Styrene, copolymers with poly

In addition to providing fully alkyl/aryl-substituted polyphosphasenes, the versatility of the process in Figure 2 has allowed the preparation of various functionalized polymers and copolymers. Thus the monomer (10) can be derivatized via deprotonation—substitution, when a P-methyl (or P—CH2—) group is present, to provide new phosphoranimines some of which, in turn, serve as precursors to new polymers (64). In the same vein, polymers containing a P—CH group, for example, poly(methylphenylphosphazene), can also be derivatized by deprotonation—substitution reactions without chain scission. This has produced a number of functionalized polymers (64,71—73), including water-soluble carboxylate salts (11), as well as graft copolymers with styrene (74) and with dimethylsiloxane (12) (75). 

The first system is based on a poly (norbornene)-supported Co salen and the second system is based on a poly(styrene) backbone. For the poly (norbornene) system, a homopolymers and several different copolymers were prepared (44), with varying fractions of Co salen side-chains and spacer side-chains (Figure 3, copolymer la-c and homopolymer Id). For the poly (styrene) system, both homopolymers of salen-containing monomers and copolymers with styrene (45,46) were prepared (Figure 3, copolymer 2a-c and homopolymer 2d). 

One of the earliest examples of photodecomposable, but thermally stable, polymeric systems contains pendant perester substituted benzophenone moieties, the photodissociation of the former group being promoted by the benzophenone chromophore which behaves as a triplet sensitizer. Indeed, the homopolymer of 4-vinylbenzoyl-4 -tert-butyl perbenzoate and its copolymers with styrene [poly(VBPE) and poly(VBPE-co-St), respectively] have been prepared and checked as photoinitiators in the polymerization of styrene and MMA by irradiation at 366 nm [79,80]. 

Poly(l,4-butadiene) segments prepared by the ruthenium-mediated ROMP of 1,5-cyclooctadiene can be incorporated into the ABA-type block copolymers with styrene (B-106) and MMA (B-107).397 The synthetic method is based on the copper-catalyzed radical polymerizations of styrene and MMA from the telechelic poly(butadiene) obtained by a bifunctional chain-transfer agent such as bis(allyl chloride) or bis-(2-bromopropionate) during the ROMP process. A more direct route to similar block copolymers is based on the use of a ruthenium carbene complex with a C—Br bond such as Ru-13 as described above.67 The complex induced simultaneous or tandem block copolymerizations of MMA and 1,5-cyclooctadiene to give B-108, which can be hydrogenated into B-109, in one pot, catalyzed by the ruthenium residue from Ru-13. 

Copolymers with styrene and alkyl methacrylates were synthesized also. The coupling method was initially developed by Asami et al. (200. 210) who succeeded in preparing polymerizable oligomers from living poly(THF) by coupling with vinyl phenolate (CH2=CH-C H -0 ) or with vinylbenzyl alcoholate (CH2=CH-C H -CH20 ). The horaopolymerization and copolymerization of these Macroraers were studied (209). 

Clarke and Shanks have examined the influence of sample thickness on the benzoin photoinitiated polymerization of butyl acrylate. They found that as the photoinitiator concentration increases so the extent of polymerization become less susceptible to changes in sample thickness. Grauchak et al. have successfully photopolymerized acrylic monomers in polyamide matrices with aromatic carbonyl compounds. In the photocycloaddition of olefins to poly(4,-vinylbenzo-phenone) and its copolymers with styrene, the rate of addition was found to be independent of the glass transition temperature suggesting that large-scale molecular motion is unimportant in this photoreaction. 

Poly BD marketed by Atochem North America, Inc. is a family of hydroxyl-terminated butadiene homopolymers and copolymers with styrene or acrylonitrile. These materials are usually reacted with isocyanates to produce pol)mrethanes that have excellent resistance to boiling water. 

An interesting trend is the increasing use of in situ NMR to study polymerization kinetics, curing reactions, or to determine the comonomer reactivity ratios (127). High-pressurCy high resolution NMR has been employed to study polymer/solvent interactions in poly(l,l-hydroperfluorooctyl acrylate) and its copolymer with styrene (128). 

Also copolymers with styrene or methylmethacrylate PVP was also replaced by poly-7V-vinylimidazole [77-79,83,84],... 

Poly(p-formylamino styrene) and its copolymers with styrene, methyl methacrylate and n-butyl methacrylate... 

Figure 9.17 Plot of log [i ]M versus retention volume for various polymers, showing how different systems are represented by a single calibration curve when data are represented in this manner. The polymers used include linear and branched polystyrene, poly(methyl methacrylate), poly(vinyl chloride), poly(phenyl siloxane), polybutadiene, and branched, block, and graft copolymers of styrene and methyl methacrylate. [From Z. Grubisec, P. Rempp, and H. Benoit, Polym. Lett. 5 753 (1967), used with permission of Wiley.]...

The combination of stmctural strength and flotation has stimulated the design of pleasure boats using a foamed-in-place polyurethane between thin skins of high tensUe strength (231). Other ceUular polymers that have been used in considerable quantities for buoyancy appHcations are those produced from polyethylene, poly(vinyl chloride), and certain types of mbber. The susceptibUity of polystyrene foams to attack by certain petroleum products that are likely to come in contact with boats led to the development of foams from copolymers of styrene and acrylonitrUe which are resistant to these materials... 

Fig. 8. Thermogravimetric analysis of polymers and copolymers of styrene in nitrogen at 10°C/min A represents PS B, poly(vinyltoluene) C, poly(a-methylstyrene) D, poly(styrene-i (9-acrylonitrile), with 71.5% styrene E, poly(styrene-i (9-butadiene), with 80% styrene and F,...

Some commercial durable antistatic finishes have been Hsted in Table 3 (98). Early patents suggest that amino resins (qv) can impart both antisHp and antistatic properties to nylon, acryUc, and polyester fabrics. CycHc polyurethanes, water-soluble amine salts cross-linked with styrene, and water-soluble amine salts of sulfonated polystyrene have been claimed to confer durable antistatic protection. Later patents included dibydroxyethyl sulfone [2580-77-0] hydroxyalkylated cellulose or starch, poly(vinyl alcohol) [9002-86-2] cross-linked with dimethylolethylene urea, chlorotria2ine derivatives, and epoxy-based products. Other patents claim the use of various acryUc polymers and copolymers. Essentially, durable antistats are polyelectrolytes, and the majority of usehil products involve variations of cross-linked polyamines containing polyethoxy segments (92,99—101). 

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. 

The poly(styrene-b-isoprene) (P(S-b-IP)) and poly(-styrene-b-2-vinyl pyridine) (P(S-b-2VP)) block copolymers with narrow molecular weight distributions for blending with the microspheres were also synthesized using the additional anionic polymerization technique. The number-average molecular weights (Mns) and PS contents are also shown in Table 1. 

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