Oxygen permeable copolymers

Copolymers of diallyl itaconate [2767-99-9] with AJ-vinylpyrrolidinone and styrene have been proposed as oxygen-permeable contact lenses (qv) (77). Reactivity ratios have been studied ia the copolymerization of diallyl tartrate (78). A lens of a high refractive iadex n- = 1.63) and a heat distortion above 280°C has been reported for diallyl 2,6-naphthalene dicarboxylate [51223-57-5] (79). Diallyl chlorendate [3232-62-0] polymerized ia the presence of di-/-butyl peroxide gives a lens with a refractive iadex of n = 1.57 (80). Hardness as high as Rockwell 150 is obtained by polymerization of triaHyl trimeUitate [2694-54-4] initiated by benzoyl peroxide (81). 

Fig. 4. Oxygen permeability in a vinylidene chloride copolymer film at selected levels of plasticizer (Citroflex A-4). Plasticizer level in parts pet hundred resin...

Cross-linked versions of water-soluble polymers swollen in aqueous media are broadly referred to as hydrogels (52) and have a growing commercial utility in such apphcations as oxygen-permeable soft contact lenses (qv) (53) (Table 4) and controUed-release pharmaceutical dmg deflvery devices (54). Cross-linked PVP and selected copolymers fit this definition and are of interest because of the following stmcture/performance characteristics ... 

Fig. 2. Oxygen permeabilities of ethylene—vinyl alcohol copolymers at 20°C (10). See Table 1 for unit conversions.

Fig. 15. Oxygen permeability versus 1/specific free volume at 25 °C (30). 1. Polybutadiene 2. polyethylene (density 0.922) 3. polycarbonate 4. polystyrene 5. styrene-acrylonitrile 6. poly(ethylene terephthalate) 7. acrylonitrile barrier polymer 8. poly(methyl methacrylate) 9. poly(vinyl chloride) 10. acrylonitrile barrier polymer 11. vinyUdene chloride copolymer 12. polymethacrylonitrile and 13. polyacrylonitrile. See Table 1 for unit conversions.

Certain copolymers of this type have been found to have excellent gas barrier properties, with the dry polymer having an oxygen permeability only about 1/lOth that of polyvinylidene chloride. Unsurprisingly, the copolymer has a high moisture absorption and a high moisture vapour transmission rate. Where the material is swollen by water, gas permeability is also higher. 

Commerical grades of EVOH typically have vinyl alcohol contents in the range 56-71%, but in contrast to the corresponding EVA materials these copolymers are crystalline. Furthermore, an increase in the vinyl alcohol content results in an increase in such properties as crystalline melting point, tensile strength and tensile modulus together with a decrease in oxygen permeability. This is a reflection of the fact that the ethylene and vinyl alcohol units in the chain are essentially isomorphous (see Sections 4.4 and 14.3.1). 

Polybutadiene (PB), 9 558 14 246 24 703 commercial block copolymers, 7 648t oxygen permeability at 25°C, 3 400 physical properties of, 4 376t in rubber compounding, 21 764-765 synthesis, 4 375-377 in tire compounding, 21 807 nel-Polybutadiene, 7 610t Polybutadiene-based urethane sealants, 22 36... 

Styrene markets, 23 345 Styrene - methacrylonitrile copolymers oxygen permeability of block and random, 3 386... 

Copolymers having enhanced oxygen permeability and water transport properties consisting of 3-methacryloxypropyltris(trimethyl-siloxy)silane, (V), and 2-methacryloyloxymethyl-18-crown-6, (VI), were prepared by Salamone et al. (6) and used as contact lenses. 

Vinylidene chloride polymers are more impermeable to a wider variety of gases and liquids than other polymers. For example, commercial copolymers are available with oxygen permeabilities of 0.03 nmol/m s-GPa. This is a consequence of the combination of high density and high crystallinity in the polymer. An increase m either tends to reduce permeability. Permeability is affected by the kind and amounts of comonomer as well as crystallinity. A more polar comonomer, e.g., an AN comonomer, increases the water-vapor transmission more than VC when other factors are constant. All VDC copolymers, are very impel meable to... 

The electron beam irradiation of poly(e-CL) and cross-linked PDXO in argon yielded a secondary alkyl ether radical and a tertiary alkyl radical, respectively. When the irradiation was carried out in an air atmosphere, peroxy radicals were detected in poly(e-CL) but not in PDXO (150). Oxygen permeabilities of poly(e-CL), and its tri-block copolymer poly(e-CL-b-PEG-b-e-CL) were in the range of 10 10 to 10 9 cm3 (STP) cm/cm2sec cm Hg [184]. 

The effect of plasticizers and temperature on the permeability of small molecules in a typical vinylidene chloride copolymer has been studied thoroughly. The oxygen permeability doubles with the addition of about 1.7 parts per hundred resin (phr) of common plasticizers, or a temperature increase of 8°C (91). The effects of temperature and plasticizer on the permeability are shown in Figure 4. The moisture (water) vapor transmission rate (MVTR or WVTR) doubles with the addition of about 3.5 phr of common plasticizers (92). The dependence of the WVTR on temperature is a litde more complicated. WVTR is commonly reported at a constant difference in relative humidity and not at a constant partial pressure difference. WVTR is a mixed term that increases with increasing temperature because both the fundamental permeability and the fundamental partial pressure at constant relative humidity increase. Carbon dioxide permeability doubles with the addition of about 1.8 phr of common plasticizers, or a temperature increase of 7°C (93). 

In addition to these materials, several others, such as polyurethanes, polysulfones, polyvinyl alcohol, and various copolymers, have been tried or are under development. Recently, silicon hydrogel lenses with high oxygen permeability were marketed. The future... 

Black copolymer 31 forms free standing films which are non-tacky and have good mechanical properties while maintaining oxygen permeability which is fairly close to that of 25 d. 

Figure 18.19. Predicted oxygen permeability of amorphous random copolymers of styrene and oxytrimethylene at room temperature, as a function of the composition.

Hydrolyzed ethylene—vinyl acetate copolymers [24937-78-8]> commonly known as ethylene—vinyl alcohol (EVOH) copolymers [25067-34-9], are usually used as extrusion resins, although some may be used in solvent-coating applications. As the ethylene fraction of these semicrystalline copolymers increases, the melting temperature decreases, the permeabilities increase, and the sensitivity to humidity decreases. The permeabilities as a function of polymer composition and humidity are shown in Figure 2. Vinyl alcohol homopolymer [9002-89-5] has a very low oxygen permeability in dry conditions however, the polymer is water-soluble. Trade names for these barrier polymers include Eval, Soamol, Selar OH, and Qarene. Table 6 lists the compositions... 

---