Copolymer Depiction

Lewis acid effects 435 1UPAC recommendations copolymer depiction 335 living polymerization 452 polymer structure 2... 

Fig. 4 Representation of the various types of internal organisation that may occur in micelles formed through co-assembly of charged block copolymers. Depicted are micelles with a corona consisting of two different neutral monomers (shown in blue and green) that are (a) mixed, (b) laterally segregated, (c) radially segregated, and (d) laterally and radially segregated. Both cen-trosymmetric micelles (a, c) and non-centrosymmetiic micelles (b, d) are depicted. The micelle with a laterally segregated corona is generally referred to as a Janus micelle (b). The micelle depicted in (c) is most commonly known as onion-like or core-shell-corona micelle. The micelle with a laterally and radially segregated corona (d) is usually called a patched micelle. Note that in the case of (c) and (d) the blue and the red/black chains may also switch position...

Fig. 48 Assembly of a lamellar-forming polypeptide-coil diblock copolymer depicting the main techniques employed in our studies. Small-angle X-ray scattering (SAXS) is employed for the domain spacing, d. C NMR and wide-angle X-ray scattering (WAXS) are employed to identify the type of the peptide secondary structure (a-helical in the schematic). WAXS is further employed to specify the lateral self-assembly of a-helices within the polypeptide domain (a hexagonal lattice is indicated). Dielectric spectroscopy (DS) and site-specific NMR techniques are employed for the dynamics. Furthermore, the most intense DS process provides the persistence length. Ip, of a-helical segments [181]...

Most of the polymers we have described so far are homopolymers, polymers made from a single monomer. But the variety and utility of chain-growth polymerization can sometimes be enhanced (as we have just seen with SBR synthetic rubber) by using mrjdures of monomers to give copolymers. Figure 14.2 summarizes some of the ways in which monomers can be arranged in homo- and copolymers. The copolymers depicted are limited to two different monomers (A and B) in principle, of course, the possibilities are unlimited. 

Figure 5.12 Schematical representation of the grafting-through polymerization approach to synthesize molecular brush copolymers depicting that the block brush...

Figire 32 Assembly of a lamellar-forming polypeptide-coil diblock copolymer depicting the main techniques employed in their charaaerization. Small-angle X-ray scattering (SAXS) is employed for the domain spacing, d... 

The properties of SAN resins depend on their acrylonittile content. Both melt viscosity and hardness increase with increasing acrylonittile level. Unnotched impact and flexural strengths depict dramatic maxima at ca 87.5 mol % (78 wt %) acrylonitrile (8). With increasing acrylonitrile content, copolymers show continuous improvements in barrier properties and chemical and uv resistance, but thermal stabiUty deteriorates (9). The glass-transition... 

Butyl Rubber. Butyl mbber was the first low unsaturation elastomer, and was developed ia the United States before World War II by the Standard Oil Co. (now Exxon Chemical). It is a copolymer of isobutylene and isoprene, with just enough of the latter to provide cross-linking sites for sulfur vulcanization. Its molecular stmcture is depicted ia Table 1. 

IUPAC recommendations suggest that a copolymer structure, in this case poly(methyl methacrylate-co-styrene) or copoly(methyl methacrylate/slyrene), should be represented as 1. The most substituted carbon of the configurational repeat unit should appear first. This same rule would apply to the copolymer segments shown in Section 7.1. However, as was mentioned in Chapter I, in this book, because of the focus on mechanism, we have adopted the more traditional depiction 2 which follows more readily from the polymerization mechanism. 

Polyelectrolytes are polymers having a multiplicity of ionizable groups. In solution, they dissociate into polyions (or macroions) and small ions of the opposite charge, known as counterions. The polyelectrolytes of interest in this book are those where the polyion is an anion and the counterions are cations. Some typical anionic polyelectrolytes are depicted in Figure 4.1. Of principal interest are the homopolymers of acrylic acid and its copolymers with e.g. itaconic and maleic adds. These are used in the zinc polycarboxylate cement of Smith (1968) and the glass-ionomer cement of Wilson Kent (1971). More recently, Wilson Ellis (1989) and Ellis Wilson (1990) have described cements based on polyphosphonic adds. 

In our own research, the functional termination of the living siloxanolate with a chlorosilane functional methacrylate leading to siloxane macromonomers with number average molecular weights from 1000 to 20,000 g/mole has been emphasized. Methacrylic and styrenic monomers were then copolymerized with these macromonomers to produce graft copolymers where the styrenic or acrylic monomers comprise the backbone, and the siloxane chains are pendant as grafts as depicted in Scheme 1. Copolymers were prepared with siloxane contents from 5 to 50 weight percent. 

Various substituted styrene-alkyl methacrylate block copolymers and all-acrylic block copolymers have been synthesized in a controlled fashion demonstrating predictable molecular weight and narrow molecular weight distributions. Table I depicts various poly (t-butylstyrene)-b-poly(t-butyl methacrylate) (PTBS-PTBMA) and poly(methyl methacrylate)-b-poly(t-butyl methacrylate) (PMMA-PTBMA) samples. In addition, all-acrylic block copolymers based on poly(2-ethylhexyl methacrylate)-b-poly(t-butyl methacrylate) have been recently synthesized and offer many unique possibilities due to the low glass transition temperature of PEHMA. In most cases, a range of 5-25 wt.% of alkyl methacrylate was incorporated into the block copolymer. This composition not only facilitated solubility during subsequent hydrolysis but also limited the maximum level of derived ionic functionality. 

In the past, ionomers have generally consisted of 10-12 mole percent of ions and it is our intention to be consistent with the corresponding random ionomers previously discussed in the literature. In addition to gel permeation chromatography (GPC), H and 3C NMR can readily be utilized to verify the relative amount of monomer successfully incorporated into the block copolymer. For example, the composition of a PMMA-PTBMA diblock can be verified by H NMR ratioing the methyl ester integration (3.5 ppm) to the t-butyl ester integration (1.36 ppm). Figure 1 depicts the t-butyl ster chemical shift which appears reproducibly at 1.J6 ppm. C or FTIR can be utilized in certain instances when H NMR chemical shifts overlap. For... 

The films were then thermally cycled at tOO, 200 and 300°C for an hour at each temperature in a forced air convection oven to complete the cyclization. The solution imidization procedure has been further described by Summers, et. al. (42,43). A representative structure for the poly(imide siloxane) copolymers is depicted in Figure 5. 

Weight average molecular weights of poly(HAMCL) with saturated or unsaturated pendent groups are relatively low, compared to Mw s of poly(HASCL), and in the range of 60,000 to 360,000 g mol as depicted in Table 2 [4,30,35,36]. Also for the poly(HAMCL) copolymers, the molecular weight distributions are unimodal. Their polydispersities are in the range of 1.6-2.4, which is narrower than the polydispersity of poly(3HB-co-3HV) copolymers, and close to the theoretical value of 2.0 for synthetic polycondensates such as chemically synthesized polyesters [54]. 

PLLA-b-PEO)3 star-block copolymers have been synthesized by a combination of ROP and post-polymerization reactions [152], as depicted in Scheme 76. Glycerol was employed for the synthesis of a 3-arm PLLA star... 

The morphologies of various copolymers composed of polyethylene oxide), PEO, and poly (1,2-butylene oxide), PBut, were recently reviewed by Ryan et al. [61]. The corresponding phase diagrams of PEO-fr-PBut, PBut-fo-PEO-fo-PBut and PEO-fo-PBut-fo-PEO melts are depicted in Fig. 11. In all phase diagrams the semi-crystalline lamellar phase was not attained because of the copolymers low melting points. 

Fig. 34 Illustration of A B miktoarm star-block copolymer, a AB4 diblock copolymer with A arm depicted by dashed line and B arms depicted by solid lines. b AB interfaces for A15 phase shown in Pm 3 n unit cell (extracted from SCFT results for n = 5 at yN = 40 and tfi = 0.349 [along Hex-Al5 phase boundary] vide infra). From [112]. Copyright 2004 American Chemical Society, c A B miktoarm-star block copolymer with n = 4. From [121]. Copyright 2003 American Chemical Society... 

The phase behaviour of a blend of two PS-fo-PI copolymers depending on the components molecular weight and their ratio was investigated by Yamaguchi et al. [178-181]. Both copolymers were of nearly symmetric composition however, they differed in their molecular weights. For a given molecular weight ratio of the two constituent PS-fo-PIs the parameter space of temperature and blend composition is depicted in Fig. 59. 

Finally, we have designed and synthesized a series of block copolymer surfactants for C02 applications. It was anticipated that these materials would self-assemble in a C02 continuous phase to form micelles with a C02-phobic core and a C02-philic corona. For example, fluorocarbon-hydrocarbon block copolymers of PFOA and PS were synthesized utilizing controlled free radical methods [104]. Small angle neutron scattering studies have demonstrated that block copolymers of this type do indeed self-assemble in solution to form multimolecular micelles [117]. Figure 5 depicts a schematic representation of the micelles formed by these amphiphilic diblock copolymers in C02. Another block copolymer which has proven useful in the stabilization of colloidal particles is the siloxane based stabilizer PS-fr-PDMS [118,119]. Chemical... 

It is possible to produce a block copolymer by the anionic polymerisation of styrene and butadiene as depicted below. The polystyrene and polybutadiene are mutually incompatible and hence phase separate to give the morphology also depicted below ... 

It was found that in spite of the large excess of modifying amine (N-isopropyl-, -diethyl, -dipropyl, -diisopropyl, -n-hexyl, -cyclohexyl, -n-octyl), the extent of substitution did not exceed 5-10 molar %. For the case of the N-isopropyl derivative, i.e. [poly(AAm-co-NiPAAm)], the authors connected such results with the temperature-induced conformational transformation of partially hydrophobized copolymer acquiring the contracted conformation, "... which made it difficult for N-isopropylamine to react further with the amide groups [22], Unfortunately, no data on the solution behaviour of these interesting copolymers have been reported to date, although there is a high probability that they would demonstrate certain properties of the protein-like macromolecules. At least, in favour of similar supposition is supported by the results of our studies [23] of somewhat different PAAm partially hydrophobized derivative, whose preparation method is depicted in Scheme 3. 

Fig. 4 Curves Xsp versus copolymer composition X = X for macromolecules of length / = 103 at values of parameters (Eq. 20) equal to b- 0.01 and h-2 (2) 5 (3) 15 (4). Asymptotic dependences at h 0 and h oo are depicted by thin lines (Eq. 1) and (Eq. 5), respectively. Volume fraction of monomeric units in a globule = 0.9...

The copolymer composition produced by these two catalysts can be estimated using the Mayo-Lewis equation [38] and these values of i and r2. Figure 10 depicts the hypothetical comonomer content in the polymer (F2) as a function of the mole fraction of comonomer in the reactor (f2). The good incorporator produces a material with higher F2 as f2 increases. In contrast, the composition from the poor incorporator is relatively flat across a broad range and increases only at very high values of/2. The F2 required to render the copolymer amorphous is comonomer-dependent for 1-octene, this value is near 0.19. In this hypothetical system, the good incorporator produces that composition at f2 = 0.57, at which the poor incorporator incorporates very little comonomer (F2 = 0.01). 

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