Polymers, unsaturated aromatic

Another important use of BCl is as a Ftiedel-Crafts catalyst ia various polymerisation, alkylation, and acylation reactions, and ia other organic syntheses (see Friedel-Crafts reaction). Examples include conversion of cyclophosphasenes to polymers (81,82) polymerisation of olefins such as ethylene (75,83—88) graft polymerisation of vinyl chloride and isobutylene (89) stereospecific polymerisation of propylene (90) copolymerisation of isobutylene and styrene (91,92), and other unsaturated aromatics with maleic anhydride (93) polymerisation of norhornene (94), butadiene (95) preparation of electrically conducting epoxy resins (96), and polymers containing B and N (97) and selective demethylation of methoxy groups ortho to OH groups (98). 

Engineering polymers are often used as a replacement for wood and metals. Examples include polyamides (PA), often called nylons, polyesters (saturated and unsaturated), aromatic polycarbonates (PCs), polyoxymethylenes (POMs), polyacrylates, polyphenylene oxide (PPO), styrene copolymers, e.g., styrene/ acrylonitrile (SAN) and acrylonitrile/butadiene/styrene (ABS). Many of these polymers are produced as copolymers or used as blends and are each manufactured worldwide on the 1 million tonne scale. 

In alkyllithium initiated, solution polymerization of dienes, some polymerization conditions affect the configurations more than others. In general, the stereochemistry of polybutadiene and polyisoprene respond to the same variables Thus, solvent has a profound influence on the stereochemistry of polydienes when initiated with alkyllithium. Polymerization of isoprene in nonpolar solvents results largely in cis-unsaturation (70-90 percent) whereas in the case of butadiene, the polymer exhibits about equal amounts of cis- and trans-unsaturation. Aromatic solvents such as toluene tend to increase the 1,2 or 3,4 linkages. Polymers prepared in the presence of active polar compounds such as ethers, tertiary amines or sulfides show increased 1,2 (or 3,4 in the case of isoprene) and trans unsaturation.4. 1P U It appears that the solvent influences the ionic character of the propagating ion pair which in turn determines the stereochemistry. 

Among the polymers containing aromatic rings and unsaturated hydrocarbon groups in the backbone are poly(phenylene-ethynylenes) (PPE). This type of polymer has been synthesized by alkyne metathesis of 1,4-dipropynylated benzenes [11] and has applications in optical and electronic industry. A comprehensive study on thermal decomposition of several poly(substituted p-phenylene-ethynylenes) is available [12], The general formula for this group of polymers is the following ... 

The polymer also contains 0.1-0.6% unsaturated aromatic sulfonic acid for stabilization. 

Polymers with aromatic side groups smoke heavily, even when flaming. The most important representative of this group is polystyrene (the conventional unsaturated polyester products are also rated here by their styrene content). 

An aromatic polymer is one having an unsaturated hydrocarbon with one or more benzene ring structures in the monomer. The polymeric structure, which can be expressed as a chain of aromatic rings, is also known as a ladder polymer. The aromatic structure generally provides increased thermal stability. 

For the purposes of this chapter, polyolefins are defined as polymers based on unsaturated aliphatic hydrocarbons containing one double bond per molecule. Polymers derived from unsaturated aromatic hydrocarbons and dienes are considered in later chapters. At the present time the principal commercial polyolefins are polyethylene (polythene), polypropylene, polyisobutene, polybut-l-ene and poly-4-methylpent-l-ene together with related copolymers. These polymers are considered individually in subsequent sections after a brief account of relevant raw materials. 

Papadimitriou KD, Paloukis F, Neophytides SG et al (2011) Cross-linking of side chain unsaturated aromatic polyethers for high temperature polymer electrolyte membrane fuel cell applications. Macromoiecuies 44 4942-4951... 

Polymers. The molecular weights of polymers used in high energy electron radiation-curable coating systems are ca 1,000—25,000 and the polymers usually contain acryUc, methacrylic, or fumaric vinyl unsaturation along or attached to the polymer backbone (4,48). Aromatic or aUphatic diisocyanates react with glycols or alcohol-terrninated polyether or polyester to form either isocyanate or hydroxyl functional polyurethane intermediates. The isocyanate functional polyurethane intermediates react with hydroxyl functional polyurethane and with acryUc or methacrylic acids to form reactive p olyurethanes. 

Reactive (unsaturated) epoxy resins (qv) are reaction products of multiple glycidyl ethers of phenoHc base polymer substrates with methacrylic, acryhc, or fumaric acids. Reactive (unsaturated) polyester resins are reaction products of glycols and diacids (aromatic, aUphatic, unsaturated) esterified with acryhc or methacrylic acids (see POLYESTERS,unsaturated). Reactive polyether resins are typically poly(ethylene glycol (600) dimethacrylate) or poly(ethylene glycol (400) diacrylate) (see PoLYETPiERs). 

Process Oils, Plasticizers. Petroleum-based mbber process oils generally contain a mixture of paraffinic, naphthenic, and aromatic components. These oils vary in composition from grade to grade, but most contain some unsaturated moieties and this unsaturation can compete with the polymer for curatives. Therefore, state of cure can be decreased. This is not easily detected because oil softens the compound which masks the loss of state of cure. 

Some polymers like PE and NR get cross-linked on exposure to radiation while others like those based on vinylidene polymers, e.g., polymethylmethacrylate (PMMA), polyisobutylene, degrade. Certain other types of polymer stmctures (high aromatic content or thermoset) resist degradation by high-energy radiation. Coating polymers usually contain acrylic, methacryUc, or fumaric vinyl unsaturation along or attached to the backbone. 

Functionalized copolymers from dienes and p-alkylstyrenes can serve as dispersants and viscosity index improvers. The functionalities are introduced via the aromatic units [233,234]. The polymers are selectively hydrogenated to produce polymers that have highly controlled amounts of unsaturation, permitting a highly selective functionalization. The dispersant substances may also include a carrier fluid to provide concentrates of the dispersant. 

Unsaturated groups are very interesting for application development because this specific functionality opens up a broad range of possibilities for further (chemical) modification of the polymer structure, and therefore its physical and material properties. The direct microbial incorporation of other functional substituents to the polymer side chains, e.g. epoxy-, hydroxy-, aromatic-, and halogen functional groups, influences the physical and material properties of poly(HAMCL) even further [28,33,35,39-41]. This features many possibilities to produce tailor-made polymers, depending on the essential material properties that are needed for the development of a specific application. 

Due to the unsaturation present in the main chain, protection is required against oxygen, UV and ozone. Oil resistance is poor and the polymer is not resistant to aromatic, aliphatic and halogenated hydrocarbons. 

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