Methyl methacrylate specificity

Unlike most crystalline polymers, PVDF exhibits thermodynamic compatibiUty with other polymers (133). Blends of PVDF and poly(methyl methacrylate) (PMMA) are compatible over a wide range of blend composition (134,135). SoHd-state nmr studies showed that isotactic PMMA is more miscible with PVDF than atactic and syndiotactic PMMA (136). MiscibiUty of PVDF and poly(alkyl acrylates) depends on a specific interaction between PVDF and oxygen within the acrylate and the effect of this interaction is diminished as the hydrocarbon content of the ester is increased (137). Strong dipolar interactions are important to achieve miscibility with poly(vinyhdene fluoride) (138). PVDF blends are the object of many papers and patents specific blends of PVDF and acryflc copolymers have seen large commercial use. 

Electrical Properties. Poly(methyl methacrylate) has specific electrical properties that make it unique (Table 4). The surface resistivity of poly(methyl methacrylate) is higher than that of most plastic materials. Weathering and moisture affect poly(methyl methacrylate) only to a minor degree. High resistance and nontracking characteristics have resulted in its use in high voltage appHcations, and its excellent weather resistance has promoted the use of poly(methyl methacrylates) for outdoor electrical appHcations (22). 

Fig. 15. Oxygen permeability versus 1/specific free volume at 25 °C (30). 1. Polybutadiene 2. polyethylene (density 0.922) 3. polycarbonate 4. polystyrene 5. styrene-acrylonitrile 6. poly(ethylene terephthalate) 7. acrylonitrile barrier polymer 8. poly(methyl methacrylate) 9. poly(vinyl chloride) 10. acrylonitrile barrier polymer 11. vinyUdene chloride copolymer 12. polymethacrylonitrile and 13. polyacrylonitrile. See Table 1 for unit conversions.

Comparison of Table 5.4 and 5.7 allows the prediction that aromatic oils will be plasticisers for natural rubber, that dibutyl phthalate will plasticise poly(methyl methacrylate), that tritolyl phosphate will plasticise nitrile rubbers, that dibenzyl ether will plasticise poly(vinylidene chloride) and that dimethyl phthalate will plasticise cellulose diacetate. These predictions are found to be correct. What is not predictable is that camphor should be an effective plasticiser for cellulose nitrate. It would seem that this crystalline material, which has to be dispersed into the polymer with the aid of liquids such as ethyl alcohol, is only compatible with the polymer because of some specific interaction between the carbonyl group present in the camphor with some group in the cellulose nitrate. 

The successful development of eye contact lenses led in turn to a demand for soft contact lenses. Such a demand was eventually met by the preparation of copolymers using a combination of an acrylic ester monomer such as methyl methacrylate, a cross-linkable monomer such as a dimethacrylate, and a monomer whose homopolymer is soluble or highly swollen in water such as N-vinyl pyrrolidone. Such copolymers swell in water (hence the term hydrophilic), the degree of swelling being controlled by the specific type and amount of the monomers used. In use the lens is swollen to equilibrium in water, a typical soft lens having a water content of about 75%. 

There are probably several factors which contribute to determining the endo exo ratio in any specific case. These include steric effects, dipole-dipole interactions, and London dispersion forces. MO interpretations emphasize secondary orbital interactions between the It orbitals on the dienophile substituent(s) and the developing 7t bond between C-2 and C-3 of the diene. There are quite a few exceptions to the Alder rule, and in most cases the preference for the endo isomer is relatively modest. For example, whereas cyclopentadiene reacts with methyl acrylate in decalin solution to give mainly the endo adduct (75%), the ratio is solvent-sensitive and ranges up to 90% endo in methanol. When a methyl substituent is added to the dienophile (methyl methacrylate), the exo product predominates. ... 

The theory of radiation-induced grafting has received extensive treatment. The direct effect of ionizing radiation in material is to produce active radical sites. A material s sensitivity to radiation ionization is reflected in its G value, which represents the number of radicals in a specific type (e.g., peroxy or allyl) produced in the material per 100 eV of energy absorbed. For example, the G value of poly(vinyl chloride) is 10-15, of PE is 6-8, and of polystyrene is 1.5-3. Regarding monomers, the G value of methyl methacrylate is 11.5, of acrylonitrile is 5.6, and of styrene is >0.69. 

Likewise, poly (methyl methacrylate) and polyfvinylidene fluoride), the chemical structures of which are shown in Fig. 10.2, make a miscible blend because of the strong specific interactions between the oxygen atoms on the methacrylate and the fluoride group in the vinylidene fluoride group. 

For some polymers, like polystyrene or poly(methyl methacrylate), narrow standards of known molar mass and small polydispersity are commercially available, which can be used for calibration. Unfortunately, such standards are not available for all polymers and then the obtained true molar masses of a specific polymer might differ by a factor of two from the value obtained by calibration with, e.g., polystyrene [30] (see Section 9.1). This problem can be resolved by the so-called universal calibration, which is based on the finding that the retention volume of a polymer is a single-valued function of the hydrodynamic volume of the polymer, irrespective of its chemical nature and... 

Peracetic acid, formed in situ from acetic acid and hydrogen peroxide in acid aqueous solution, was found to initiate graft copolymerization of vinyl monomers, e.g. methyl methacrylate and 4-vinyl pyridine, onto wood and cellulosic fibers at a good rate (1-3 h time) at 60°C2. The initiati on reaction is not specific for grafting and considerable amounts of homopolymer is formed. 

Fig. 56. Dependence of specific refractive index increment on conversion of monomers to polymer for a styrene/acrylonitrile/methyl methacrylate terpolymer in methyl ethyl ketone at 20 °C and 436 nm. (a) - partial azeotrope, (b) terpolymer with composition distribution163 ...

ISO 10366-1 2002 Plastics - Methyl methacrylate-acrylonitrile-butadiene-styrene (MABS) moulding and extrusion materials - Part 1 Designation system and basis for specifications ISO 10366-2 2003 Plastics - Methyl methacrylate-acrylonitrile-butadiene-styrene (MABS) moulding and extrusion materials - Part 2 Preparation of test specimens and determination of properties... 

Analysis of the poly(methyl methacrylate) sequences obtained by anionic polymerization was undertaken at the tetrad level in terms of two different schemes (10) one, a second-order Markov distribution (with four independent conditional probabilities, Pmmr Pmrr, Pmr Prrr) (44), the other, a two-state mechanism proposed by Coleman and Fox (122). In this latter scheme one supposes that the chain end may exist in two (or more) different states, depending on the different solvation of the ion pair, each state exerting a specific stereochemical control. A dynamic equilibrium exists between the different states so that the growing chain shows the effects of one or the other mechanism in successive segments. The deviation of the experimental data from the distribution calculated using either model is, however, very small, below experimental error, and, therefore, it is not possible to make a choice between the two models on the basis of statistical criteria only. 

Methanol concentrations in blood and urine have been found to correlate with methyl methacrylate exposure. The lack of specificity of methanol to methyl methacrylate exposure limits its usefulness as a biological indicator. 

There are important modifications of alkyds that help in specific applications. Phenolics can be added to improve film hardness and water resistance, but these confer increased yellowing tendencies on the final coating. Silicones impart heat resistance and exterior durability. Styrene increases the drying speed. Methyl methacrylate when added gives faster drying properties and improves the color and durability of the coating. 

Thus, the synthesis of a styrene-methyl methacrylate block polymer requires that styrene be the first monomer. Further, it is useful to decrease the nucleophilicity of polystyryl carbanions by adding a small amount of 1,1-diphenylethene to minimize attack at the ester function of MMA [Quirk et al., 2000]. Block copolymers of styrene with isoprene or 1,3-butadiene require no specific sequencing since crossover occurs either way. Block copolymers of MMA with isoprene or 1,3-butadiene require that the diene be the first monomer. The length of each segment in a block copolymer is controlled by the ratio of each monomer to initiator. The properties of the block copolymer vary with the block lengths of the different monomers. 

An appropriate formalism for Mark-Houwink-Sakurada (M-H-S) equations for copolymers and higher multispecies polymers has been developed, with specific equations for copolymers and terpolymers created by addition across single double bonds in the respective monomers. These relate intrinsic viscosity to both polymer MW and composition. Experimentally determined intrinsic viscosities were obtained for poly(styrene-acrylonitrile) in three solvents, DMF, THF, and MEK, and for poly(styrene-maleic anhydride-methyl methacrylate) in MEK as a function of MW and composition, where SEC/LALLS was used for MW characterization. Results demonstrate both the validity of the generalized equations for these systems and the limitations of the specific (numerical) expressions in particular solvents. 

Figure 2 shows survey Raman spectra of the hcmopolymers, poly(methyl methacrylate)(PMMA.), poly(3-oximino-2-hutannone methacrylate)(pom), and poly(methacrylonitrile)(PMAN), and one terpolymer(P(M-0M-CN)) with a S/N ratio of about 10 1. Each of the polymers has a band specific to that polymer 8l2 dcm-1 (vg (C-O-C) for IMMA), 1622 hem" (Vg(C=N) for POM), and 2237 dcm l(vg(CHN) for PMAN). Additionally, there is an asymmetric C-H bending mode at 1 53 Acm l, common to all three homopolymers, which serves as an internal standard. These bands are indicated by arrows in Figure 2. A broad fluorescence background is evident, but it can be reduced to acceptable levels by exposure to high laser power for 10-30 minutes, depending on the sample. Residual background fluorescence may be due to the oximino chromophore itself. Figure 3 depicts an example of actual data for a 75 15 10 terpolymer with a S/N ratio of about 50 1.

As a result of specific interactions, molecules of one component are surrounded by molecules of the second component in the segments of helix form. On the basis of these findings it is possible to assume that similar structures are formed during polymerization of methyl methacrylate in the presence of the isotactic template, or polymerization of methacrylic acid in the presence of poly(L-lysine). However, more experimental results are still needed. 

The most widely used acrylic plastics are PMMA (Lucite) or copolymers of methyl methacrylate with small amounts (2 to 18%) of methyl or ethyl acrylate (Plexiglas). These commercial products, which are available as sheets and as molding powders, have a specific gravity of about 1.2, a heat deflection temperature of about 95 C, a refractive index of about 1.5, and a water absorption of 0.2%. PMMA is more resistant to impact than PS or glass, but its scratch resistance is inferior to that of glass,... 

In polymers that exhibit tacticity, the extent of the stereoregularity determines the crystallinity and the physical properties of the polymers. The placement of the monomer units in the polymer is controlled first by the steric and electronic characteristics of the monomer. However, the presence or absence of tacticity, as well as the type of tacticity, is controlled by the catalyst employed in the polymerization reaction. Some common polymers, which can be prepared in specific configuration, include poly(olefins), poly(styrene), poly(methyl methacrylate), and poly(butadiene). 

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