Methyl methacrylate influence

The cross-linking reaction mechanism is also influenced by the presence of other monomers. Methyl methacrylate is often used to improve the uv resistance of styrene-based resins. However, the disparate reaction rates of styrene and methacrylate monomer with the fumarate unsaturation not only preclude the use of more than 8% of the methacrylate monomer due to the significant slowing of the cross-linking reaction but also result in undercured products. 

The acetone supply is strongly influenced by the production of phenol, and so the small difference between total demand and the acetone suppHed by the cumene oxidation process is made up from other sources. The largest use for acetone is in solvents although increasing amounts ate used to make bisphenol A [80-05-7] and methyl methacrylate [80-62-6]. a-Methylstyrene [98-83-9] is produced in controlled quantities from the cleavage of cumene hydroperoxide, or it can be made directly by the dehydrogenation of cumene. About 2% of the cumene produced in 1987 went to a-methylstyrene manufacture for use in poly (a-methylstyrene) and as an ingredient that imparts heat-resistant quaUties to polystyrene plastics. 

Pure polymeric acrylonitrile is not an interesting fiber and it is virtually undyeable. In order to make fibers of commercial iaterest acrylonitrile is copolymerized with other monomers such as methacrylic acid, methyl methacrylate, vinyl compounds, etc, to improve mechanical, stmctural, and dyeing properties. Eibers based on at least 85% of acrylonitrile monomer are termed acryHc fibers those containing between 35—85% acrylonitrile monomer, modacryhc fibers. The two types are in general dyed the same, although the type and number of dye sites generated by the fiber manufacturing process have an influence (see Eibers, acrylic). 

Poly(methyl methacrylate) is a good electrical insulator for low-frequency work, but is inferior to such polymers as polyethylene and polystyrene, particularly at high frequencies. The influence of temperature and frequency on the dielectric constant is shown in Figure 15.9. 

The state of the surface of a brittle solid has been found to exert a considerable influence on the mechanical behaviour observed it is at least as important as the underlying molecular constitution in this regard. The presence of microscopic scratches, voids, or other imperfections will seriously weaken the tensile strength of specimens of glassy polymer, such as poly(methyl methacrylate) at ambient temperatures. 

A third factor influencing the value of Tg is backbone symmetry, which affects the shape of the potential wells for bond rotations. This effect is illustrated by the pairs of polymers polypropylene (Tg=10 C) and polyisobutylene (Tg = -70 C), and poly(vinyi chloride) (Tg=87 C) and poly(vinylidene chloride) (Tg =- 19°C). The symmetrical polymers have lower glass transition temperatures than the unsymmetrical polymers despite the extra side group, although polystyrene (100 C) and poly(a-meth-ylstyrene) are illustrative exceptions. However, tacticity plays a very important role (54) in unsymmetrical polymers. Thus syndiotactic and isoitactic poly( methyl methacrylate) have Tg values of 115 and 45 C respectively. 

Much work on the preparation of nonaqueous polymer dispersions has involved the radical polymerization of acrylic monomers in the presence of copolymers having the A block the same as the acrylic polymer in the particle core 2). The preparation of polymer dispersions other than polystyrene in the presence of a PS-PDMS diblock copolymer is of interest because effective anchoring of the copolymer may be influenced by the degree of compatibility between the PS anchor block and the polymer molecules in the particle core. The present paper describes the interpretation of experimental studies performed with the aim of determining the mode of anchoring of PS blocks to polystyrene, poly(methyl methacrylate), and poly(vinyl acetate) (PVA) particles. 

Werner (1980) has studied devolatilization in corotating twin-screw extruders when the volatile component was stripped from the polymeric solution by applying a vacuum to the system. Rough estimates of the equilibrium partial pressure of the volatile component in the feedstream for each of the systems studied by Werner indicate that this pressure was less than the applied pressure, which means that bubbles could have been formed. Figure 17 shows the influence of the externally applied pressure on the exit concentration for a methyl methacrylate-poly(methyl methacrylate) system of fixed concentration. Note that the exit concentration decreases as the pressure is decreased, but seems to approach an asymptotic value at the lowest pressures studied. Werner also reported that at a fixed flow rate and feed concentration the exit concentration did not vary with screw speed (over the range 150-300 min" ), which also suggests that ky alay, is independent of screw speed. Figure 18 is a plot of data obtained by Werner on an ethylene-low-density poly(ethylene) system and also shows that decreases in the applied pressure result in decreases in the exit concentration, but here a lower asymptote is not observed. 

A critical survey of the literature on free radical polymerizations in the presence of phase transfer agents indicates that the majority of these reactions are initiated by transfer of an active species (monomer or initiator) from one phase to another, although the exact details of this phase transfer may be influenced by the nature of the phase transfer catalyst and reaction medium. Initial kinetic studies of the solution polymerization of methyl methacrylate utilizing solid potassium persulfate and Aliquat 336 yield the experimental rate law ... 

Crystallinity. Is one of the key factors influencing properties. You can think of crystallinity in terms of how well a polymer fits in an imaginary pipe, as in Figure 22-6. Linear, straight chains are highly crystalline and fit very well. Bulky groups, coiled chains, and branched chains are not able to line up to fit in the pipe. They are amorphous, the opposite of crystalline. In a spectrum from totally amorphous, to almost totally crystalline, there is methyl methacrylate, polypropylene, low-density polyethylene, linear low-density polyethylene, high-density polyethylene, and nylon. 

FIGURE 14.9 Influence of temperature on the stress-strain behavior of a sample of poly(methyl methacrylate). (Modeled after Carswell, T.S. and Nason, H.K. Effects of Environmental Conditions on the Mechanical Properties of Organic Plastics, 1944. Copyright, ASTM, Philadelphia, PA. With permission.)... 

The stereoselective polymerization of various acrylates and methacrylates has been studied using initiators such as atkyllithium [Bywater, 1989 Pasquon et al., 1989 Quirk, 1995, 2002]. Table 8-12 illustrates the effects of counterion, solvent, and temperature on the stereochemistry of the anionic polymerization of methyl methacrylate (MMA). In polar solvents (pyridine and THF versus toluene), the counterion is removed from the vicinity of the propagating center and does not exert an influence on entry of the next monomer unit. The tendency is toward syndiotactic placement via chain end control. The extent of syndiotacticity... 

Figure 5.67 Influence of temperature on the stress-strain response of (a) cellulose acetate and (b) poly(methyl methacrylate). Reprinted, by permission, from J. M. G. Cowie, Polymers Chemistry Physics of Modem Materials, 2nd ed., p. 283. Copyright 1991 by J. M. G. Cowie.

However, if increasing amounts of free radical acceptors are added to the system, the block and graft polymerization gradually decreases, as saturation of free macroradicals proceeds faster than the addition of monomers. In Table 2, the influence of benzoquinone on the graft polymerization of vinyl chloride on poly(methyl methacrylate) is shown (20). 

Influence of Interpolymer Properties. As stated earlier, the physical and chemical properties of interpolymers markedly influence the reaction rate after the induction period. If the monomer present yields a polymer comparable in viscosity with the initial mixture the rate of scission will not accelebrate. For example, the polymerization rate of chloroprene on mastication with natural rubber does not increase as markedly with conversion (69), see Fig. 19, as with methyl methacrylate and styrene. The reason is the chloroprene-rubber system remained elastic and softer than the original rubber. 

A review is given on the kinetics of the anionic polymerization of methyl methacrylate and tert.-butyl methacrylate in tetrahydrofuran and 1,2-dimethoxy-ethane, including major results of the author s laboratory. The Arrhenius plots for the propagation reaction+are linear and independent of the counterion (i.e. Na, Cs). The results are discussed assuming the active centre to be a contact ion pair with an enolate-like anion the counterion thus exhibiting little influence on the reactivity of the carbanion. 

Figure 1. Influence of preirradiation dose of poly (vinyl chloride) films in vacuo on the extent of grafting observed after heating in methyl methacrylate at 50°C. for 1 hr, (Curve 1) and 2 hrs. (Curve 2) (5)...

Table 3. Influence of monomeric arrangements of styrene-methyl methacrylate Copolymers upon R f valuesc...

Table VII the electron-beam exposure characteristics are given for the soluble poly (triphenylmethyl methacrylate-co-methyl methacrylate)s. The sensitivity on alkaline development was strongly influenced by the copolymer composition. The highest sensitivity was obtained on the copolymer containing 93.7 mol% methyl methacrylate. The copolymer of highest sensitivity showed the 7-value of 6.3, which was nearly twice as large as that for poly(methyl methacrylate). Formation of methacrylic acid units on exposure is obvious from the infrared spectrum. However, the mechanism of the occurrence should be different from the case of the a,a-dimethylbenzyl methacrylate polymer since there are no /3-hydrogen atoms in the triphenylmethyl group, and may be similar to the case of poly (methyl methacrylate). This will be explored in the near future.

In connection with the cause of the field influences on the cationic homopolymerization, it is interesting to study how free radical polymerizations are affected by an electric field. Table 1 shows that both the polymer yield and the degree of polymerization were not affected at all by the field, though the intensity was much higher than that applied to cationic systems. The situation was the same for free radical polymerizations of styrene by benzoylperoxide (72), and of methyl methacrylate by benzoylperoxide and azobisisobutyronitiile (77). 

F14. —, and S. Loshaek Cross-linked polymers. I. Factors influencing the efficiency of crosslinking in copolymers of methyl methacrylate and glycol dimethacrylates. J. Am. Chem. Soc. 75, 3544 (1953). 

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