Polyacrylonitrile cross-linking

Combination techniques such as microscopy—ftir and pyrolysis—ir have helped solve some particularly difficult separations and complex identifications. Microscopy—ftir has been used to determine the composition of copolymer fibers (22) polyacrylonitrile, methyl acrylate, and a dye-receptive organic sulfonate trimer have been identified in acryHc fiber. Both normal and grazing angle modes can be used to identify components (23). Pyrolysis—ir has been used to study polymer decomposition (24) and to determine the degree of cross-linking of sulfonated divinylbenzene—styrene copolymer (25) and ethylene or propylene levels and ratios in ethylene—propylene copolymers (26). 

Secondary bonds are considerably weaker than the primary covalent bonds. When a linear or branched polymer is heated, the dissociation energies of the secondary bonds are exceeded long before the primary covalent bonds are broken, freeing up the individual chains to flow under stress. When the material is cooled, the secondary bonds reform. Thus, linear and branched polymers are generally thermoplastic. On the other hand, cross-links contain primary covalent bonds like those that bond the atoms in the main chains. When a cross-linked polymer is heated sufficiently, these primary covalent bonds fail randomly, and the material degrades. Therefore, cross-linked polymers are thermosets. There are a few exceptions such as cellulose and polyacrylonitrile. Though linear, these polymers are not thermoplastic because the extensive secondary bonds make up for in quantity what they lack in quahty. 

The commercial appearance of phenolic resins fibres in 1969 is, at first consideration, one of the more unlikelier developments in polymer technology. By their very nature the phenolic resins are amorphous whilst the capability of crystallisation is commonly taken as a prerequisite of an organic polymer. Crystallisability is not, however, essential with all fibres. Glass fibre, carbon fibre and even polyacrylonitrile fibres do not show conventional crystallinity. Strength is obtained via other mechanisms. In the case of phenolic resins it is obtained by cross-linking. 

In another report polyphosphazene copolymers were synthesized from bis (2-methylphenoxy) phosphazene, which was sulfonated after polymerization. Polymers such as polyvinylidene fluoride, polyhexa-fluoropropylene, and polyacrylonitrile were used to produce a blended membrane system. Polymer blends, cross-linking, and other means of re-enforcement are... 

PBDEs are used in different resins, polymers, and substrates at levels ranging from 5 to 30% by weight (EU 2001). Plastic materials that utilize PBDEs as flame retardants include ABS polyacrylonitrile (PAN) polyamide(PA) polybutylene terephthalate (PBT) polyethylene (PE) cross-linked polyethylene (XPE) polyethylene terephthalate (PET) polypropylene (PP) polystyrene (PS) high-impact polystyrene (HIPS) polyvinyl chloride (PVC) polyurethane (PUR) and unsaturated polyester (UPE). These polymers and examples of their final products are summarized inTable 5-2 (Hardy 2002 WHO 1994a). 

ABS = Acrylonitrile Butadene Styrene PA = Polyamide PAN = Polyacrylonitrile PBT = Polybbutylene Terephthalate PE= Polyethylene PET = Polyethylene Terephthalate PP = Polypropylene PUR = Polyirethane PVC = Polyvinyl chloride UPE = Un saturated polyester XPE = Cross-linked polyethylene ... 

Superabsorbent polymers are now commonly made from the polymerization of acrylic acid blended with sodium hydroxide in the presence of an initiator to form a polyacrylic acid, sodium salt (sometimes referred to as cross-linked sodium polyacrylate). Some of the polymers include polyacrylamide copolymer, ethylene maleic anhydride copolymer, cross-linked carboxy-methyl-cellulose, polyvinyl alcohol copolymers, cross-linked polyethylene oxide, and starch grafted copolymer of polyacrylonitrile to name a few. The latter is one of the oldest SAP forms created. 

Cross-linking Polyacrylonitrile, poly(oxy-m-xylene) Char (and HCN), char... 

Polyacrylonitrile (PAN) is the most common precursor used to make carbon fibers. A flow diagram showing the steps involved in making PAN-based carbon fiber is shown in Fig. 8.3. The PAN precursor has a flexible polymer chain structure like any other polymer, but it has an all carbon backbone chain that contains polar nitrile groups, as shown in Fig. 8.4. During the stabilization treatment, the PAN precursor fiber is heated to 200-220 C, under tension. When this is done oxygen is absorbed, and it serves to cross-link the chains the fibers turn black, and a stable ladder structure is formed. A ladder polymer is a rigid... 

The first direct evidence for second-order nonlinearity in partially cross-linked polyacrylonitrile is reported. The crosslinking in y-ray-induced polymerized neat acrylonitrile is supported by CPMAS solid-state NMR. Poly(dimethylsiloxane) and polyacrylonitrile have been observed to form inclusion complexes (ICs) with y-cyclodextrin. CP-MAS C-NMR spectra of... 

A membrane designated "Solrox" made by Sumitomo Chemical Company is closely related to the above plasma polymerized composite membranes. A 1980 report by T. Sano described the Sumitomo process (31). A support film was cast from a polyacrylonitrile copolymer containing at least 40 mole percent acrylonitrile. The support film was dried and exposed to a helium or hydrogen plasma to form a tight cross-linked surface skin on the porous polyacrylonitrile support film. Data in a U.S. Patent issued in 1979 to Sano et al showed that the unmodified support film had a water flux of 87 gfd (145 L/ sq m/hr) at 142 psi (10 kg/sq cm). After the plasma treatment a reverse osmosis test using 0.55 percent NaCl at 710 psi (4895 kPa) showed 10.5 gfd (17.5 L/sq m/hr) flux at 98.3 percent salt rejection (32). This membrane appears to fall between a conventional asymmetric membrane and a composite membrane. If the surface skin is only cross-linked, one might call it a modified asymmetric membrane. However, if the surface skin is substantially modified chemically to make it distinct from the bulk of the membrane it could be considered as a composite type. 

Previous work has shown that gels formed from cross-linked polyacrylamide (6), alginate (6), hydrolyzed starch-polyacrylonitrile (7), and a cross-linked poly(acrylic acid) (8), consist of discontinuous structures with microregions of extremely low viscosity. Such microscopic heterogeneity has been attributed to permanent or diffusing fluctuations within the gel (i) or to a structure of closely packed, swollen microgels in a continuous water phase (2, 3). 

Ethylene, vinyl acetate, and acrylonitrile are polymerized in this way. The redox initiated polymerization of acrylonitrile is an example of precipitation polymerization where the polyacrylonitrile formed is insoluble in water and separates as a powder. This can lead to undesirable side reactions known as popcorn polymerizations when tough cross-linked nodules of polymer grow rapidly and foul the feed lines in industrial plants. 

Scheme 7.15 Main-chain cleavage and cross-linking of polyacrylonitrile.

In the case of thermosets, deliberate and extensive orientation is virtually unknown. This appears to be the result of the practical difficulties involved, rather than from any theoretical obstacle. For example, it is possible that the fibre Kynol produced by the Carborundum Corporation is oriented to some extent. This is produced from a melt-spun Novolak phenol-formaldehyde resin, which is later further cross-linked with formaldehyde. It is, of course, legitimate to consider carbon fibres as extreme examples of thermosets. Formed by the cyclisation and subsequent graphitisation of polyacrylonitrile (or other suitable precursors), they are highly oriented. 

Investigation of ERC by dielectric and ultrasound methods [138] detected three relaxation transitions. The low-temperature transition (220-246 K at 10 -10 Hz) is related to the molecular mobility of the polyacrylonitrile butadiene. Relaxation transitions related to molecular mobility, either in the boundary layer between the rubber and the resin or in the regions of structure formed in the course of the cross-linking, correspond to higher temperatures. But, as this paper points out, the higher-temperature relaxation transitions do not appear in the frequency dependences. They can be detected only in the dependence of the modulus of elasticity on the temperature. 

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