Polymerizability

While most vesicles are formed from double-tail amphiphiles such as lipids, they can also be made from some single chain fatty acids [73], surfactant-cosurfactant mixtures [71], and bola (two-headed) amphiphiles [74]. In addition to the more common spherical shells, tubular vesicles have been observed in DMPC-alcohol mixtures [70]. Polymerizable lipids allow photo- or chemical polymerization that can sometimes stabilize the vesicle [65] however, the structural change in the bilayer on polymerization can cause giant vesicles to bud into smaller shells [76]. Multivesicular liposomes are collections of hundreds of bilayer enclosed water-filled compartments that are suitable for localized drug delivery [77]. The structures of these water-in-water vesicles resemble those of foams (see Section XIV-7) with the polyhedral structure persisting down to molecular dimensions as shown in Fig. XV-11. 

Surfactants provide temporary emulsion droplet stabilization of monomer droplets in tire two-phase reaction mixture obtained in emulsion polymerization. A cartoon of tliis process is given in figure C2.3.11. There we see tliat a reservoir of polymerizable monomer exists in a relatively large droplet (of tire order of tire size of tire wavelengtli of light or larger) kinetically stabilized by surfactant. 

The generally low chemical, mechanical and thennal stability of LB films hinders their use in a wide range of applications. Two approaches have been studied to solve this problem. One is to spread a polymerizable monomer on the subphase and to polymerize it either before or following transfer to the substrate. The second is to employ prefonned polymers containing hydrophilic and hydrophobic groups. 

Uchida M, Tanizaki T, Gda T and Ka]iyama T 1991 Control of surface chemical-structure and functional property of Langmuir-Blodgett-film composed of new polymerizable amphiphile with a sodium-sulfonate Maoromoieouies 24 3238-43... 

Elbert R, Laschewsky A and Ringsdorf H 1985 Hydrophilic spacer groups in polymerizable lipids— formation of biomembrane models from bulk polymerized lipids J. Am. Ohem. Soc. 107 4134-41... 

It might be noted that most (not all) alkenes are polymerizable by the chain mechanism involving free-radical intermediates, whereas the carbonyl group is generally not polymerized by the free-radical mechanism. Carbonyl groups and some carbon-carbon double bonds are polymerized by ionic mechanisms. Monomers display far more specificity where the ionic mechanism is involved than with the free-radical mechanism. For example, acrylamide will polymerize through an anionic intermediate but not a cationic one, A -vinyl pyrrolidones by cationic but not anionic intermediates, and halogenated olefins by neither ionic species. In all of these cases free-radical polymerization is possible. 

Fig. 7. Chemistiy of a diy-filin, negative-acting photoresist, (a) Polymerizable layer sandwiched between a polyolefin carrier sheet and a polyester cover...

The utihty of these adhesives arises from the electron-withdrawing character of the groups adjacent to the polymerizable double bond, which accounts for both the extremely high reactivity or cure rate and thek polar nature, which enables the polymers to adhere tenaciously to many diverse substrates. 

In order to faciUtate heat transfer of the exothermic polymerization reaction, and to control polymerizate viscosity, percent reactives are adjusted through the use of inert aromatic or aUphatic diluents, such as toluene or heptane, or higher boiling mixed aromatic or mixed aUphatic diluents. Process feed streams are typically adjusted to 30—50% polymerizable monomers. 

Polymerizations are typically quenched with water, alcohol, or base. The resulting polymerizates are then distilled and steam and/or vacuum stripped to yield hard resin. Hydrocarbon resins may also be precipitated by the addition of the quenched reaction mixture to an excess of an appropriate poor solvent. As an example, aUphatic C-5 resins are readily precipitated in acetone, while a more polar solvent such as methanol is better suited for aromatic C-9 resins. 

G-9 Aromatic Petroleum Resins. Feedstocks typically used for aromatic petroleum resin synthesis boil in the approximate range of 100—300°C at atmospheric pressure, with most boiling in the 130—200°C range. The C-9 designation actually includes styrene (C-8) through C-10 hydrocarbons (eg, methylindene). Many of the polymerizable monomers identified in Table 1 for coumarone—indene type cmdes from coal tar are also present in aromatic fractions from cracked petroleum distillates. Therefore, the technology developed for the polymerization of coal-tar cmdes is also appHcable to petroleum-derived aromatic feedstocks. In addition to availabiHty, aromatic petroleum resins offer several advantages over coumarone—indene resins. These include improved color and odor, as weU as uv and thermal stabiHty (46). 

The majority of thermal polymerizations are carried out as a batch process, which requires a heat-up and a cool down stage. Typical conditions are 250—300°C for 0.5—4 h in an oxygen-free atmosphere (typically nitrogen) at approximately 1.4 MPa (200 psi). A continuous thermal polymerization has been reported which utilizes a tubular flow reactor having three temperature zones and recycle capabiHty (62). The advantages of this process are reduced residence time, increased production, and improved molecular weight control. Molecular weight may be controlled with temperature, residence time, feed composition, and polymerizate recycle. 

Methacrylate monomers do not generally polymerize by a cationic mechanism. In fact, methacrylate functionaUty is often utilized as a passive pendent group for cationicaHy polymerizable monomers. Methacrylate monomers also have been used as solvents or cosolvents for cationic polymerizations (90,91). 

Block, Gr ft, ndSta.r Copolymers. A host of copolymers of these types have been prepared. They iaclude block copolymers from S-caprolactam and PTMEG as well as block copolymers from PTHF and other cationicaHy polymerizable heterocycles, including... 

Equation 1 is an oversimplification of the actual process. The polymerizable sulfur source for the PPS polymerization consists of a dehydrated product of A/-meth5i-2-pyrrohdinone [872-50-4] (NMP) and aqueous sodium sulfide feedstocks. During the course of this dehydration, one equivalent of NMP is hydrolyzed to form sodium A/-methyl-4-aminobutanoate (SMAB) (eq. 3). 

Aniline—formaldehyde resins were once quite important because of their excellent electrical properties, but their markets have been taken over by newer thermoplastic materials. Nevertheless, some aniline resins are stiU. used as modifiers for other resins. Acrylamide (qv) occupies a unique position in the amino resins field since it not only contains a formaldehyde reactive site, but also a polymerizable double bond. Thus it forms a bridge between the formaldehyde condensation polymers and the versatile vinyl polymers and copolymers. 

LB Films of Polymerizable Amphiphiles. Stxidies of LB films of polymerizable amphiphiles include simple olefinic amphiphiles, conjugated double bonds, dienes, and diacetylenes (4). In general, a monomeric ampbipbile can be spread and polymerization can be induced either at tbe air—water interface or after transfer to a soHd substrate. Tbe former polymerization results in a rigid layer tbat is difficult to transfer. 

The catalysts are primarily DCPD-soluble derivatives of tungsten and molybdenum and the activators are aluminum alkyls (63—64). Polymerization is accompHshed by mixing equal amounts of Hquid DCPD (at >32° C), one part of which contains the catalyst and the other of which contains the activator. The mixture is rapidly injected into a mold, where the polymerization takes place. Polymerization times are from under 30 seconds to several minutes, depending on the size of the part, mold temperature, and modifiers added to the polymerizate. 

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