Methacrylate butadiene systems

Butadiene is used primarily in the production of synthetic rubbers, including styrene-butadiene rubber (SBR), polybutadiene nibber (BR), styrene-butadiene latex (SBL), chloroprene rubber (CR) and nitrile rubber (NR). Important plastics containing butadiene as a monomeric component are shock-resistant polystyrene, a two-phase system consisting of polystyrene and polybutadiene ABS polymers consisting of acrylonitrile, butadiene and styrene and a copolymer of methyl methacrylate, butadiene and styrene (MBS), which is used as a modifier for poly(vinyl chloride). It is also used as an intermediate in the production of chloroprene, adiponitrile and other basic petrochemicals. The worldwide use pattern for butadiene in 1981 was as follows (%) SBR + SBL, 56 BR, 22 CR, 6 NR, 4 ABS, 4 hexamethylenediamine, 4 other, 4. The use pattern for butadiene in the United States in 1995 was (%) SBR, 31 BR, 24 SBL, 13 CR, 4 ABS, 5 NR, 2 adiponitrile, 12 and other, 9 (Anon., 1996b). 

In the polymer impregnated gels, some porosity typically remains. Although some copolymers of methyl methacrylate, butadiene and styrene have been used to impregnate silica, the best known system is still silica impregnated with polymethyl methacrylate (PMMA)150-153. While this type of hybrid was important at first, it has been surpassed by other methods of hybrid synthesis that are simpler, with fewer steps and shorter times. 

Composite particles which have been made using the monomer-starved process (8) include the poly(styrene-co-butadiene)-poly(ethyl acrylate-co-methacrylic acid) system. 

Pearson and Lee (1991) examined the effects of particle-size and particle-distribution effects on rubber-toughened epoxy resins. They examined a variety of CTBN liquid rubbers and a methacrylated butadiene styrene core-shell particle in a DGEBA-piperidine system. They found that the toughening mechanism for small particles was internal cavitation of the... 

Poly(vinyl chloride) (PVC) homopolymer is a stiff, rather brittle plastic with a glass temperature of about 80°C. While somewhat more ductile than polystyrene homopolymer, it is still important to blend PVC with elastomer systems to improve toughness. For example, methyl methacrylate-butadiene-styrene (MBS) elastomers can impart impact resistance and also optical clarity (see Section 3.3). ABS resins (see Section 3.1.2) are also frequently employed for this purpose. Another of the more important mechanical blends of elastomeric with plastic resins is based on poly(vinyl chloride) as the plastic component, and random copolymers of butadiene and acrylonitrile (AN) as the elastomer (Matsuo, 1968). On incorporation of this elastomeric phase, PVC, which is ordinarily a stiff, brittle plastic, can be toughened greatly. A nonpolar homopolymer rubber such as polybutadiene (PB) is incompatible with the polar PVC. Indeed, electron microscopy shows... 

Impact Modifiers Impact modifiers are either systems with spherical elastomer particles in a rigid polymer matrix or they are systems with a honeycomb, network type of dispersed elastomeric phase. For the spherical elastomeric particles, examples are acrylonitrile butadiene styrene (ABS), methacrylate-butadiene-styrene (MBS) and acrylics. These systems are either graft copolymers of methyl methacrylate-butyl acrylate-styrene or methyl methacrylate-ethylhexyl acrylate-styrene. For the honeycomb, network type of dispersed elastomeric phase ethylene vinyl acetate (EVA) and chlorinated polyethylene (CPE) or directly dispersed rubber are examples. Both of these two impact modifiers exist in the polymeric form, hence they can hardly migrate and evaporate because of their size. As a result, they pose almost no problems to health. For PVC window frame production, usually the first type (and acrylic impact modifiers) are used while MBS modifiers are found to be very effective in plasticised as well as in rigid PVC. CPE is mainly used in PVC for products like sheet, pipe, gutters and sidings. 

Acryhc stmctural adhesives have been modified by elastomers in order to obtain a phase-separated, toughened system. A significant contribution in this technology has been made in which acryhc adhesives were modified by the addition of chlorosulfonated polyethylene to obtain a phase-separated stmctural adhesive (11). Such adhesives also contain methyl methacrylate, glacial methacrylic acid, and cross-linkers such as ethylene glycol dimethacrylate [97-90-5]. The polymerization initiation system, which includes cumene hydroperoxide, N,1S7-dimethyl- -toluidine, and saccharin, can be apphed to the adherend surface as a primer, or it can be formulated as the second part of a two-part adhesive. Modification of cyanoacrylates using elastomers has also been attempted copolymers of acrylonitrile, butadiene, and styrene ethylene copolymers with methylacrylate or copolymers of methacrylates with butadiene and styrene have been used. However, because of the extreme reactivity of the monomer, modification of cyanoacrylate adhesives is very difficult and material purity is essential in order to be able to modify the cyanoacrylate without causing premature reaction. 

Isocyanates can be added to solvent-borne CR adhesive solutions as a two-part adhesive system. This two-part adhesive system is less effective with rubber substrates containing high styrene resin and for butadiene-styrene block (thermoplastic rubber) copolymers. To improve the specific adhesion to those materials, addition of a poly-alpha-methylstyrene resin to solvent-borne CR adhesives is quite effective [76]. An alternative technique is to graft a methacrylate monomer into the polychloroprene [2]. 

Copolymerization of methacrylic acid with butadiene and isoprene was photoinitiated by Mn2(CO)io without any halide catalyst [28,29]. The po]ymerization system is accompanied by a Dieis-Alder additive. Cross propagation reaction was promoted by adding trieth-y]aluminum chioride. 

Platinum-cobalt alloy, enthalpy of formation, 144 Polarizability, of carbon, 75 of hydrogen molecule, 65, 75 and ionization potential data, 70 Polyamide, 181 Poly butadiene, 170, 181 Polydispersed systems, 183 Polyfunctional polymer, 178 Polymerization, of butadiene, 163 of solid acetaldehyde, 163 of vinyl monomers, 154 Polymers, star-shaped, 183 Polymethyl methacrylate, 180 Polystyrene, 172 Polystyril carbanions, 154 Potential barriers of internal rotation, 368, 374... 

Notice that the tt system in methyl methacrylate is nearly the same as that in butadiene. The only difference is the replacement of one C atom by an O atom. Both systems have four overlapping p orbitals, giving rise to two bonding MOs and two antibonding MOs, so it is reasonable that the tt systems are quite similar. 

ISO 10366-1 2002 Plastics - Methyl methacrylate-acrylonitrile-butadiene-styrene (MABS) moulding and extrusion materials - Part 1 Designation system and basis for specifications ISO 10366-2 2003 Plastics - Methyl methacrylate-acrylonitrile-butadiene-styrene (MABS) moulding and extrusion materials - Part 2 Preparation of test specimens and determination of properties... 

Bauer et al. describe the use of a noncontact probe coupled by fiber optics to an FT-Raman system to measure the percentage of dry extractibles and styrene monomer in a styrene/butadiene latex emulsion polymerization reaction using PLS models [201]. Elizalde et al. have examined the use of Raman spectroscopy to monitor the emulsion polymerization of n-butyl acrylate with methyl methacrylate under starved, or low monomer [202], and with high soUds-content [203] conditions. In both cases, models could be built to predict multiple properties, including solids content, residual monomer, and cumulative copolymer composition. Another study compared reaction calorimetry and Raman spectroscopy for monitoring n-butyl acrylate/methyl methacrylate and for vinyl acetate/butyl acrylate, under conditions of normal and instantaneous conversion [204], Both techniques performed well for normal conversion conditions and for overall conversion estimate, but Raman spectroscopy was better at estimating free monomer concentration and instantaneous conversion rate. However, the authors also point out that in certain situations, alternative techniques such as calorimetry can be cheaper, faster, and often easier to maintain accurate models for than Raman spectroscopy, hi a subsequent article, Elizalde et al. found that updating calibration models after... 

Although this method yields a mixture of homopolymer and graft copolymer, and probably also ungrafted backbone polymer, some of the systems have commercial utility. These are high-impact polystyrene (HIPS) [styrene polymerized in the presence of poly(l,3-buta-diene)], ABS and MBS [styrene-acrylonitrile and methyl methacrylate-styrene, respectively, copolymerized in the presence of either poly(l,3-butadiene) or SBR] (Sec. 6-8a). 

Since the late 1960 s a few papers have demonstrated compositional analysis of various polymer systans by Raman spectroscopy. For example, Boerio and Yuann (U) developed a method of analysis for copolymers of glycidyl methacrylate with methyl methacrylate and styrene. Sloane and Bramston-Cook (5) analyzed the terpolymer system poly(methyl methacrylate-co-butadiene-co-styrene). The composition of copolymers of styrene-ethylene dimethacrylate and styrene-divinylbenzene was determined by Stokr et (6). Finally, Water (7) demonstrated that Raman spectroscopy could determine the amount of residual monomer in poly(methyl methacrylate) to the % level. This was subsequently lowered to less than 0.1% (8). In spite of its many advantages, the potential of Raman spectroscopy for the analysis of polymer systems has never been fully exploited. 

The mechanical degradation and production of macroradicals can also be performed by mastication of polymers brought into a rubbery state by admixture with monomer several monomer-polymer systems were examined (10, 11). This technique was for instance studied for the cold mastication of natural rubber or butadiene copolymers in the presence of a vinyl monomer (13, 31, 52). The polymerization of methyl methacrylate or styrene during the mastication of natural rubber has yielded copolymers which remain soluble up to complete polymerization vinyl acetate, which could not produce graft copolymers by the chain transfer technique, failed also in this mastication procedure. Block and graft copolymers were also prepared by cross-addition of the macroradicals generated by the cold milling and mastication of mixtures of various elastomers and polymers, such as natural rubber/polymethyl methacrylate (74), natural rubber/butadiene-styrene rubbers (76) and even phenol-formaldehyde resin/nitrile rubber (125). 

The importance of the graft handle on a 62/38 butadiene-methyl methacrylate rubber can be illustrated by its effect on the optical properties of the polyblend. From Table II it can be seen that the reduction in percent haze is dramatic for an increase of methyl methacrylate graft from 0 to 27% by weight, while there is no apparent change in the light transmission. The blend resin in this polyblend system was an 88-12 methyl methacrylate-styrene copolymer, and the total resin to backbone rubber ratio was kept at 2.5-1.0. The measured refractive indices are included for each component (the graft rubber and the blend resin). The difference in refractive index amounts to no more than 0.004 unit for any of the components. 

Emulsion polymerization is used for 10-15% of global polymer production, including such industrially important polymers as poly(acrylonitrile-butadiene-styrene) (ABS), poly (styrene), poly(methyl methacrylate), and polyvinyl acetate.38 These are made from aqueous solutions with high concentrations of suspended solids. The important components have unsaturated carbon-carbon double bonds. These systems are ideal for Raman spectroscopy and a challenge for other approaches, though NIR spectroscopy has been used. 

For the styrene-butadiene-methacrylic acid copolymers, meth-acrylic acid was also found in the serum, on the particle surface, and buried inside the particles. At 23% degree of neutralization, less methacrylic acid was found in the serum and on the particle surface than with acrylic acid, i.e., more was buried inside the particle. At 3.0% methacrylic acid, the amount incorporated into the particle was fairly constant, independent of the degree of neutralization. The different distributions of methacrylic and acrylic acids were explained by their different distributions between the monomer-polymer and aqueous phases. Thus these characterization results show the effect of vinyl carboxylic acid type and concentration on the loci of the carboxyl groups. Similar correlations could be made with other systems. 

The radical polymerization in aqueous solution of a series of monomers—e.g., vinyl esters, acrylic and methacrylic acids, amides, nitriles, and esters, dicarboxylic acids, and butadiene—have been studied in a flow system using ESR spectrometry. Monomer and polymer radicals have been identified from their ESR spectra. fi-Coupling constants of vinyl ester radicals are low (12-13 gauss) and independent of temperature, tentatively indicating that the /3-CH2 group is locked with respect to the a-carbon group. In copolymerization studies, the low reactivity of vinyl acetate has been confirmed, and increasing reactivity for maleic acid, acrylic acid, acrylonitrile, and fumaric acid in this order has been established by quantitative evaluation of the ESR spectra. This method offers a new approach to studies of free radical polymerization. 

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