐cresol as model drug molecules

In this work, the synthesis, characterization, and kinetic investigation of the free‐radical polymerization of 4‐acetylaminobenzene propenoic ester (ABPE) and 4‐methylbenzene propenoic ester (MBPE) were studied. The kinetic behaviors of ABPE and MBPE in the polymerization initiated by azobisisobutyronitrile in dimethylformamide solutions at temperatures between 50 and 120°C were investigated, and experimental and theoretical conversion–time curves were compared. Both monomers showed a polymerization ceiling temperature (T_c). T_c was calculated with experimental values of k_p/k with a constant concentration of 0.7 mol/L for monomers. T_c was about 141 and 131°C for ABPE and MBPE, respectively. In addition, the solvent effect on the polymerization reaction was investigated via the calculation of the solvent chain‐transfer constant (C_s) for the ABPE monomer. Then, C_s was determined from the average degree of polymerization measured with gel permeation chromatography and the calculation of the overall rate of polymerization at 60°C. The results showed that dimethylformamide as a solvent had no effect on the rate of polymerization. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4369–4374, 2006     

Heterogeneous bulk polymerization of styrene in the presence of polybutadiene: Calculation of the macromolecular structure

A mathematical model is presented that simulates the polymerization of styrene in the presence of polybutadiene (PB) for producing high‐impact polystyrene (HIPS) via the heterogeneous bulk process. The model follows the polymerization in two phases; and calculates in each phase the main reaction variables and the molecular structure of the three polymeric components: free polystyrene (PS), unreacted PB, and graft copolymer. Two polymerizations (at 90 and 120°C) were carried out and simulated. The model was validated with measurements of the monomer conversion, the grafting efficiencies, and the average molecular weights. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3023–3039, 2006     

A new method to determine monomer concentration in the polymer particles of emulsion polymerization systems by dynamic light scattering

Emulsifier‐free emulsion polymerization of styrene was performed in the presence of small amount of methacrylic and itaconic acids as carboxylic acid monomers and potassium persulfate as an initiator at 70°C to prepare monodisperse polymer particles. Diameter of monomer swollen polymer particles (d_pswol) was measured by dynamic light scattering for samples taken from the reaction mixture during the Intervals II and III of the emulsion polymerization. Graphically treatment of d_pswol versus conversion data allowed us for the first time to directly determine the critical monomer conversion (x_c), from which constant monomer concentration in the polymer particles (C_MP) during the Interval II was then calculated. x_c and C_MP were obtained to be 0.379 and 5.68, respectively. C_MP value is in good agreement with that obtained by centrifugation method and those reported in the literature for the similar system. Attempts were also made to evaluate the average number of growing chain per particle ( ) during the Interval II of emulsion polymerization of styrene. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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

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

Microemulsion polymerization of 1,3-butadiene

One-phase microemulsion regions at 25 and 60 °C and the polymerization at 60 °C in o/w microemulsion formed by 1,3-butadiene, water, and a mixture of the surfactants, dodecyltrimethylammonium bromide, and didodecyldimethylamonium bromide (3/1 w/w), are reported. The polybutadienes obtained here have similar characteristics to those of their homologous obtained by emulsion polymerization, with the only difference that the average particle size of the former (25–30 nm) was smaller by an order of magnitude. The obtained polymer had high average molecular weights, but the gel content at high conversion is lower than the value for a conventional emulsion polymerization. The DSC measurements showed that the polymer has a single glass transition temperature at −72.5 ± 1.5 °C.     

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

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

Atom Transfer Radical Block Copolymerization of 2‐(N,N‐Dimethylamino)ethyl Methacrylate and 2‐Hydroxyethyl Methacrylate

Block copolymerization of 2‐(N,N‐dimethylamino)ethyl methacrylate (DMAEMA) with 2‐hydroxyethyl methacrylate (HEMA) via atom transfer radical polymerization (ATRP) was studied in methanol using a macroinitiator method and a “one‐pot” sequential addition method. The polymerization sequence of the two monomers strongly affected the block copolymer formation. When DMAEMA was used as the first monomer, both methods produced block copolymer samples containing significant amounts of DMAEMA homopolymer chains, because of the elimination of active halogen chain‐ends during the preparation of polyDMAEMA. Well‐controlled block copolymers with various block lengths were obtained via the macroinitiator method when polyHEMA was used as macroinitiator to initiate the polymerization of DMAEMA. The sequential addition method, in which HEMA was polymerized first with 90% conversion and DMAEMA was subsequently added, also yielded controlled block copolymers when the polymerization was carried out at room temperature with the DMAEMA conversion below 60%. Increasing the temperature to 60 °C promoted the copolymerization rate but the reaction suffered from gel formation. The addition of water to the system accelerated the polymerization rate, but led to the loss of the system livingness.

Gel permeation chromatograms of poly(HEMA‐b‐DMAEMA). The samples were prepared in methanol at room temperature with different block molecular weights using the macroinitiator method.     

Preparation of controlled molecular weight and narrow distribution HALS and its application

A polymerizable hindered amine light stabilizer (HALS) 1,2,2,6,6-pentamethyl-piperidin-4-yl acrylate (PMPA) was synthesized, and it was copolymerized with styrene to prepare poly(St-co-PMPA) by reversible addition fragmentation chain transfer (RAFT) polymerization. The reaction conditions, such as chain transfer agent (CTA)/initiator ratio, monomer/CTA ratio, and St/PMPA ratio, were found to affect the polymerization reaction. Poly(St-co-PMPA) with high molecular weight and narrow distribution could be obtained under suitable conditions. The molecular weight is about 3.0 × 10³ to 5.0 × 10³ and the molecular weight distribution is about 1.07 to 1.25. The result showed that PMPA was effectively added to the polymer chain and the polymerizations were found to proceed in controlled fashions under a lower conversion. Moreover, the tensile strength and notched impact strength of ABS/poly(St-co-PMPA) are significantly improved, respectively, after 800-h UV irradiation, which was both higher than that of pure ABS. The results showed that poly(St-co-PMPA) was an effective high molecular weight HALS.     

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

Abstract

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

Graft copolymerization onto starch. II. Grafting of acrylonitrile to granular native potato starch by manganic pyrophosphate initiation. Effect of reaction conditions on grafting parameters

The effect of reaction conditions on the composition of native potato starch–polyacrylonitrile graft copolymers initiated by manganic pyrophosphate onto starch slurries at 30°C has been examined. In general, when the Mn³⁺ ion concentration was increased from 0.15 × 10^?3M to 3.0 × 10^?3M (other conditions kept constant), an increase in conversion of monomer to polymer and % add-on was observed, whereas frequency of grafts (anhydroglucose units, AGU, per grafted chain) decreased. Also, the average molecular weights of grafts showed a decrease from 2.2 × 10⁵ to 1.5 × 10⁵. Increasing the concentration ratio of starch to monomer during polymerization by a factor of 3 produced an increase in the conversion of monomer to polymer, whereas an increase in frequency of grafts (AGU/chain) was obtained. Values of % add-on and average molecular weights of the grafts showed, however, a decreasing tendency. It was observed that grafting onto starch took place readily even at acid additions as low as 10 × 10^?3M H₂SO₄ (pH ?1.8). Selective solvent extraction of homopolymer and extremely low conversions of monomer to polymer (0.1%–1.5%) in duplicate runs without addition of starch indicated that grafting efficiencies were high in all cases. An attempt has been made to interpret the results in terms of variations in factors such as initial ratio of (Mn³⁺)/(AGU), termination rate of acrylonitrile chain radicals by oxidation by Mn³⁺ ions, oxidation rate of radicals formed on anhydroglucose units by Mn³⁺ ions, and physical factors such as diffusion rate of Mn³⁺ ions through the polyacrylonitrile-grafted starch granules for terminating the radicals.