Monolayer polymerization

Monolayer Polymerization. Polymerization of the highly ori-ented monomer films can simply be achieved by UV irradiation under nitrogen (Figure 8.). The polymerization of the diacetylene monomers (2, 5-9) is a topochemical reaction (32,38) that only takes place, if the monomers are perfectly orderecTT i.e. in the crystalline state or in oriented mono- (32) or multilayers (39) and leads to the formation of conjugated Tlue and red colorecT polymer backbones (Eqn. I.). 

Due to the low preparation cost, monolayer polymeric membranes have been widely used as separators for LIBs. However, limited by the relatively single function of mono-layer polymeric membranes with relatively poor puncture strength and thermal stability, monolayer polymeric membranes may not be able to meet many application demands. 

Monolayer polymeric membranes cannot satisfy all of the optimal characteristics that are related to the LIB safety and performance. Therefore, microporous multilayer separators combining different polymers with different functions have been fabricated. A variety of... 

Day, D. and J.B. Lando. 1980. Morphology of crystalline diacetylene monolayers polymerized at the gas-water interface. Macromolecules 13 1478. 

A similar although not topochemieally governed ap-proaeh to polymerize thiol-bearing monomers has been recently reported using mercaptomethyl styrene monomer [26]. Assembly of the monomer into dense-paeked mono-layers on gold is followed by free radical- or photo-induced polymerization in situ. Presence of httle residual monomer or ohgomer by mass spectrometry supports other speetroseopie evidence for monolayer polymerization. 

Since the polymer ist stron y birefringent, the crystalline morphology of individual monolayers can easily be visualized between crossed polarizers in an optical microscope Monolayers polymerized at the air-water interface and... 

Polymer monolayers. Polymeric spread films at the air-water interface are examples of polymers in pseudo-two-dimensional situations. The nature of such films is germane to the preparation of Langmuir-Blodgett films. 

The monolayer polymerization of substituted butadienes (9) is also well known [25]. The aqueous subphase is critical for the materials, since it provides the vehicle for orienting the molecules such that polymerization can take place. The polymerization of other forms of these materials (crystalline, solution or melt) was found to be unsuccessful. 

Barnes and co-workers have studied mixed-monolayer systems [278,281,283,284] and found some striking nonidealities. Mixed films of octadecanol and cholesterol, for example, show little evaporation resistance if only 10% cholesterol is present [278] apparently due to an uneven granular microstructure in films with cholesterol [284]. Another study of cellulose decanoate films showed no correlation between holes in the monolayer and permeation rate [285]. Polymerized surfactants make relatively poor water evaporation retarders when compared to octadecanol [286]. There are problems in obtaining reproducible values for r [287] due to impurities in the monolayer material or in the spreading solvent. 

Photopolymerization reactions of monolayers have become of interest (note Chapter XV). Lando and co-workers have studied the UV polymerization of 16-heptadecenoic acid [311] and vinyl stearate [312] monolayers. Particularly interesting is the UV polymerization of long-chain diacetylenes. As illustrated in Fig. IV-30, a zipperlike process can occur if the molecular orientation in the film is just right (e.g., polymerization does not occur readily in the neat liquid) (see Refs. 313-315). 

Chemical properties of deposited monolayers have been studied in various ways. The degree of ionization of a substituted coumarin film deposited on quartz was determined as a function of the pH of a solution in contact with the film, from which comparison with Gouy-Chapman theory (see Section V-2) could be made [151]. Several studies have been made of the UV-induced polymerization of monolayers (as well as of multilayers) of diacetylene amphiphiles (see Refs. 168, 169). Excitation energy transfer has been observed in a mixed monolayer of donor and acceptor molecules in stearic acid [170]. Electrical properties have been of interest, particularly the possibility that a suitably asymmetric film might be a unidirectional conductor, that is, a rectifier (see Refs. 171, 172). Optical properties of interest include the ability to make planar optical waveguides of thick LB films [173, 174]. 

For structures with a high curvature (e.g., small micelles) or situations where orientational interactions become important (e.g., the gel phase of a membrane) lattice-based models might be inappropriate. Off-lattice models for amphiphiles, which are quite similar to their counterparts in polymeric systems, have been used to study the self-assembly into micelles [ ], or to explore the phase behaviour of Langmuir monolayers [ ] and bilayers. In those systems, various phases with a nematic ordering of the hydrophobic tails occur. 

Biddle M B, Lando J B, Ringsdorf H, Schmidt G and Schneider J 1988 Polymeric amphiphiles with hydrophilic main chain spacers—studies in monolayers and Langmuir-Blodgett multilayers Oollold Polymer Scl. 266 806-13... 

Sun F, Castner D G and Grainger D W Ultrathin 1993 Self-assembled polymeric films on solid-surfaces. 2. Formation of 11-(n-pentyldithio)undecanoate-bearing polyacrylate monolayers on gold Langmuirs 3200-7... 

In tbe first attempt to prepare a two-dimensional crystalline polymer (45), Co y-radiation was used to initiate polymerization in monolayers of vinyl stearate (7). Polymerization at the air—water interface was possible but gave a rigid film. The monomeric monolayer was deposited to give X-type layers that could be polymerized in situ This polymerization reaction, quenched by oxygen, proceeds via a free-radical mechanism. 

The pursuit of further miniaturization of electronic circuits has made submicrometer resolution Hthography a cmcial element in future computer engineering. LB films have long been considered potential candidates for resist appHcations, because conventional spin-coated photoresist materials have large pinhole densities and variations of thickness. In contrast, LB films are two-dimensional, layered, crystalline soHds that provide high control of film thickness and are impermeable to plasma down to a thickness of 40 nm (46). The electron beam polymerization of CO-tricosenoic acid monolayers has been mentioned. Another monomeric amphiphile used in an attempt to develop electron-beam-resist materials is a-octadecylacryUc acid (8). 

LB Films of Polymeric Amphiphile. Since the first successful deposition of a polymeric LB film (61), there have been a large number of studies examining different stmctural parameters on the transferabiHty and stabiHty of the polymeric LB films (4). One interesting idea for polymers for LB films is the use of a spacer group (mosdy hydrophilic) to decouple the motion of the polymer from that of the Hpid membrane (62,63). Monolayers from a poljmier (10) having hydrophilic phosphate groups and a tetraethylene oxide spacer were used to link a glycerol diether to the polymer chain (63). 

High quahty SAMs of alkyltrichlorosilane derivatives are not simple to produce, mainly because of the need to carefully control the amount of water in solution (126,143,144). Whereas incomplete monolayers are formed in the absence of water (127,128), excess water results in facile polymerization in solution and polysiloxane deposition of the surface (133). Extraction of surface moisture, followed by OTS hydrolysis and subsequent surface adsorption, may be the mechanism of SAM formation (145). A moisture quantity of 0.15 mg/100 mL solvent has been suggested as the optimum condition for the formation of closely packed monolayers. X-ray photoelectron spectroscopy (xps) studies confirm the complete surface reaction of the —SiCl groups, upon the formation of a complete SAM (146). Infrared spectroscopy has been used to provide direct evidence for the hiU hydrolysis of methylchlorosilanes to methylsdanoles at the soHd/gas interface, by surface water on a hydrated siUca (147). 

Patterns of ordered molecular islands surrounded by disordered molecules are common in Langmuir layers, where even in zero surface pressure molecules self-organize at the air—water interface. The difference between the two systems is that in SAMs of trichlorosilanes the island is comprised of polymerized surfactants, and therefore the mobihty of individual molecules is restricted. This lack of mobihty is probably the principal reason why SAMs of alkyltrichlorosilanes are less ordered than, for example, fatty acids on AgO, or thiols on gold. The coupling of polymerization and surface anchoring is a primary source of the reproducibihty problems. Small differences in water content and in surface Si—OH group concentration may result in a significant difference in monolayer quahty. Alkyl silanes remain, however, ideal materials for surface modification and functionalization apphcations, eg, as adhesion promoters (166—168) and boundary lubricants (169—171). 

Adsorption of dispersants at the soHd—Hquid interface from solution is normally measured by changes in the concentration of the dispersant after adsorption has occurred, and plotted as an adsorption isotherm. A classification system of adsorption isotherms has been developed to identify the mechanisms that may be operating, such as monolayer vs multilayer adsorption, and chemisorption vs physical adsorption (8). For moderate to high mol wt polymeric dispersants, the low energy (equiUbrium) configurations of the adsorbed layer are typically about 3—30 nm thick. Normally, the adsorption is monolayer, since the thickness of the first layer significantly reduces attraction for a second layer, unless the polymer is very low mol wt or adsorbs by being nearly immiscible with the solvent. 

If the swelling effects in the polymeric phase are considered, the evaluation of the adsorbed macromolecules as a monolayer seems to be too approximate. The mean-square end-to-end distance of the polystyrene coil (M = 10000) in... 

Dorn, K., Hupfer, B., and Ringsdorf, H. Polymeric Monolayers and Liposomes as Models for Biomembranes How to Bridge the Gap Between Polymer Science and Membrame Biology Vol. 64, pp. 1 —54. 

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