Copolymers defining

Fig. 7. Data of Parsonage et al. [77] on the adsorption of a series of block copolymers of polystyrene-poly-2-vinylpyridine. The ordinate is the measured surface density ( d 2) reduced by the density required for the nonadsorbing chains to overlap the abscissa is the solvent-enhanced size asymmetry of the block copolymer defined under Eq. 26. The form of this plot is that suggested by Eq. 28...

Copolymers may be described as alternating copolymers, block copolymers or graft copolymers. The molecular architecture of copolymers may, however, be more complicated than represented in Fig. 8.1. Homopolymers can be linear, star or branched (Fig. 8.2), giving rise to so-called star block copolymers defined by the number of arms (n). 

Concerning EO/PO random copolymers, defining the composition in all the possible situations is necessary to know the reactivity of both primary and secondary hydroxyls with EO and PO, as already mentioned. 

Alternatively, one can measure the volume fraction of the chains that participate in aggregates, using a set of simulations performed at various (p. This volume fraction of the aggregates is then extrapolated to zero, and the value of

critical micelle concentration [35]. When simulations are performed with the only nonzero energies being Eab = Sas = ffi critical micelle concentration of the ABA triblock copolymers defined by this latter approach is found to obey a power law of the form... 

The differences in the IR and Raman spectra of random copolymers, block copolymers, and polymer mixtures, A and B , will be covered in a moment. It should be appreciated that it is difficult to distinguish between polymer mixtures of the form A - - B and block copolymers defined as A -B from either IR or Raman spectra, because the chemical bonding between species A and B is only one of many bonds within a polymer chain. Column chromatographic separation followed by IR or Raman spectral identification or a GPC-IR method [16] is needed to determine whether a sample is a block copolymer or a mixture. In the case of a random copolymer in which component B is very small, B is mixed into the A A chain sequence in the form -A -B-A ,-. While the IR and Raman spectra of the A sequences may stay essentially the same as the A homopolymer, the spectra of B in an... 

In a dilute solution in a common good solvent for both blocks, the interactions between. different copolymers may be studied using the same direct renormalization procedures as the interactions between two homopolymers A and B equivalent to the two blocks.As for blends, in the asymptotic limit of infinite molecular masses, the chemical difference between the two blocks is irrelevant and the dimensionless virial coefficient gc between block copolymers defined by Eq. (10) is equal to the same value g as for homopolymers. The interactions which may provoke the formation of mesophases are here again due to the corrections to the scaling behavior ... 

Stockmayer and Kennedy (1975) constructed generalized plots showing how the block length ratio 6 and terminal relaxation times Tj and Tjg of the respective constituent components may affect the reduced zero-shear viscosity F of a block copolymer, defined by... 

The parameters rj and T2 are the vehicles by which the nature of the reactants enter the copolymer composition equation. We shall call these radical reactivity ratios, although similarly defined ratios also describe copolymerizations that involve ionic intermediates. There are several important things to note about radical reactivity ratios ... 

Figure 7.2 The product rii2 for copolymers whose components define the intersection where the numbers appear. See the text for details of placement. The value marked is determined in Example 7.5. Other values are from Ref. 4.

A similar logic can be applied to copolymers. The story is a bit more complicated to tell, so we only outline the method. If penultimate effects operate, then the probabilities Ph, Pi2> and so on, defined by Eqs. (7.32)-(7.35) should be replaced by conditional probabilities. As a matter of fact, the kind of conditional probabilities needed must be based on the two preceding events. Thus reactions (7.E) and (7.F) are two of the appropriate reactions, and the corresponding probabilities are Pj n and V i2 - Rather than work out all of the possibilities in detail, we summarize the penultimate model as follows ... 

If we define p and Pj. as the probability of addition occurring in the meso and racemic modes, respectively, then p Pr since there are only two possibilities. The probability p is the analog of Pjj for copolymers hence, by analogy with Eq. (7.30), this equals the fraction of isotactic dyads among all dyads. In terms of the kinetic approach of the last section, p is equal to the rate of an iso addition divided by the combined rates of iso and syndio additions ... 

A mechanism in which the stereochemistry of the growing chain does exert an influence on the addition might exist, but at least two repeat units in the chain are required to define any such stereochemistry. Therefore this possibility is equivalent to the penultimate mechanism in copolymers. In this case the addition would be described in terms of conditional probabilities, just as Eq. (7.49) does for copolymers. Thus the probability of an isotactic triad controlled by the stereochemistry of the growing chain would be represented by the reaction... 

In this equation the summations are over all values of n of the specified type. Also remember that the r s and n s in this discussion (with subscript i or s) are defined differently from the p s and n s defined earlier in the chapter for copolymers (where they had subscript 1 or 2). Using Eq. (7.71) and remembering... 

The properties of these new materials are being studied. Hydroboration is also appHed for the conversion of double bonds in polymers into hydroxyl groups (450—454). Well-defined copolymers of ethylene—vinyl alcohol can be prepared (455). 

High density polyethylene (HDPE) is defined by ASTM D1248-84 as a product of ethylene polymerisation with a density of 0.940 g/cm or higher. This range includes both homopolymers of ethylene and its copolymers with small amounts of a-olefins. The first commercial processes for HDPE manufacture were developed in the early 1950s and utilised a variety of transition-metal polymerisation catalysts based on molybdenum (1), chromium (2,3), and titanium (4). Commercial production of HDPE was started in 1956 in the United States by Phillips Petroleum Company and in Europe by Hoechst (5). HDPE is one of the largest volume commodity plastics produced in the world, with a worldwide capacity in 1994 of over 14 x 10 t/yr and a 32% share of the total polyethylene production. 

A number of high melting poiat semiaromatic nylons, iatroduced ia the 1990s, have lower moisture absorption and iacreased stiffness and strength. Apart from nylon-6 /6,T (copolymer of 6 and 6,T), the exact stmcture of these is usually proprietary and they are identified by trade names. Examples iaclude Zytel HTN (Du Pont) Amodel, referred to as polyphthalamide or PPA (Amoco) and Aden (Mitsui Petrochemical). Properties for polyphthalamide are given ia Table 2. A polyphthalamide has been defined by ASTM as "a polyamide ia which the residues of terephthaUc acid or isophthahc acid or a combination of the two comprise at least 60 molar percent of the dicarboxyhc acid portion of the repeating stmctural units ia the polymer chain" (18). 

The search for new, high performance materials requites the synthesis of weU-defined, narrow molecular weight distribution, cycHc-free, homo- and copolymers. Synthesis of these polymers can be accompHshed by the kinetically controUed polymerization of the strained monomer. 

A living cationic polymeriza tion of isobutylene and copolymeriza tion of isobutylene and isoprene has been demonstrated (22,23). Living copolymerizations, which proceed in the absence of chain transfer and termination reactions, yield the random copolymer with narrow mol wt distribution and well-defined stmcture, and possibly at a higher polymerization temperature than the current commercial process. The isobutylene—isoprene copolymers are prepared by using cumyl acetate BCl complex in CH Cl or CH2CI2 at —30 C. The copolymer contains 1 8 mol % trans 1,4-isoprene... 

Rubbery materials are defined by ASTM (D1566) as those which will have less than 50% permanent set after one minute when recovering from a strain of 100% applied for one minute. Of the many rubbery materials available, block copolymers are by far the most common used in hot melts. 

In a somewhat wider sense, one can define amphiphiles as molecules in which chemically very different units are linked together. For example, the structures formed by A B block copolymers in demixed A and/or B homopolymer melts and their phase behavior are very similar to those of classical amphiphiles in water and/or oil [13,14]. Copolymers are used not only to disperse immiscible homopolymer phases in one another, but also to create new, mesoscopically structured materials with unusual and interesting properties [15]. 

There has been a conventional sense that the PVAc latexes prepared in the presence of PVA as a protective colloid contain the graft copolymer of PVA and PVAc, so that PVAc particles in the dried latex film are not extracted at a high ratio with solvents. In this Chapter, it has been defined without an influence by the usual sense that the porous PVA-PVAc composite can be prepared from the PVAc latex film with acetone extraction. The porous film consists of the spherical cells of PVA... 

The block copolymer produced by Bamford s metal carbonyl/halide-terminated polymers photoinitiating systems are, therefore, more versatile than those based on anionic polymerization, since a wide range of monomers may be incorporated into the block. Although the mean block length is controllable through the parameters that normally determine the mean kinetic chain length in a free radical polymerization, the molecular weight distributions are, of course, much broader than with ionic polymerization and the polymers are, therefore, less well defined,... 

Several different types of copolymers can be defined, depending on the distribution of monomer units in the chain. If monomer A is copolymerized with monomer B, for instance, the resultant product might have a random... 

Figure 16 1. Schematic representation of copolymers with well-defined conjugation length A is a conjugated chromophorc, B is an interruption unit (a) alternating copolymer (b) polymer with slereo-chcmically defined non-coplanar linkages.

The existence of an azeotropic composition has some practical significance. By conducting a polymerization with the monomer feed ratio equal to the azeotropic composition, a high conversion batch copolymer can be prepared that has no compositional heterogeneity caused by drift in copolymer composition with conversion. Thus, the complex incremental addition protocols that arc otherwise required to achieve this end, are unnecessary. Composition equations and conditions for azeotropic compositions in ternary and quaternary eopolymerizations have also been defined.211,21... 

The multifunctional initiators may be di- and tri-, azo- or peroxy-compounds of defined structure (c.g. 20256) or they may be polymeric azo- or peroxy-compounds where the radical generating functions may be present as side chains 57 or as part of the polymer backbone."58"261 Thus, amphiphilic block copolymers were synthesized using the polymeric initiator 21 formed from the reaction between an a,to-diol and AIBN (Scheme 7.22).26 Some further examples of multifunctional initiators were mentioned in Section 3.3.3.2. It is also possible to produce less well-defined multifunctional initiators containing peroxide functionality from a polymer substrate by autoxidalion or by ozonolysis.-0... 

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