Graft copolymers methacrylate /styrene

Figure 9.17 Plot of log [i ]M versus retention volume for various polymers, showing how different systems are represented by a single calibration curve when data are represented in this manner. The polymers used include linear and branched polystyrene, poly(methyl methacrylate), poly(vinyl chloride), poly(phenyl siloxane), polybutadiene, and branched, block, and graft copolymers of styrene and methyl methacrylate. [From Z. Grubisec, P. Rempp, and H. Benoit, Polym. Lett. 5 753 (1967), used with permission of Wiley.]...

A series of polymine-graft copolymers of styrene [92-95] and hydroxyethyl methacrylate [96-98] were found to form a microdomain structure and exhibit unique biomedical behavior at the interface with living cells, such as blood platelets and lymphocytes. The most intensive studies were made with poly(hydroxyethyl methacryIate)-0ra/t-polyamine copolymers (HA) ... 

Jones, M. H. Graft copolymers of styrene and methyl methacrylate. I. Synthesis. Canad. J. Chem. 34, 948 (1956). 

In 1992, low-gloss, moldable blends, with electrostatic discharge properties were developed. They comprised PC, ABS, and either a graft copolymer of styrene, hydroxyethyl methacrylate, and... 

Y. Amagi, M. Ohya, Z. Shiiki, and H. Yusa, PVC Blended with Cross-linked Graft Copolymers of Styrene and Methyl Methacrylate onto a Butadiene Polymer, U.S. Pat. 3,775,514 (1973). MBS resins in latex form. Triple IPN in latex form. Clear, impact-resistant PVC. 

PVC blended with BR-grafted-(methyl methacrylate)-styrene copolymer PVC MBS... 

Fig. 3.26 Universal calibration curve for crosslinked polystyrene gels with tetrahydrofuran as solvent %y linear polystyrene 0 branched polystyrene (comb type) +, branched polystyrene (star type) A, branched block copolymer of styrene methyl methacrylate x, poly (methyl methacrylate) poly (vinyl chloride) V, graft copolymer of styrene methyl methacrylate , polybutadiene (reprinted with permission from Comprehensive Polymer Science, copyright 1989, Pergammon Press pic).

A waterborne system for container coatings was developed based on a graft copolymerization of an advanced epoxy resin and an acryHc (52). The acryhc-vinyl monomers are grafted onto preformed epoxy resins in the presence of a free-radical initiator grafting occurs mainly at the methylene group of the aHphatic backbone on the epoxy resin. The polymeric product is a mixture of methacrylic acid—styrene copolymer, soHd epoxy resin, and graft copolymer of the unsaturated monomers onto the epoxy resin backbone. It is dispersible in water upon neutralization with an amine before cure with an amino—formaldehyde resin. 

At one time butadiene-acrylonitrile copolymers (nitrile rubbers) were the most important impact modifiers. Today they have been largely replaced by acrylonitrile-butadiene-styrene (ABS) graft terpolymers, methacrylate-buta-diene-styrene (MBS) terpolymers, chlorinated polyethylene, EVA-PVC graft polymers and some poly acrylates. 

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]. 

Recently it has been shown that anionic functionalization techniques can be applied to the synthesis of macromonomers — macromolecular monomers — i.e. linear polymers fitted at chain end with a polymerizable unsaturation, most commonly styrene or methacrylic ester 69 71). These species in turn provide easy access to graft copolymers upon radical copolymerization with vinylic or acrylic monomers. 

The same procedure can be employed to make well defined comb-like polymers Living polystyrene can be grafted onto a partially chloromethylated polystyrene89 146), or onto a random copolymer of styrene and methyl methacrylate containing less than 10% of the latter monomer I48). 

II. B polyethylene glycol, ethylene oxide, polystyrene, diisocyanates (urethanes), polyvinylchloride, chloroprene, THF, diglycolide, dilac-tide, <5-valerolactone, substituted e-caprolactones, 4-vinyl anisole, styrene, methyl methacrylate, and vinyl acetate. In addition to these species, many copolymers have been prepared from oligomers of PCL. In particular, a variety of polyester-urethanes have been synthesized from hydroxy-terminated PCL, some of which have achieved commercial status (9). Graft copolymers with acrylic acid, acrylonitrile, and styrene have been prepared using PCL as the backbone polymer (60). 

In our own research, the functional termination of the living siloxanolate with a chlorosilane functional methacrylate leading to siloxane macromonomers with number average molecular weights from 1000 to 20,000 g/mole has been emphasized. Methacrylic and styrenic monomers were then copolymerized with these macromonomers to produce graft copolymers where the styrenic or acrylic monomers comprise the backbone, and the siloxane chains are pendant as grafts as depicted in Scheme 1. Copolymers were prepared with siloxane contents from 5 to 50 weight percent. 

MBS (methyl methacrylate-butadiene-styrene) graft copolymers are known as one of the most efficient non-reactive impact modifiers for PET and also poly(vinyl chloride) (PVC). MBS is used commercially as an effective impact modifier for PET recyclate [27], Typical MBS rubber particles contain an elastomeric core of... 

MBS (poly(methyl methacrylate)-g-poly(butadiene/styrene) graft copolymer) Paraloid EXL Rohm Haas... 

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). 

The idea of the preparation of porous polymers from high internal phase emulsions had been reported prior to the publication of the PolyHIPE patent [128]. About twenty years previously, Bartl and von Bonin [148,149] described the polymerisation of water-insoluble vinyl monomers, such as styrene and methyl methacrylate, in w/o HIPEs, stabilised by styrene-ethyleneoxide graft copolymers. In this way, HIPEs of approximately 85% internal phase volume could be prepared. On polymerisation, solid, closed-cell monolithic polymers were obtained. Similarly, Riess and coworkers [150] had described the preparation of closed-cell porous polystyrene from HIPEs of water in styrene, stabilised by poly(styrene-ethyleneoxide) block copolymer surfactants, with internal phase volumes of up to 80%. 

Graft copolymers of polyamides using pre-irradiation gamma-rays techniques have been reported for styrene (130), in solution, in the presence of water (40), in alcohols or acetone solution (131), vinyl acetate (130), methacrylic acid in water (132) or methanol solution (129), methyl (133) and ethyl (130) acrylates, 2-ethylhexyl acrylate (55,134), methyl methacrylate (130), in methanol solution (129), 2-dimethylamino ethyl methacrylate quaternary salts (135), acrylamide in aqueous medium (128,136), acrylonitrile (130,137), and 4-vinyl pyridine in aqueous solution (128). 

The composition of the grafted side chain copolymer has also been determined by Sakurada (113) and found to be different from the normal copolymer formed with acrylonitrile and butadiene. With styrene the grafted copolymers were found to be richer in acrylonitrile than the normal copolymer. Similar differences were found by Resting (114) with methyl methacrylate and styrene grafted to cotton and by Odian et al. (115) with grafting mixed monomers to Teflon and to polyethylene. It is believed that one monomer may be preferentially sorbed or diffused faster than the other, leading to a different monomer ratio at the actual site of grafting. 

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