Reactive monomer

VDP processes using means other than the pyrolytic cleavage of DPX (Gorham process) to generate the reactive monomer are also known, although none are practiced commercially at the time of this writing (ca 1997). 

To an experienced operator trained in the handling of industrial chemicals, the dimers present Httle cause for concern in handling or storage. The finished polymer coating presents even less of a health problem contact with the reactive monomer is unlikely. In the ancillary operations, such as cleaning or adhesion promotion, the operator must observe suitable precautions. Before using the process chemicals, operators must read and understand the current Material Safety Data Sheets, which are available from the manufacturers. 

Peioxydicaibonates are efficient polymerization initiators for most vinyl monomer polymerizations, especially for monomers such as acrylates, ethylene, and vinyl chloride. They are particularly good initiators for less reactive monomers such as those containing aHyl groups. They are also effective for curing of unsaturated polyester mol ding resins. 

When using a cation source in conjunction with a Friedel-Crafts acid the concentration of growing centers is most often difficult to measure and remains unknown. By the use of stable carbocation salts (for instance trityl and tropyhum hexachloroantimonate) the uncertainty of the concentration of initiating cations is eliminated. Due to the highly reproducible rates, stable carbocation salts have been used in kinetic studies. Their use, however, is limited to cationicaHy fairly reactive monomers (eg, A/-vinylcarbazole, -methoxystyrene, alkyl vinyl ethers) since they are too stable and therefore ineffective initiators of less reactive monomers, such as isobutylene, styrene, and dienes. 

Figure 4c also describes the spontaneous polymerisation ofpara- s.yX en.e diradicals on the surface of soHd particles dispersed in a gas phase that contains this reactive monomer (16) (see XylylenePOLYMERS). The poly -xylylene) polymer produced forms a continuous capsule sheU that is highly impermeable to transport of many penetrants including water. This is an expensive encapsulation process, but it has produced capsules with impressive barrier properties. This process is a Type B encapsulation process, but is included here for the sake of completeness. 

Partial hydrolysis of a metal alkoxide to form reactive monomers. 

Amine Cross-Linking. Two commercially important, high performance elastomers which are not normally sulfur-cured are the fluoroelastomers (FKM) and the polyacrylates (ACM). Polyacrylates typically contain a small percent of a reactive monomer designed to react with amine curatives such as hexamethylene-diamine carbamate (Diak 1). Because the type and level of reactive monomer varies with ACM type, it is important to match the curative type to the particular ACM ia questioa. Sulfur and sulfur-beating materials can be used as cure retarders they also serve as age resistors (22). Fluoroelastomer cure systems typically utilize amines as the primary cross-linking agent and metal oxides as acid acceptors. 

Complexation of the initiator and/or modification with cocatalysts or activators affords greater polymerization activity (11). Many of the patented processes for commercially available polymers such as poly(MVE) employ BE etherate (12), although vinyl ethers can be polymerized with a variety of acidic compounds, even those unable to initiate other cationic polymerizations of less reactive monomers such as isobutene. Examples are protonic acids (13), Ziegler-Natta catalysts (14), and actinic radiation (15,16). 

Although reactivity ratios indicate that VP is the more reactive monomer, reaction conditions such as solvent polarity, initiator type, percent conversion, and molecular weight of the growing radical can alter these ratios (138). Therefore, depending on polymerization conditions, copolymers produced by one manufacturer may not be identical to those of another, especially if the end use appHcation of the resin is sensitive to monomer sequence distribution and MWD. 

Thermosetting Reactive Polymers. Materials used as thermosetting polymers include reactive monomers such as urea—formaldehyde, phenoHcs, polyesters, epoxides, and vinyls, which form a polymerized material when mixed with a catalyst. The treated waste forms a sponge-like material which traps the soHd particles, but not the Hquid fraction the waste must usually be dried and placed in containers for disposal. Because the urea—formaldehyde catalysts are strongly acidic, urea-based materials are generally not suitable for metals that can leach in the untrapped Hquid fractions. Thermosetting processes have greater utiHty for radioactive materials and acid wastes. 

Surface modification of a contact lens can be grouped into physical and chemical types of treatment. Physical treatments include plasma treatments with water vapor (siUcone lens) and oxygen (176) and plasma polymerization for which the material surface is exposed to the plasma in the presence of a reactive monomer (177). Surfaces are also altered with exposure to uv radiation (178) or bombardment with oxides of nitrogen (179). Ion implantation (qv) of RGP plastics (180) can greatiy increase the surface hardness and hence the scratch resistance without seriously affecting the transmission of light. 

In order to enhance the reactivity of the chlorine atom, a second reactive monomer can be adopted giving dual cure sites. According to the Hterature, the second monomer can contain carboxyl (22—24), cyanoalkyl (25), hydroxypropyl (26), or epoxy groups (27,28). 

Many other acids, glycols and reactive monomers have been described in the literature but these remain of either minor or academic importance. In a number of cases this is simply because of the high cost of the chemical and a reduction in cost due to its widespread use in some other application could well lead to extensive use in polyester resins. 

Intentional hranching may improve the properties of the product polymer through grafting. A graft copolymer can he obtained by creating active sites on the polymer backbone. The addition of a different monomer then reacts at the active site and forms a branch. For example, polyethylene irradiated with gamma rays and then exposed to a reactive monomer, such as acrylonitrile, produces a polyethylene-polymer with acrylonitrile branches ... 

Polymerization reactions can occur in bulk (without solvent), in solution, in emulsion, in suspension, or in a gas-phase process. Interfacial polymerization is also used with reactive monomers, such as acid chlorides. 

Interfacial polymerization is mainly used in polycondensation reactions with very reactive monomers. One of the reactants, usually an acid... 

The values of these ratios change appreciably by passing from the heterogeneous (suspension) to the homogeneous (DMF) system. In the case of copolymerization in suspension in the presence of the K2S208—AgN03 oxidation-reduction system at 30—40 °C, the ratios were found to be ry = 0,77 0,2 and r2 = 1,09 0,04, whereas in the case of the copolymerization in solution they are = 0,52 and r2 = 1,7. The difference in these values seems to be the result of the different solubility of the monomers in water and of the different rate of diffusion of the monomers to the surface of the precipitated copolymer20. From this it follows that 4 is the more reactive monomer in this binary system. 

This peculiar form applies when a dimeric molecule dissociates to a reactive monomer that then undergoes a first-order or pseudo-first-order reaction. This scheme is considered in Section 4.3. Unless one can work at either of the limits, the form is such that a numerical solution or the method of initial rates will be needed, since the integrated equation has no solution for [A]r. 

Electron-donating groups strongly activate sulfonylation at ortho or para positions, with para sulfonylation more favored due to less steric hindrance. Variables, such as highly reactive monomers, elevated reaction temperatures, and high... 

The difficulties encountered in the early studies of anionic polymerization of methyl methacrylate arose from the unfortunate choice of experimental conditions the use of hydrocarbon solvents and of lithium alkyl initiators. The latter are strong bases. Even at —60 °C they not only initiate the conventional vinyl poly-addition, but attack also the ester group of the monomer yielding a vinyl ketone1, a very reactive monomer, and alkoxide 23). Such a process is described by the scheme. 

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