Methacrylate polymers, cross-linking

The most recent experimental work to settle the controversy regarding the factor B is the swelling pressure work of Van de Kraats (105,106). This author used poly( >-nitrophenyl methacrylate) gels, cross-linked in solution by aminolysis with hexamethylene diamine. A typical example of his results is shown in Fig. 14, where it is seen that % is a constant over a range in polymer concentration from 5 to 20%. 

Ghazaly, H. M., E. S. Daniels, V. L. Dimonie, A. Klein, and M. S. El-Aasser, Miniemulsion copolymerization of n-butyl methacrylate with cross-linking monomers. J. Appl. Polym. Sci. 81 (2001) 1721-1730. 

The temperature dependence of the relaxation activation energy of hydroxy-terminated polybutadiene-methyl methacrylate AB cross-linked polymer in the glass transition region is shown in Figure 4.8. The parameters C, = 8.77 °C, C2 = 85.07 °C and = 340 K were measured by means of the dynamic mechanical spectra 381 K was chosen as the reference temperature Tq. 

Figure 4.8 Relaxation activation energy of hydroxy-terminated polybutadicne-methyl methacrylate AB cross-linked polymer in the gla.ss transition region as a function of temperature (Tj. = 340 K, T = 380 K) [141...

Fig. 5-2. Molecular structures of some of the most commonly used polymer systems. (A) Polystyrene, a copolymer of styrene and divinylbenzene, (B) polyacrylamide, a copolymer of acrylamide and methylenebisacrylamide, (C) HEMA, a copolymer of ethylene glycol methacrylate and bisethylene glycol methacrylate, (D) cross-linked dextran, (E) agarose, (F) cellulose.

Anaerobic stmctural adhesives are typically formulated from acryhc monomers such as methyl methacrylate [80-62-6] C Hg02, and methacrylic acid [79-41-4] (see Acrylic ester polymers). Very often, cross-linking agents such as dimethacrylates are also added. A peroxide, such as cumene... 

Other Polymers. Besides polycarbonates, poly(methyl methacrylate)s, cycfic polyolefins, and uv-curable cross-linked polymers, a host of other polymers have been examined for their suitabiUty as substrate materials for optical data storage, preferably compact disks, in the last years. These polymers have not gained commercial importance polystyrene (PS), poly(vinyl chloride) (PVC), cellulose acetobutyrate (CAB), bis(diallylpolycarbonate) (BDPC), poly(ethylene terephthalate) (PET), styrene—acrylonitrile copolymers (SAN), poly(vinyl acetate) (PVAC), and for substrates with high resistance to heat softening, polysulfones (PSU) and polyimides (PI). 

Fig. 26. Qualitative compatison of substrate materials for optical disks (187) An = birefringence IS = impact strength BM = bending modulus HDT = heat distortion temperature Met = metallizability WA = water absorption Proc = processibility. The materials are bisphenol A—polycarbonate (BPA-PC), copolymer (20 80) of BPA-PC and trimethylcyclohexane—polycarbonate (TMC-PC), poly(methyl methacrylate) (PMMA), uv-curable cross-linked polymer (uv-DM), cycHc polyolefins (CPO), and, for comparison, glass.

Organic peroxides are used in the polymer industry as thermal sources of free radicals. They are used primarily to initiate the polymerisation and copolymerisation of vinyl and diene monomers, eg, ethylene, vinyl chloride, styrene, acryUc acid and esters, methacrylic acid and esters, vinyl acetate, acrylonitrile, and butadiene (see Initiators). They ate also used to cute or cross-link resins, eg, unsaturated polyester—styrene blends, thermoplastics such as polyethylene, elastomers such as ethylene—propylene copolymers and terpolymers and ethylene—vinyl acetate copolymer, and mbbets such as siUcone mbbet and styrene-butadiene mbbet. 

Poly(methyl methacrylate) and poly(vinyl acetate) precipitate from the resin solution as it cures. This mechanism offsets the contraction in volume as the polyester resin cross-links, resulting in a nonshrinking thermoset. Other polymer additives such as poly(butylene adipate) provide similar shrinkage... 

Interpenetrating networks of DMPPO and polymers such as polystyrene, polybutadiene, poly(urethane acrylate), and poly(methyl methacrylate) have been prepared by cross-linking solutions of DMPPO containing bromomethyl groups with ethylenediamine in the presence of the other polymer (68). 

Hydrogels, ie, gelatin and agar, have been known for a long time. In the late nineteenth century, Herschel proposed the use of jelly materials on the cornea for the correction of vision (108). In 1960, the use of synthetic hydrogels for contact lenses was proposed and several U.S. patents were obtained for the invention of cross-linked hydrophilic polymers, eg, systems based on 2-hydroxethyl methacrylate [868-77-9] (HEMA) (5) (109—112). 

Third Monomers. In order to achieve certain property improvements, nitrile mbber producers add a third monomer to the emulsion polymerization process. When methacrylic acid is added to the polymer stmcture, a carboxylated nitrile mbber with greatly enhanced abrasion properties is achieved (9). Carboxylated nitrile mbber carries the ASTM designation of XNBR. Cross-linking monomers, eg, divinylbenzene or ethylene glycol dimethacrylate, produce precross-linked mbbers with low nerve and die swell. To avoid extraction losses of antioxidant as a result of contact with fluids duriag service, grades of NBR are available that have utilized a special third monomer that contains an antioxidant moiety (10). FiaaHy, terpolymers prepared from 1,3-butadiene, acrylonitrile, and isoprene are also commercially available. 

Other developments in recent years have been the appearance of tough and heat-resistant materials closely related to poly(methyl methacrylate) and to interesting cross-linked polymers. Amongst these are the so-called hydrophilic polymers used in the making of soft contact lenses. 

Beaded methacrylate polymers, poly(hydroxyethylmethacrylate), Spheron, Separon (29), and poly(glycidylmethacrylate), Eupergin (30,31), are studied extensively at the Czechoslovak Academy of Macromolecular Sciences. An addition to this type of support is poly(oxyethylene-dimethacrylate) (32). Heitz et al. (33) described the preparation of beaded poly(methylacrylates) cross-linked with ethanedimethacrylates. 

For the classical form of size exclusion chromatography in organic solvents, packings based on highly cross-linked styrene-divinylbenzene are used. For SEC of polar polymers using polar or aqueous solvents, packings based on a polar methacrylate polymer are used. Diol-derivatized silica is used for the separation of proteins and other polar polymers. The different packings will be discussed in sections dedicated to their different application areas. 

When the polymer was prepared by the suspension polymerization technique, the product was crosslinked beads of unusually uniform size (see Fig. 16 for SEM picture of the beads) with hydrophobic surface characteristics. This shows that cardanyl acrylate/methacry-late can be used as comonomers-cum-cross-linking agents in vinyl polymerizations. This further gives rise to more opportunities to prepare polymer supports for synthesis particularly for experiments in solid-state peptide synthesis. Polymer supports based on activated acrylates have recently been reported to be useful in supported organic reactions, metal ion separation, etc. [198,199]. Copolymers are expected to give better performance and, hence, coplymers of CA and CM A with methyl methacrylate (MMA), styrene (St), and acrylonitrile (AN) were prepared and characterized [196,197]. 

The furfuryl esters of acrylic and methacrylic acid polymerize via a free-radical mechanism without apparent retardation problems arising from the presence of the furan ring. Early reports on these systems described hard insoluble polymers formed in bulk polymerizations and the cross-linking ability of as little as 2% of furfuryl acrylate in the solution polymerization of methylacrylate121. ... 

---