Styrene in polymers

Figure 10.7. Instantaneous copolymer composition in free-radical copolymerization of styrene and 2-vinyl thiophene mole fraction of styrene in polymer as function of initial mole fraction and fractional conversion of styrene calculated with reactivity ratios pa = 0.35 and pb = 3.10 (from Mayo and Walling [127]).

Problem 6.50 The experimental value of dynamic concentration of styrene in polymer latex particles under the conditions of constant rate in emulsion polymerization has been found to be 5.2 mol/liter. Assuming this value to be applicable, calculate the rate of polymerization per liter of aqueous phase in stage II of the reaction of the emulsion polymerization recipe given in Problem... 

Moles of Monomer Remaining Mole Fraction of Styrene in Monomer Instantaneous Mole Fraction of Styrene in Polymer Cumulative Mole Fraction of Styrene in Polymer... 

Shanks has determined residual butadiene and styrene in polymers with an analytical sensitivity of 0.05 to 5 ppm by analysis of the equilibrated headspace over polymer solutions and determined acrylonitrile, alpha-methyl styrene and styrene monomers by headspace analysis over heated solid polymer samples. 

Styrene-Acrylonitrile (SAN) Copolymers. SAN resins are random, amorphous copolymers whose properties vary with molecular weight and copolymer composition. An increase in molecular weight or in acrylonitrile content generally enhances the physical properties of the copolymer but at some loss in ease of processing and with a slight increase in polymer color. 

ACRYLONmiD.EPOLYTffiRS - SURVEY AND SAN (STYRENE-ACRYLONmULECO-POLYTffiRS)] (Vol 1) -in polymer blends pOLYMERBLENDS] (Vol 19)... 

Acrylics. Acetone is converted via the intermediate acetone cyanohydrin to the monomer methyl methacrylate (MMA) [80-62-6]. The MMA is polymerized to poly(methyl methacrylate) (PMMA) to make the familiar clear acryUc sheet. PMMA is also used in mol ding and extmsion powders. Hydrolysis of acetone cyanohydrin gives methacrylic acid (MAA), a monomer which goes direcdy into acryUc latexes, carboxylated styrene—butadiene polymers, or ethylene—MAA ionomers. As part of the methacrylic stmcture, acetone is found in the following major end use products acryUc sheet mol ding resins, impact modifiers and processing aids, acryUc film, ABS and polyester resin modifiers, surface coatings, acryUc lacquers, emulsion polymers, petroleum chemicals, and various copolymers (see METHACRYLIC ACID AND DERIVATIVES METHACRYLIC POLYMERS). 

In polymers such as polystyrene that do not readily undergo charring, phosphoms-based flame retardants tend to be less effective, and such polymers are often flame retarded by antimony—halogen combinations (see Styrene). However, even in such noncharring polymers, phosphoms additives exhibit some activity that suggests at least one other mode of action. Phosphoms compounds may produce a barrier layer of polyphosphoric acid on the burning polymer (4,5). Phosphoms-based flame retardants are more effective in styrenic polymers blended with a char-forming polymer such as polyphenylene oxide or polycarbonate. 

The principal use of the peroxodisulfate salts is as initiators (qv) for olefin polymerisation in aqueous systems, particularly for the manufacture of polyacrylonitrile and its copolymers (see Acrylonitrile polymers). These salts are used in the emulsion polymerisation of vinyl chloride, styrene—butadiene, vinyl acetate, neoprene, and acryhc esters (see Acrylic ester polymers Styrene Vinyl polymers). 

Fig. 4. MiceUular gelation mechanism. A shows micelle nuclei, highly cross-linked B, boundary where micelle growth terminates in styrene block polymers.

A large number of hindered phenoHc antioxidants are based on the Michael addition of 2,6-di-/ f2 -butylphenol and methyl acrylate under basic catalysis to yield the hydrocinnamate which is a basic building block used in the production of octadecyl 3-(3,5-di-/ f2 butyl-4-hydroxyphenyl)propionate, [2082-79-3], tetrakis(methylene-3(3,5-di-/ f2 butyl-4-hydroxylphenyl)propionate)methane [6683-19-8], and many others (63,64). These hindered phenolic antioxidants are the most widely used primary stabilizers in the world and are used in polyolefins, synthetic and natural mbber, styrenics, vinyl polymers, and engineering resins. 2,6-Di-/ f2 -butylphenol is converted to a methylene isocyanate which is trimerized to a triazine derivative... 

Antistatic polystyrenes have been developed in terms of additives or coatings to minimise primarily dust collecting problems in storage (see Antistatic agents). Large Hsts of commercial antistatic additives have been pubhshed (41). For styrene-based polymers, alkyl and/or aryl amines, amides, quaternary ammonium compounds, anionics, etc, are all used. 

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,...

Many mbber-modified styrene plastics are fabricated into sheet by extmsion primarily for subsequent thermoforming operations. Much consideration has been given to the problem of achieving good surface quaUty in extmded sheet (230,231). Excellent surface gloss and sheet uniformity can be obtained with styrene-based polymers. 

Butadiene is used primarily in polymers, including SBR, BR, ABS, SBL, and NR. In 1989 these uses accounted for about 79% of butadiene consumed in the United States (268,269). Styrene—butadiene mbber, the single largest user of butadiene, consumes about 540,000 kg of butadiene, or 32% of the total. It ... 

ABS is the sixth largest volume thermoplastic resin and the principal engineering (stmctural or load bearing) plastic (89). ABS is a terpolymer manufactured by copolymerizing acrylonitrile and styrene in the presence of polybutadiene mbber. Important producers of ABS plastics include General Electric, Monsanto (Lustran), and Dow (Abtec) (see Acrylonitrile polymers). 

Today the common practice is first to dissolve the rubber in the styrene monomer and then to polymerise the styrene in the usual way. By this process the resultant blend will contain not only rubber and polystyrene but also a graft polymer where short styrene side chains have been attached to the rubber molecules. This gives a marked improvement in the impact strengths that can be obtained. 

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 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. 

Polycarbonates based on tetramethylbisphenol A are thermally stable and have a high Vicat softening point of 196°C. On the other hand they have lower impact and notched impact resistance than the normal polymer. Blends with styrene-based polymers were introduced in 1980, and compared with PC/ABS blends, are claimed to have improved hydrolytic resistance, lower density and higher heat deflection temperatures. Suggested applications are as dishes for microwave ovens and car headlamp reflectors. 

Block copolymer chemistry and architecture is well described in polymer textbooks and monographs [40]. The block copolymers of PSA interest consist of anionically polymerized styrene-isoprene or styrene-butadiene diblocks usually terminating with a second styrene block to form an SIS or SBS triblock, or terminating at a central nucleus to form a radial or star polymer (SI) . Representative structures are shown in Fig. 5. For most PSA formulations the softer SIS is preferred over SBS. In many respects, SIS may be treated as a thermoplastic, thermoprocessible natural rubber with a somewhat higher modulus due to filler effect of the polystyrene fraction. Two longer reviews [41,42] of styrenic block copolymer PSAs have been published. 

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