Vinylidene chloride, poly with acrylonitrile

Poly(vinyhdene chloride) (PVDC) film has exceUent barrier properties, among the best of the common films (see Barrier polymers). It is formulated and processed into a flexible film with cling and tacky properties that make it a useful wrap for leftovers and other household uses. As a component in coatings or laminates it provides barrier properties to other film stmctures. The vinyUdene chloride is copolymerized with vinyl chloride, alkyl acrylates, and acrylonitrile to get the optimum processibUity and end use properties (see Vinylidene chloride monomer and polymers). 

Copolymers of acrylonitrile and vinylidene chloride have been used for many years to produce films of low gas permeability, often as a coating on another material. Styrene-acrylonitrile with styrene as the predominant free monomer (SAN polymers) has also been available for a long time. In the 1970s materials were produced which aimed to provide a compromise between the very low gas permeability of poly(vinylidene chloride) and poly(acrylonitrile) with the processability of polystyrene or SAN polymers (discussed more fully in Chapter 16). These became known as nitrile resins. 

Dual lifetime referencing (DLR) is another powerful technique that enables referenced measurements in case of fluorescent indicators [23]. In this method, the analyte-dependent signal from an indicator is referenced against the signal from an inert luminophore. This can be realized in both the time domain [24] and in the frequency domain [25]. Often, a luminescent reference dye is embedded into gas blocking nanobeads to avoid oxygen quenching. Polymers with very low gas permeability such as poly(acrylonitrile) [24] or poly(vinylidene chloride-co-acry-lonitrile) [26] are the best choice here. 

Poly(vinylidene chloride) (XLII) and its copolymers with vinyl chloride, acrylonitrile, and acrylates, usually produced by the suspension or emulsion process, are useful as oil, fat, oxygen, and moisture-resistant packaging films (Saran wrap), containers, coatings, tank liners, and monofilaments in drapery fabrics and industrial filter cloths. 

Poly(vinylidene chloride-co-acrylonitrile) is widely used as a latex coating for cellophane, polyethylene and paper. Since this copolymer is soluble in organic solvents, it is also used as a solution coating. Tile resistance to vapor permeability and the ease of printing on polyethylene and cellophane is increased by coating with this vinylidene chloride copolymer. 

The DHI s may be solution cast with certain polymers. Examples of photochromic plastics prepared this way are poly (methyl methacrylate), poly (n-butyl methacrylate), copoly (vinylidene chloride-acrylonitrile) (e.g., SARAN F), polycarbonate, and polystyrene-butadiene (e.g., Panarez). 

Inverse gas chromatography, IGC, has been used to study water sorption of two poly (vinylidene chloride-vinyl chloride) and poly (vinylidene chloride-acrylonitrile) copolymers, at temperatures between 20 and 50°C and low water uptakes. It was found that the specific retention volume of water increases with decreasing amount of water injected, increases dramatically with decreasing temperature and strongly depends on the type of copolymer. Thermodynamic parameters of sorption namely free energy, entropy, enthalpy of sorption and activity coefficient were calculated. 

Four polymers with different surface compositions were used in this study—polystyrene (PS), poly(methyl methacrylate) (PMMA), polyacrylamide (PAM), and a poly(vinylidene chloride) (PVeC) copolymer (containing 20% polyacrylonitrile). Polystyrene has essentially a hydrocarbon surface, whereas the surfaces of poly (methyl methacrylate) and polyacrylamide contain ester and amide groups, respectively. The surface of the poly(vinylidene chloride) copolymer on the other hand will contain a relatively large number of chlorine atoms. The presence of acrylonitrile in the poly(vinylidene chloride) copolymer improved the solubility characteristics of the polymer for the purposes of this study, but did not appreciably alter, its critical surface tension of wetting. Values of y of these polymers ranged from 30 to 33 dynes per cm. for polystyrene to approximately 40 dynes per cm. for the poly(vinylidene chloride) copolymer. No attempt was made to determine e crystallinity of the polymer samples, or to correlate crystallinity with adsorption of the fluorocarbon additives. 

Surface oxidation reactions have been carried out on a number of polymers, particularly polyethylene. Surface oxidation techniques include the use of corona discharge, ozone, hydrogen peroxide, nitrous acid, alkaline hypochloride, UV irradiation, oxidizing flame, and chromic acid The reactions lead initially to the formation of hydroperoxides, which catalyze the formation of aldehydes and ketones and finally, acids and esters. Surface oxidation treatment has been used to increase the printabdity of polyethylene and poly(ethylene terephthalate) and to improve the adhesion of polyethylene and polypropylene to polar polymers and that of polytetrafluoroethylene to pressure-sensitive tapes. Surface-oxidized polyethylene, when coated with a thin film of vinylidene chloride, acrylonitrile, and acryhc acid terpolymers becomes impermeable to oxygen and more resistant to grease, oil, abrasion, and high temperatures. The greasy feel of polyethylene has also been removed by surface oxidation. 

Void-free fibers have been produced by incorporating hydrophilic comonomers, such as sulfonated monomers, acrylamide derivatives, and hydroxyalkyl acrylates [451]. Polymer blends are also effective in reducing macrovoids. Examples include blends of hydrophilic polymers such as polyvinyl methyl formamide [452], poly Ai-vinylpyrrolidone, and acryloni-trile-dimethylacrylamide copolymer [453,454]. Dense fibers can be produced by incorporating comonomers, such as vinylidene chloride, with small molar volumes relative to acrylonitrile. 

Poly(vinylidene chloride) (PVDC). The homopolymer is intractable in the conventional plastics processing techniques. For this reason, copolymers of vinylydene chloride with vinyl chloride or terpolymers with vinyl chloride and acrylonitrile are used. Due to its exceptionally low vapour, gas, and aroma permeability, PVDC films are used for packaging and for the barrier layer in composite films. Paper varnished by PVDC is a widespread packaging material. Trade names Diofan (FRG), Ixan (B), Saran (USA). 

Of critical importance, analysis of poly(methyl methacrylate) (PMMA) showed that at a saturation temperature, T, of 40°C, a saturation pressure, P%, of 1,500 psig (at these conditions, carbon dioxide is considered a supercritical fluid), and a saturation time, ts, of 24 h, a 1 mm thick disk absorbed 16.4 wt% carbon dioxide. Additionally, at a foaming temperature, Tf, of 120°C and a foaming time, tf, of 1 min, PMMA had a stable volumetric expansion ratio of 20. Other polymers also absorbed significant quantities of carbon dioxide, such as polystyrene (PS) and poly(vinylidene chloride-co-acrylonitrile) (P(VDC-AN)), which absorbed 8.9 and 2 wt% carbon dioxide, respectively, yet the stable foams that were formed had expansion ratios of less than 2 at the same conditions used to form the PMMA samples. Another polymer poly(vinyl methyl ketone) (PVMK) achieved an expansion ratio of 20. However, the foams were unstable, readily collapsed, and exhibited large voids ( 5 mm diameter), which are inconsistent with microcellular foams. The fact that PVMK readily collapsed after the foaming process made it difficult to determine the concentration of carbon dioxide in the sample. These results led to the eventual incorporation of the MMA monomer into the polymer formulation from the standpoint of carbon dioxide-induced microcellular foamability. 

The thermal degradation of poly(vinylidene chloride) and vinylidene chloride (VDC) copolymers usually occurs with the evolution of hydrogen chloride at elevated temperature. For the homopolymer, the degradation occurs rapidly when heated to its melting point, making it difficult to formulate through extrusion processes. As a consequence, only the copolymers with vinyl chloride, alkyl acrylate and acrylonitrile, etc., are of commercial... 

The observations of critical swelling in polymer-monomer systems was demonstrated by Ceresa, who used this method to synthesize many block copolymers, for example, poly(methyl methacrylate) with acrylonitrile, styrene, vinylidene chloride, or vinyl acetate polyethylene with methyl methacrylate or styrene and cellulose acetate with acrylonitrile [114, 168, 170-172]. For the last system, the critical change in swelling rate occurred after 40 min at a monomer uptake of 15%. Below this point no polymerization occurred (see Table 5.23 [114]). 

The content of acrylonitrile units in modacrylic fibres is, by definition, between 35 and 85 wt%. These fibres usually have a high concentration of halogen-containing comonomers (such as vinylidene dichloride, vinyl bromide and vinyl chloride) which improve their flame resistance. Related to modacrylic fibres, but with a higher content of halogen-containing monomers, are chlorofibres, produced only in small quantities from poly(vinyl chloride), poly(vinylidene dichloride) and from their copolymers, e.g. with vinyl acetate. ... 

---