Methyl methacrylate modification of polyolefin in a batch mixer and a twin‐screw extruder experiment and kinetic model

Free radical grafting with methyl methacrylate onto molten polypropylene was investigated in both an internal mixer and a modular co‐rotating twin‐screw extruder. There has been little open literature on melt free radical grafting copolymerization of methyl methacrylate. There is also little information on the evolution of grafting reaction with respect to reaction time in an internal mixer and along the screw axes with methyl methacrylate. The influence of residence time on the degree of grafting in an internal mixer and a twin‐screw extruder was studied through measuring reaction yields with respect to reaction time in a mixer and evolution of reaction yield along the screw axis. The degree of grafting increased with initial monomer and peroxide concentration. The grafting reactions with three different peroxides were also investigated. The grafting levels were similar to maleic anhydride and suggested that only an individual methyl methacrylate unit be grafted. The melt viscosity was dramatically reduced with addition of peroxide. A kinetic scheme of our reaction system for methyl methacrylate was proposed and compared with the experimental results.     

Copolymerization of styrene and methyl methacrylate. Part I: Experimental kinetics and mathematical modeling

A population balance approach is described to follow the time evolution of molecular properties in free-radical copolymerization. The model formulation is based on the two dimensional orthogonal collocation on finite difference (2-OCFD) and method of generating functions (GF) which was properly adopted to calculate time-conversion behavior of styrene-methyl methacrylate copolymerization. A comprehensive model which uses the free volume theory to account for diffusion controlled termination and propagation reactions as well as the variation of the initiator efficiency with respect to the monomer conversion was developed. The model is capable of predicting the conversion, composition and molecular weight development up to limiting conversions. The plasticizing effect of a blowing agent on the rate of copolymerization has been investigated. The phenomenological aspect of rate data is analyzed for the copolymerization of styrene with methyl methacrylate over a full range of conversion and the gel effect index is used to systematize the observations.     

On the gel effect in the presence of a chain transfer agent in methyl methacrylate polymerization and its copolymerization with various acrylates

The kinetics of methyl methacrylate (MMA) polymerization, and of its copolymerization with various acrylates, at high conversions in the presence of a chain transfer agent, are investigated with a dilatometer over the entire course of reaction. The displacement to higher conversions of the onset of the gel effect in the MMA homopolymerization, in the presence of a chain transfer agent, was determined. Similar information is also provided for the MMA-acrylate copolymerization systems. An increase in polymerization temperature slightly delays the onset of the gel effect in the MMA-acrylate copolymerization, but considerably increases the final conversion. The final conversion in copolymerization for a constant concentration of the chain transfer agent is independent of the initiator concentration, but is a function of the polymerization temperature. The reaction time for reaching the limiting conversion in copolymerization is increased with an increasing amount of the second monomer, as well as with an increasing number of carbon atoms in the acrylate used as the second monomer. © 1993 John Wiley & Sons, Inc.     

Kinetic modeling of atom transfer radical copolymerization of methyl methacrylate and 2‐(trimethylsilyl) ethyl methacrylate in a train of continuous stirred‐tank reactors

A comprehensive model was developed using the method of moments to describe the atom transfer radical copolymerization (ATRcoP) of methyl methacrylate and 2‐(trimethylsilyl) ethyl methacrylate in a train of continuous stirred‐tank reactors (CSTRs). The use of a train of CSTRs effectively decreases the residence time distribution and molecular weight distribution. Two different constraint conditions (i.e., constant feeding flow rate and constant total average residence time) were simulated. At constant feeding flow rate, the monomer conversion and average molecular weight are significantly improved by increasing the number of CSTRs in the train. Moreover, a constant total average residence time increases the productivity of copolymers with the increase in the number of CSTRs in the series. Thus, a train of CSTRs can be used to produce copolymers continuously with consistent quality. This method is important in obtaining a balance between the quality and quantity of the copolymer production for ATRcoP. POLYM. ENG. SCI., 55:1030–1038, 2015. © 2014 Society of Plastics Engineers     

Thermal decomposition of copolymers of methyl methacrylate and alkyl methacrylates obtained from a CSTR

Thermal decomposition of the copolymers of methyl methacrylate (MMA) with ethyl methacrylate (EMA) or n-butyl methacrylate (BMA) were investigated. The copolymers were obtained in a continuous stirred tank reactor (CSTR) using toluene and benzoyl peroxide, as solvent and initiator, respectively, at 80C. The volume was 1.2 litters and residence time was 3 hours. The thermal decomposition followed the second order kinetics for both MMA/EMA and MMA/BMA copolymers, which were almost in accordance with the order of copolymerization in a CSTR. The activation energies of thermal decomposition were in the ranges of 32-37 kcal/mol and 27-37 kcal/mole for MMA/EMA and MMA/BMA copolymers, respectively and a good additivity rule was observed against each composition for both copolymers. The thermogravimetric trace curve agreed well with the theoretical calculation.     

Graft copolymerization onto starch. I. Complexes of Mn3+ as initiators

Advantages in using the pyrophosphate complex of trivalent managanese over the sulfate complex as initiator for graft copolymerization onto starch are discussed. The first successful attempts to graft copolymerize acrylonitrile, methyl methacrylate, and acrylamide to starch and starch derivatives are described using managanic pyrophosphate as initiator. Selective solvent extraction of the reaction products and very low conversions of monomer to homopolymer in absence of starch substrates provide evidence for high grafting efficiencies obtained with acrylonitrile and methyl methacrylate. With acrylamide as monomer, however, low grafting efficiencies and considerable amounts of homopolymer are obtained under the experimental conditions investigated. Reaction mechanisms responsible for initiation of graft copolymerization are discussed. These are (a) glycol cleavage in the anhydroglucose units by Mn³⁺ ions leading to formation of a radical, and (b) enolization and further oxidation of oxidized starch by Mn³⁺ ions also leading to radical species. Mechanisms are also proposed for homopolymerization through Mn³⁺ oxidation of enols which probably are formed by “vinylogous” addition of water molecules to acrylamide and methyl methacrylate.     

Macromers by carbocationic polymerization

Summary The reactivity ratio of -(p-vinylphenyl) polyisobutylene (p-polyisobutenylstyrene, PIB-St) macromers in copolymerization with methyl methacrylate (MMA) and styrene (St) has been examined at various conversions in various solvents and with three macromer chain lengths. Examination of copolymerization reactivity ratios in PIB-St/MMA and PIB-St/St systems indicate that the reactivity of PIB-St with respect to MMA and St comonomers in various solvents is the same as that of styrene. Larger than expected small-comonomer reactivity ratios (r₂) obtained at high conversions and high macromer molecular weights have been attributed to the onset of microphase separation during copolymerization.     

Copolymerization of 6-vinyl-1,4-benzodioxane with methyl methacrylate andn-butyl acrylate

Summary 6-Vinyl-1,4-benzodioxane was synthesized and its copolymerization with methyl methacrylate and n-butyl acrylate was investigated. In this work concentration ladder type copolymerizations were performed. The results of copolymerization were analyzed using a nonlinear least squares method and reactivity ratios were calculated from the analysis. The 6-vinyl-1,4-benzodioxane was found to be a more reactive monomer than either the methyl methacrylate or butyl acrylate, but only slightly so in the methyl methacrylate case.     

Free radical copolymerization of methyl methacrylate and allyl acetate Part 2 structure and properties

The structure of the product from the free radical bulk copolymerization of methyl methacrylate (MMA) and allyl acetate (AAc) was investigated. The mole fraction of AAc plays an important role in the copolymerization of these two monomers. Molecular weight (MW) and molecular weight distribution (MWD) are completely altered when the feed composition is dominantly AAc. NMR spectroscopy confirmed the incorporation of AAc into the polymer. However, no allyl–allyl linkages were observed at low conversions. T_g was found to be affected by the incorporation of AAc into the polymer. © 2001 Society of Chemical Industry     

Bulk copolymerization of dimethyl meta-isopropenyl benzyl isocyanate (TMI®): Determination of reactivity ratios

Dimethyl meta-isopropenyl benzyl isocyanate (TMI®) is a bifunctional monomer with an unsaturation and an isocyanate group. Bulk copolymerizations of TMI with styrene, methyl methacrylate, and n-butyl acrylate were investigated. Polymerizations were carried out to low conversions in sealed test tubes at 70°C. The copolymer composition was determined using Fourier transform infrared (FTIR) spectroscopy. The data were analyzed using the terminal, as well as restricted penultimate, model of copolymerization. The method of Kelen-Tudos was used to calculate the reactivity ratios according to the terminal model. A nonlinear regression analysis was also carried out. Low reactivity ratio values for TMI were obtained for the copolymerizations with styrene and methyl methacrylate as a result of the inability of TMI to undergo homopolymerization. The value was higher for the copolymerization with n-butyl acrylate. Composition diagrams were generated, and the range of TMI concentration in the monomer charge for the preferential incorporation of TMI in the copolymer was identified. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 559–568, 1998     

Mechanochemical copolymerization of methyl methacrylate and styrene initiated by the grinding of quartz

The copolymerization of methyl methacrylate and styrene mechanochemically initiated by the grinding of quartz in the monomer mixture was investigated by using a vibrating ball mill. The effect of the grinding of quartz on the copolymerization was investigated by characterizing both the polymer formed and the ground quartz. The copolymerization proceeds apparently from the quartz grindings and was closely related to the total surface area of the ground quartz. The molecular weight distributions of the copolymers formed were unimodal as found in a homopolymer of only methyl methacrylate. It was clear from the composition analysis of the copolymer that the mechanochemical copolymerization of methyl methacrylate and styrene proceeded with a radical polymerization mechanism because of radicals on the quartz surface produced by the grinding. The monomer reactivity ratios obtained by the Fineman‐Ross method suggested that the copolymers formed were alternating copolymers. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2011–2017, 2002; DOI 10.1002/app.10544     

连续萃取酯化法制取甲基丙烯酸甲酯的探讨

本文探讨了萃取酯化法自甲基丙烯酰胺硫酸盐制取甲基丙烯酸甲酯的可行性。在带搅拌的塔式反应器中,以环己烷为萃取剂,进料的摩尔比为甲基丙烯酰胺:甲醇:水:环己烷=1:2:3:0.7,反应温度363K,物料停留时间为5小时时,酯收率可达86％,比同样条件下,不加萃取剂时的酯收率增加了13％。     

Copolymerization behavior of 2-vinylselenophene

Summary 2-Vinylselenophene was synthesized and its copolymerization with methyl methacrylate and n-butyl acrylate was investigated. The copolymerization data was analyzed by a nonlinear least squares error-in-variables method. 'Ihe results of these preliminary experiments indicate that 2-vinylselenophene is a very reactive monomer, approximately as reactive as 2-vinylthiophene in copolymerizations with methyl methacrylate and n-butyl acrylate.     

The competitive reactions of initiator fragments and growing polymer chains against the surface of carbon black

The reactivity of free radicals generated by the thermal decomposition of 2,2′-azobisisobutyronitrile (AIBN) is compared with that of the free radicals from 2,2′-azobis-2,4-dimethyl valeronitrile in nitrogen atmosphere at 60°C, and the reaction mode of the free radicals with carbon black surface is discussed. Also bulk polymerization of vinyl monomers such as styrene and methyl methacrylate was performed in the presence of furnace black in nitrogen at 60°C using AIBN as initiator. Typical retardation is found in the course of conversion of methyl methacrylate into the polymer, whereas inhibition is observed in the conversion of styrene which results in an induction period of the reaction. In addition, inhibition by carbon black is also found in the copolymerization of methyl methacrylate with a small amount of styrene. On the basis of the results of the conversions of different kinds of monomers, competitive reactions of 2-cyano-2-propyl radicals from AIBN and growing polymer radicals are suggested to occur preferentially on the surface of carbon black. The results are supported by the observation of the stability of the dispersion of the resulting carbon black in adequate solvents and also by gas chromatographic analysis of the pyrolysis products of the polymers bound to the surface of carbon black.     

Application of graft copolymers using macromonomer method to two-component polyurethane coatings

Graft copolymers as acrylic polyols in two-component polyurethane coatings were prepared by the free-radical copolymerization of methyl methacrylate, n-butyl methacrylate, n-butyl acrylate, acrylic acid, 2-hydroxyethyl methacrylate and poly(methyl methacrylate)-macromonomers. The poly(methyl methacrylate) macromonomer was prepared by the polymerization of methyl methacrylate in the presence of thiopropionic acid as a transfer agent followed by the reaction with glycidyl methacrylate. These polymers, whose numbers of poly(methyl methacrylate) macromonomer branches and the molecular weights of the poly(methyl methacrylate) macromonomer branches were controlled, offer an advantage over conventional resins with respect to the application/appearance of coatings as well as the final film properties. Some of these advantages were higher solids and a better control of the coating rheology, an increase in the cross-linking reactivity of the polyols with polyisocyanate and improvement in film toughness. The change in the morphological structure of the films under tensile stress was of particular interest.     

甲基丙烯酸甲酯与降解天然橡胶胶乳共聚的研究

研究了不同降解程度的天然橡胶胶乳与甲基丙烯酸甲酯 (MMA)共聚反应 ,发现随着降解时间增长 ,共聚物中 MMA聚合链与橡胶段的相对比例 (重量比 )明显增加。找到了一种适用于降解胶乳与 MMA共聚混合物的分离方法     

Studies in the graft copolymerization of vinyl monomers on cellulosic materials

Graft copolymerization of acrylonitrile, methyl methacrylate, and vinyl acetate on bleached holocellulose initiated by ceric ions in aqueous medium was studied at 29°C. The extent of graft copolymer formation was poly(methyl methacrylate) > polyacrylonitrile > poly(vinyl acetate), indicating the influence of polarity of monomer on graft copolymerization. It was found that, although the molecular weights of the grafted polyacrylonitrile copolymer were lower than the values obtained for poly(methyl methacrylate), the latter was less frequently incorporated on the cellulosic backbone polymer than the polyacrylonitrile grafts. The marked reductions in graft level associated with thiolation of the cellulosic material suggest that hydrogen abstraction reactions from carbon atom carrying hydroxyl groups may not be important in graft copolymer formation.     

降解天然橡胶胶乳与甲基丙烯酸甲酯共聚的研究

研究不同降解程度的天然橡胶胶乳与甲基丙烯酸甲酯（ＭＭＡ）共聚反应，找到了一种适用于降解胶乳与ＭＭＡ共聚混合物的分离方法，发现随着降解时间的增长，共聚物中ＭＭＡ聚合链段与橡胶链段的相对比例（重量比）明显增加。     

Preparation of gold nanoparticles on poly(methyl methacrylate) nanospheres with surface-grafted poly(allylamine)

A facile method for in situ anchoring of gold nanoparticles onto the surface of polymer nanospheres was successfully developed in this study. As polymer nanospheres, amphiphilic poly(methyl methacrylate) (PMMA)/poly(allylamine) (PAA) nanospheres were prepared by graft copolymerization of methyl methacrylate from PAA. The gold nanoparticles anchored were spherically symmetric and the average sizes were ∼12 nm for all samples. It was found that surface-grafted PAA effectively anchored and stabilized gold nanoparticles for a long period of time.     

Synthesis and properties of amphiphilic copolymers of butyl acrylate and methyl methacrylate with uniform polyoxyethylene grafts

Amphiphilic copolymers of butyl acrylate (BA) and methyl methacrylate (MMA) with uniform polyoxyethylene (PEO) grafts were synthesized by the copolymerization of BA and MMA with a methacrylate‐terminated PEO macromer in benzene with azobisisobutyronitrile as an initiator. The effects of various copolymerization conditions on the grafting efficiency and molecular weight of the copolymers, as well as the effect of the copolymerization time on the conversions of the macromer and the monomers, were reported. The copolymers, with uniform PEO grafts, were purified by successive extractions with water and ether/acetone (3/7) to remove unreacted macromer and ungrafted copolymers of MMA and BA, respectively. The purified graft copolymers were characterized with IR, ¹H‐NMR, membrane osmometry, gel permeation chromatography, and differential scanning calorimetry. The highest grafting efficiency was about 90%, and molecular weight of the copolymers varied around 10⁵. The average grafting number of the copolymer was about 10. A study of the crystalline properties, emulsifying properties, phase‐transfer catalytic ability, and mechanical properties of the graft copolymers showed that the emulsifying volume decreased with the increasing molecular weight of the PEO grafts but increased with the PEO content. The conversion of potassium phenolate in the Williamson solid–liquid reaction obviously increased with an increasing PEO content of the graft copolymers. The crystallinity of the graft copolymers increased with the PEO content of the graft copolymers or the molecular weight of the macromer used. The copolymers, prepared under certain conditions, behaved as thermoplastic elastomers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2982–2988, 2003