Miscellaneous Polymers and Copolymers

In addition to the polymers, copolymers and alloys already discussed, styrene and its derivatives have been used for the polymerisation of a wide range of polymers and copolymers. Two of the more important applications of styrene, in SBR and in polyester laminating resins, are dealt with in Chapters 11 and 25 respectively. 

The influence of nuclear substituents on the properties of a homopolymer depends on the nature, size and shape of the substituent, the number of the substituents and the position of entry into the benzene ring. 

Polar substituents such as chlorine increase the interchain forces and hinder free rotation of the polymer chain. Hence polydichlorostyrenes have softening points above 100°C. One polydichlorostyrene has been marketed commercially as Styramic HT. Such polymers are essentially self-extinguishing, have heat distortion temperatures of about 120°C and a specific gravity of about 1.40. 

A poly(tribromostyrene) with the bromine atoms attached to the benzene ring is marketed by the Ferro corporation as F yro-Chek 68 PB as a heat-resisting fire retardant used in conjunction with antimony oxide. The polymer has an exceptionally high specific gravity, reputedly of 2.8, and a softening point of 220°C. 

The nuclear substituted methyl styrenes have been the subject of much study and of these poly(vinyl toluene) (i.e. polymers of m- and /7-methylstyrenes) has found use in surface coatings. The Vicat softening point of some nuclear substituted methyl styrenes in given in Table 16.8. 

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Techniques and plants for polymerization have become more precise and specific but there is a possibility still that similar grades of the same material made in different units may differ in practice (in features such as the distribution of molecular weights, and colour). It will be appreciated too that many polymers and copolymers are used in combination with other substances— stabilizers, fillers, and miscellaneous additives—all of which (and especially those occurring naturally, like China clay and some types of plasticizer) may themselves differ appreciably from batch to batch. 

This volume continues in the same format as the first edition with updates on the syntheses of various types of polymers, including olefin-sulfur dioxide copolymers, polythioesters, sulfide polymers, polyisocyanates, polyoxyalkyihydroxy compounds, polyvinyl carbazole, polyvinyl acetate, polyallyl esters, polyvinyl fluoride, and miscellaneous polymer preparations. The book should be useful to academic and industrial chemists who desire typical synthetic procedures for preparing the polymers described herein. In addition to reviewing the latest journals, we survey the patent literature and give numerous additional references. 

Matsumura, S. 2005. Biodegradation of poly(vinyl alcohol) and its copolymers. Biopolymers Online, Part 9. Miscellaneous Biopolymers and Biodegradation of Polymers. 

Polymers have been grouped into the following 10 categories aliphatic polyolefins, polystyrenes, polyvinyl halides, polyvinyl esters, cellulose esters, polyvinyl ethers, poly-ethers, aromatic polymers, copolymers and miscellaneous polymers. The molar cohesive energies (Eg) were calculated from their respective group increments according to the following equation ... 

Hagman and co-workers [3] and Schmidt and co-workers [4] used dynamic headspace analysis to study volatiles in polypropylene-polyethylene copolymers and PVC and polyethylene terephthalate. In the latter method [3], volatiles from PET and PVC were collected and separated by open tubular GC. Other solid polymer headspace methods discussed include hexane, tridicane and butylated hydroxytoluene in polypropylene [5], vinyl chloride, vinyl acetate, acetaldehyde and water in vinyl and acrylic polymers and polyolefins [6], ethyl acetate and toluene in laminated polyolefins [7], miscellaneous volatiles in polymers [8] and solvents retained in plastic films [9-12]. 

ACRN is used to make acrylic fibers, acrylonitrile-butadiene-styrene (ABS), and styrene-acrylonitrile (SAN). Worldwide acrylic fiber accounts for over half of total demand while ABS and SAN consume about 30% of output. Smaller applications include nitrile rubber copolymers (4%), adiponitrile (ADN) and acrylamide. Acrylic fibers are used in carpets and clothing while ABS and SAN resins are used in pipes and fittings, automobiles, furniture, and packaging276. In the United States the ACRN uses are distributed differently 38% is used in ADN, 22% in ABS and SAN, 17% in acrylic fibers, 11% in acrylamide, 3% in nitrile elastomers, and 9% in miscellaneous, which includes polymers, polyols, barrier resins and carbon fibers277. 

I. .5.4 Block Copolymer Molecular Architecture Thermoplastics and Thermosets Hlasioniers, Fibers, and Plastics Miscellaneous Terms Polymer Nomenclature... 

NOTE Ibtals for plastics are for those products listed and exclude some small-volume plastics. Synthetic rubber data include Canada. Dry-weight basis unless otherwise specified Density 0.940 and below " Data include Canada from 2001 Density above 0.940 Data include Canada from 1995 Data include Canada from 2000 Data include Canada from 1994 Includes styrene-butadiene copolymers and othm styrene-based polymers Unmodified Includes butyl styrene-butadiene rubber latex, nitrile latex, polyisoprene, and miscellaneous others. SOURCES American Plastics Council, International Institute of Synthetic Rubber Producers. 

As indicated earlier, another powerful tool for upgrading polymer properties is the postpolymerization reaction of preformed polymers. These reactions may occur on reactive sites dispersed in the polymer main chain. Such reactions include chain extensions, cross-linking, and graft and block copolymer formation. The reactions may also occur on reactive sites attached directly or via other groups/chains to the polymer backbone. Reactions of this type are halogenation, sulfonation, hydrolysis, epoxidation, surface, and other miscellaneous reactions of polymers. In both cases these types of reactions transform existing polymers into those with new and/or improved properties. 

One of the miscellaneous fluoroolefm polymers is a copolymer of trifluoronitrosomethane and tetrafluoroethylene, an elastomer ... 

Several miscellaneous carbon chain backbone polymers have been claimed as biodegradable without clear evidence, these include copolymers of methyl methacrylate and vinyl pyridinium salts (Kawabata 1993), w here the pyridinium salt is hypothesized as a magnet for bacteria w hich then cleave the chain into small fragments w hich biodegrade completely. An ethylene/vinyl alcohol copolymer that is converted into a polyester by a Baeyer VUliger reaction (Brima 1993) (below) ... 

Miscellaneous Fractionation Methods.—Turbidimetric titration by non-solvent addition has virtually vanished since the advent of GPC, but Hay et have recently shown that the method of turbidimetric titration by temperature decrease can give useful information about the polydispersity of polymers. Nonsolvent induced turbidimetry of fractions eluted from a GPC column has been used by Hoffmann and Urban to examine composition distribution in copolymers. 

As polymers that contain both hydrophilic and hydrophobic components aroused keen interest from theoretical and practical points of view over the past years, synthesis of amphiphilic branched copolymers by ring-opening metathesis polymerization of miscellaneous macromonomers is an important goal of the actual research. Thus, in order to obtain globular shape macromolecules that would present the same features as those exhibited by certain assemblies of molecules such as the micelles or the latices, with a bulk part different from the external surface, polymerization of norbornyl polystyrene-poly(ethylene oxide) macromonomer has been conducted in the presence of Schrock-type catalyst Mo(NAr)(CH/Bu)(OC(CH3)(CF3)2)2 in toluene at room temperature to produce poly-norbornene-polystyrene-poly(ethylene oxide) block copolymers (120) [88] [Eq. (52)]. 

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