Poly copolymers films

Poly(phenylquinoxaline—arnide—imides) are thermally stable up to 430°C and are soluble in polar organic solvents (17). Transparent films of these materials exhibit electrical insulating properties. Quinoxaline—imide copolymer films prepared by polycondensation of 6,6 -meth5lene bis(2-methyl-3,l-benzoxazine-4-one) and 3,3, 4,4 -benzophenone tetracarboxyUc dianhydride and 4,4 -oxydianiline exhibit good chemical etching properties (18). The polymers are soluble, but stable only up to 200—300°C. 

Qiu et al. [241 have reported the synthesis of macromolecules having 4-tolylureido pendant groups, such as poly(N-acryloyl-N -4-tolylurea-cvi ethyl acrylate) [po-ly(ATU-co-EA)] 18, and poly(N-methacryloyl-A/ -4-tol-ylurea-co-EA) [poly(MTU-co-EA)] 19, from the copolymerization of ATU and MTU with EA, respectively. Graft copolymerization of acrylamide onto the surface of these two copolymer films took place using the Ce(lV) ion as initiator. The graft copolymerization is proposed as Scheme (12). 

ABA type poly(hydroxyethyl methacrylate) (HEMA) and PDMS copolymers were synthesized by the coupling reactions of preformed a,co-isocyanate terminated PDMS oligomers and amine-terminated HEMA macromonomers312). Polymerization reactions were conducted in DMF solution at 0 °C. Products were purified by precipitation in diethyl ether to remove unreacted PDMS oligomers. After dissolving in DMF/toluene mixture, copolymers were reprecipitated in methanol/water mixture to remove unreacted HEMA oligomers. Microphase separated structures were observed under transmission electron microscope, using osmium tetroxide stained thin copolymer films. 

Wang, Z., Masuo, S., Machida, S. and Itaya, A. (2007) Site-selective doping of dyes into polystyrene-fclock-Poly(4-vinyl pyridine) diblock copolymer films and selective laser... 

TiCU readily functionalizes hydrophilic polymers such as poly(vinyl alcohol), m-ciesol novolac and methacrylic acid copolymers as well as moderately hydrophobic polymers such as poly(methyl methacrylate), poly(vinyl acetate), poly(benzyl methacrylate) and fully acetylated m-cresol novolac. HCI4 did not react with poly(styrene) to form etch resistant films indicating that very hydrophobic films follow a different reaction pathway. RBS analysis revealed that Ti is present only on the surface of hydrophilic and moderately hydrophobic polymer films, whereas it was found diffused through the entire thickness of the poly(styrene) films. The reaction pathways of hydrophilic and hydrophobic polymers with HCI4 are different because TiCl is hydrolysed by the surface water at the hydrophilic polymer surfaces to form an etch resistant T1O2 layer. Lack of such surface water in hydrophobic polymers explains the absence of a surface TiC>2 layer and the poor etching selectivities. 

Fig. 2.63 Scanning electron micrograph showing a monolayer of pores in a PS-poly(para-phenylene) diblock copolymer film (Widawski et al. 1994). The scale bar represents 20//m.

Only recently first reports appeared describing the potential of the nanostructured thin block copolymer films for lithographic etching. A thin film of polystyrene-block-polybutadiene with a hexagonal cylindrical morphology where the poly-(butadiene) cylinders were oriented perpendicular to the substrate was deposited on a silicon wafer and selectively decomposed by treatment with ozone or converted with osmium tetroxide. By a subsequent reactive ion etching process the pattern could be inscribed into the surface of the silicon wafer yielding small holes or islands with a lattice constant of 27 nm and hole/island sizes of 13 nm [305,312]. 

In another report, a 50 nm thick poly(styrene-h-methylmethacrylate) block copolymer film with spherical domains was prepared on a sodium chloride monocrystal and coated by a thin layer of gold, replicating the domain pattern. Similar results were also obtained with poly(styrene-h-2-vinylpyridines) [113]. 

Systems that employed HREELS for interfacial-composition determinations included poly(ethylene oxide)-polystyrene diblock copolymer on Si wafers formaldehyde poly(oxymethylene) films on Cu(lOO) and Lang-muir-Blodgett films of 4,4 -oxydianiline-pyromellitic dianhydride polyimide on Au and on highly ordered pyrolytic graphite. ... 

Fig. 3.52 Left (a) Schematic of intermittent contact mode AFM and phase imaging right (b) intermittent contact AFM phase image of a 30 nm thin block copolymer films on silicon [(poly(isoprene)-b-poly(ferrocenyl dimethylsilane), 29 kg/mol/15 kg/mol], which displays a in-plane worm-like surface pattern of poly(ferrocenyl dimethylsilane) in a matrix of poly (isoprene). From the 2D FFT analysis (inset) an average repeat period of 33 nm was estimated. Reprinted with permission from [116]. Copyright 2000. American Chemical Society...

Local reactions take place, for instance, in unconventional lithography approaches. Here, the surface of a polystyrene-Woc -poly(ter/-butyl acrylate) (PS69o-fr-PtBA12io) block copolymer film comprising reactive ter/-butyl ester moieties at the film surface (skin layer of 8 nm thickness) is locally hydrolyzed by a reactant (trifluoro acetic acid) that is delivered by a soft elastomeric stamp, as shown in Fig. 4.38. Thus, the surface is locally modified to yield poly(acrylic acid), which possess higher friction forces than the unreacted tert-butylester region. 

Ethylene-tetrafluoroethylene copolymer 15.7 6 Poly-/)-xylylene film 410-590 32... 

The poly(vinylidene chloride) copolymer (Dow Chemical Co.) contained 80% vinylidene chloride and 20% acrylonitrile. A small amoxmt of a carbonyl-containing compound was the only impurity detected by means of the infrared spectra of a thin film of the copolymer. Films were prepared by the slow evaporation of tetrahydrofuran solutions otherwise they were handled in the same manner as the PMMA samples. 

Yu WH, Kang ET, Neoh KG. Controlled grafting of comb copolymer brushes on poly-(tetrafluoroethylene) films by surface-initiated living radical polymerizations. Langmuir 2005 21(l) 450-6. 

Jayasuriya AC, Schirokauer A, Scheinbeim JI (2001) Crystal-structure dependence of electroactive properties in differently prepared poly(vinylidene fluoride/hexafluoro-propylene) copolymer films. J Polym Sci Part B Polym Phys 39 2793... 

Wegener M, Hesse J, Richter K, Gerhard-Multhaupt R (2002) Ferroelectric polarization in stretched piezo- and pyroelectric poly(vinylidene fluoride-hexafluoropropylene) copolymer films. J Appl Phys 92 7442... 

Figure 2.13 Schematic illustration of the process of fabricating a porous PANI-NF film by a galvanostatic method using porous poly(styrene-block-2-vinylpyridine) diblock copolymer films as templates. (Reprinted with permission from Langmuir, One-Step Route to the Fabrication of Highly Porous Polyaniline Nanofiber Films by Using PS-b-PVP Diblock Copolymers as Templates by X. Li, S. Tian, Y. Ping et ai, 2 , 2 , 9393-9397. Copyright (2005) American Chemical Society)...

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