Copolymer constant

CHEOPS is based on the method of atomic constants, which uses atom contributions and an anharmonic oscillator model. Unlike other similar programs, this allows the prediction of polymer network and copolymer properties. A list of 39 properties could be computed. These include permeability, solubility, thermodynamic, microscopic, physical and optical properties. It also predicts the temperature dependence of some of the properties. The program supports common organic functionality as well as halides. As, B, P, Pb, S, Si, and Sn. Files can be saved with individual structures or a database of structures. 

This copolymer has useful properties from cryogenic temperatures to 180°C. Its dielectric constant is low and stable over a broad temperature and frequency range. 

Figure 3.4 is a display of data which confirms the predictions of Eq. (3.46). For T and a constant-the case in these experiments—Eq. (3.46) predicts that a plot of Uj versus 1 /M should yield a straight line with an intercept proportional to 1/M(,. The elastomers on which the experiments were conducted were copolymers of isobutylene containing a small amount of isoprene. The polymers... 

The system combines having three components and having constant composition, since the copolymer has the same composition as the homopolymer... 

Increasing the copolymer content of the system lowers the Tg of both peaks, but the effect is far more pronounced for the peak associated with I. The latter is essentially constant in height, while the B peak diminishes in height with increasing copolymer. This suggests that the copolymer dissolves preferentially in the polyisoprene. 

In this section we have seen that the copolymer composition depends to a large extent on the four propagation constants, although it is sufficient to consider these in terms of the two ratios ri and r2. In the next section we shall examine these ratios in somewhat greater detail. 

The tendency toward alternation is not the only pattern in terms of which copolymerization can be discussed. The activities of radicals and monomers may also be examined as a source of insight into copolymer formation. The reactivity of radical 1 copolymerizing with monomer 2 is measured by the rate constant kj2. The absolute value of this constant can be determined from copolymerization data (rj) and studies yielding absolute homopolymerization constants (ku) ... 

Note that this inquiry into copolymer propagation rates also increases our understanding of the differences in free-radical homopolymerization rates. It will be recalled that in Sec. 6.1 a discussion of this aspect of homopolymerization was deferred until copolymerization was introduced. The trends under consideration enable us to make some sense out of the rate constants for propagation in free-radical homopolymerization as well. For example, in Table 6.4 we see that kp values at 60°C for vinyl acetate and styrene are 2300 and 165 liter mol sec respectively. The relative magnitude of these constants can be understod in terms of the sequence above. 

Equation (7.32) shows that pjj is constant for a particular copolymer if the terminal model applies therefore the ratio NmjMi/Nmi also equals this constant. Equation (7.49) shows that Pj u is constant for a particular copolymer if the penultimate model applies therefore the ratio NmiMiMi/NmiMi equals this constant, but the ratio NmjMj/Nmj does not have the same value. 

This situation can be generalized. If the ratios do not become constant until the ratio of pentads to tetrads is considered, then the unit before the next to last-called the antepenultimate unit-plays a role in the addition. This situation has been observed for propylene oxide-maleic anhydride copolymers. 

For a growing radical chain that has monomer 1 at its radical end, its rate constant for combination with monomer 1 is designated and with monomer 2, Similady, for a chain with monomer 2 at its growing end, the rate constant for combination with monomer 2 is / 22 with monomer 1, The reactivity ratios may be calculated from Price-Alfrey and e values, which are given in Table 8 for the more important acryUc esters (87). The sequence distributions of numerous acryUc copolymers have been determined experimentally utilizing nmr techniques (88,89). Several review articles discuss copolymerization (84,85). 

Monomer compositional drifts may also occur due to preferential solution of the styrene in the mbber phase or solution of the acrylonitrile in the aqueous phase (72). In emulsion systems, mbber particle size may also influence graft stmcture so that the number of graft chains per unit of mbber particle surface area tends to remain constant (73). Factors affecting the distribution (eg, core-sheU vs "wart-like" morphologies) of the grafted copolymer on the mbber particle surface have been studied in emulsion systems (74). Effects due to preferential solvation of the initiator by the polybutadiene have been described (75,76). 

Most commercial processes involve copolymerization of ethylene with the acid comonomer followed by partial neutralization, using appropriate metal compounds. The copolymerization step is best carried out in a weU-stirred autoclave with continuous feeds of all ingredients and the free-radical initiator, under substantially constant environment conditions (22—24). Owing to the relatively high reactivity of the acid comonomer, it is desirable to provide rapid end-over-end mixing, and the comonomer content of the feed is much lower than that of the copolymer product. Temperatures of 150—280°C and pressures well in excess of 100 MPa (1000 atm) are maintained. Modifications on the basic process described above have been described (25,26). When specific properties such as increased stiffness are required, nonrandom copolymers may be preferred. An additional comonomer, however, may be introduced to decrease crystallinity (10,27). 

Several parenteral microencapsulated products have been commercialized the cote materials ate polypeptides with hormonal activity. Poly(lactide— glycohde) copolymers ate the sheU materials used. The capsules ate produced by solvent evaporation, polymer-polymer phase separation, or spray-dry encapsulation processes. They release their cote material over a 30 day period in vivo, although not at a constant rate. 

Although the reaction rate of ethylene and various copolymers differs substantially, the reaction constants can be estabUshed by using an arbitrary value of 1 for ethylene (5). Thus, a value of 0.1 would indicate that the comonomer reacts at 10 times the rate of ethylene. However, the wide range of reaction rates can present problems not only in determining the comonomer content of the final product but also in producing a homogeneous product (4,6). 

A more polar comonomer, eg, an AN comonomer, increases the water-vapor transmission more than VC when other factors are constant. For the same reason, AN copolymers are more resistant to penetrants of low cohesive energy density. AH VDC copolymers, however, are very impermeable to ahphatic hydrocarbons. Comonomers that lower T and increase the free volume in the amorphous phase increase permeability more than the polar comonomers higher acrylates are an example. Plasticizers increase permeabiUty for similar reasons. 

The effect of plasticizers and temperature on the permeabiUty of small molecules in a typical vinyUdene chloride copolymer has been studied thoroughly. The oxygen permeabiUty 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 permeabiUty 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 Htde more comphcated. 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 permeabiUty and the fundamental partial pressure at constant relative humidity increase. Carbon dioxide permeabiUty doubles with the addition of about 1.8 phr of common plasticizers, or a temperature increase of 7°C (93). 

VEs do not readily enter into copolymerization by simple cationic polymerization techniques instead, they can be mixed randomly or in blocks with the aid of living polymerization methods. This is on account of the differences in reactivity, resulting in significant rate differentials. Consequendy, reactivity ratios must be taken into account if random copolymers, instead of mixtures of homopolymers, are to be obtained by standard cationic polymeriza tion (50,51). Table 5 illustrates this situation for butyl vinyl ether (BVE) copolymerized with other VEs. The rate constants of polymerization (kp) can differ by one or two orders of magnitude, resulting in homopolymerization of each monomer or incorporation of the faster monomer, followed by the slower (assuming no chain transfer). 

Using this equation, the approximate (T — T ) value required for a film of a thermoplastic copolymer to be dry-to-touch, ie, to have a viscosity of 10 mPa-s(=cP), can be estimated (3,4). The calculated (T — T ) for this viscosity is 54°C, which, for a film to be dry-to-touch at 25°C, corresponds to a T value of —29 "C. The calculated T necessary for block resistance at 1.4 kg/cm for two seconds and 25°C, ie, rj = 10 ° mPa(=cP), is 4°C. Because the universal constants in the WLF equation are only approximations, the T values are estimates of the T requited. However, if parameters such as the mass per area appHed for blocking were larger, the time longer, or the test temperature higher, the T of the coating would also have to be higher. 

In the Type II case, the copolymerization tends toward an alternating arrangement of monomer units. Curve II of Figure 1 shows an example of an alternating copolymer that has an azeotropic copolymer composition, ie, a copolymer composition equal to the monomer feed at a single monomer feed composition. This case is analogous to a constant Foiling mixture ia vapor—Hquid equihbria.T) III... 

In a copolymer of 33% acrylonitrile, the most common composition for commercial products, the butadiene occurs in the approximate ratio of 90% trans, 8% vinyl, and 2% cis. At higher acrylonitrile content the cis configuration disappears, and at lower levels it increases to about 5% the vinyl configuration remains approximately constant (6,7). Since actual compositions of commercial nitrile mbbers are between 15 and 50% acrylonitrile, they also vary somewhat in sequence distribution and in the content of the three isomeric butadiene configurations. 

The excellent low temperature properties of FZ have been iadicated ia Table 1. Modulus curves were obtained usiag dynamic mechanical spectroscopy to compare several elastomer types at a constant 75 durometer hardness. These curves iadicate the low temperature flexibiUty of FZ is similar to fluorosihcone and ia great contrast to that of a fluorocarbon elastomer (vinyUdene fluoride copolymer) (Fig. 3) (15). 

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