Olefin sulfone copolymer

Ethoxylated methylcarboxylates Propoxyethoxy glyceryl sulfonate Alkylpropoxyethoxy sulfate as surfactant, xanthan, and a copolymer of acrylamide and sodium 2-acrylamido-2-methylpropane sulfonate Carboxymethylated ethoxylated surfactants (CME) Polyethylene oxide (PEG) as a sacrificial adsorbate Polyethylene glycols, propoxylated/ethoxylated alkyl sulfates Mixtures of sulfonates and nonionic alcohols Combination of lignosulfonates and fatty amines Alkyl xylene sulfonates, polyethoxylated alkyl phenols, octaethylene glycol mono n-decyl ether, and tetradecyl trimethyl ammonium chloride Anionic sodium dodecyl sulfate (SDS), cationic tetradecyl trimethyl ammonium chloride (TTAC), nonionic pentadecylethoxylated nonylphenol (NP-15), and nonionic octaethylene glycol N-dodecyl ether Dimethylalkylamine oxides as cosurfactants and viscosifiers (N-Dodecyl)trimethylammonium bromide Petrochemical sulfonate and propane sulfonate of an ethoxylated alcohol or phenol Petrochemical sulfonate and a-olefin sulfonate... 

Another class of "chain scission" positive resists is the poly(olefin sulfones). These polymers are alternating copolymers of an olefin and sulfur dioxide. The relatively weak C-S bond is readily cleaved upon irradiation and several sensitive resists have been developed based on this chemistry (49,50). One of these materials, poly(butene-l sulfone) (PBS) has been made commercially available for mask making. PBS exhibits an e-beam sensitivity of 1.6 pC cm-2 at 20 kV and 0.25 pm resolution. 

Stumpe and co-workers [50] have investigated the photochemistry of SCLC poly(olefin sulfone)s such as 20 and a copolymer with the same main chain but with 95% of the cinnamate groups replaced with saturated tetradecyl groups. As cast or heat-treated thin films of the polymers were irradiated at 313 nm using both nonpolarized and linearly polarized light. Initial irradiation led to an initial increase in the absorbance of the films at 280 nm followed by a decrease. The... 

The Incorporation of a weak link In the main chain of a olefin sulfone copolymer such as poly - 1 -butene sulfone Is a recent example of po mers with high G value and high sensitivity 10 coul/sq. cm. 

A free radical polymerization reaction in the presence of a peroxide or hydroperoxide can take place between an olefin and SO2. The resulting poly(olefin sulfone) may have a variable composition (variable content of SO2), but poIy(ethylene-a/f-sulfur dioxide), CAS 110711-58-5, or poly(ethylene sulfone) can be obtained. Different olefins can be used in the reaction, as well as butadiene. Poly(sulfur dioxide-co-alkenes) may have a variable composition from 1.1 mole ratio (a/t copolymer) to various other monomer ratios. 

The use of poly(olefin sulfones) in resist applications was first demonstrated by Bowden and Thompson at Bell lahoratories. They prepared them hy radical copolymerization of (liquid) SO2 with a whole range of olefins, at reaction temperatures deliberately kept low because of the low ceiling temperatures of poly(afk-ene sulfones). For poly(butene sulfone), Tc 64°C. The resulting copolymers possess a regular 1 1 alternating composition. 

Polytetramethylene ether glycol diamine Polyurethane, thermoplastic Polyvinyl butyral Pyridine Ricinoleic acid Sodium o olefin sulfonate Styrene-ethylene/butylene-styrene block copolymer Styrene/MA copolymer Sucrose octaacetate Tall oil glycerides... 

PEG-30 sorbitan tetraoleate PEG-40 sorbitan tetraoleate PEG-60 sorbitan tetraoleate PEG soyamine PEG-2 tallowate Polysorbate 61 Potassium cetyl phosphate PVM/MA copolymer Sodium cocoamphopropionate Sodium C14-16 olefin sulfonate... 

Potassium castor oil sulfate Potassium stearate PPG-5-ceteth-10 phosphate PPG-10 cetyl ether PPG-10 cetyl ether phosphate PPG-9 diethylmonium chloride PPG-40 diethylmonium chloride PPG-1 hydroxyethyl caprylamide PPG-2 hydroxyethyl cocamide PPG-3 hydroxyethyl linoleamide Ricinoleamidopropyl trimonium methosulfate Silicone glycol copolymer Silicone quaternium-2 Sodium C12-15 alkoxypropyl iminodipropionate Sodium C8-10 all l sulfate Sodium carboxyethyl tallowpolypropylamine Sodium cetearyl sulfate Sodium C14-16 olefin sulfonate Sodium C12-15 pareth-3 sulfonate Sodium C12-15 pareth-7 sulfonate Sodium C12-15 pareth-15 sulfonate Sodium laureth-4 carboxylate Sodium laureth-7... 

Poly(olefin sulfones), alternating copolymers of sulfur dioxide and an olefin, are another important class of positive resists, which exhibit a very high sensitivity [35] owing to the weak carbon-sulfur bond (see Figure 6.19). Poly(butene-l-sulfone) shows the best properties (o = 1.6 pC/cm at 20 kV) and is commercially available. 

Water-soluble l,3-bis(di(hydroxyalkyl)phosphino)propane derivatives were thoroughly studied as components of Pd-catalysts for CO/ethene (or other a-olefins) copolymerization and for the terpolymerization of CO and ethene with various a-olefins in aqueous solution (Scheme 7.17) [59], The ligands with long hydroxyalkyl chains consistently gave catalysts with higher activity than sulfonated DPPP and this was even more expressed in copolymerization of CO with a-olefins other than ethene (e.g. propene or 1-hexene). Addition of anionic surfactants, such as dodecyl sulfate (potassium salt) resulted in about doubling the productivity of the CO/ethene copolymerization in a water/methanol (30/2) solvent (1.7 kg vs. 0.9 kg copolymer (g Pd)" h" under conditions of [59]) probably due to the concentration of the cationic Pd-catalyst at the interphase region or around the micelles which solubilize the reactants and products. Unfortunately under such conditions stable emulsions are formed which prevent the re-use... 

PBS (Figure 30) is an alternating copolymer of sulfur dioxide and 1-butene. It undergoes efficient main chain scission upon exposure to electron beam radiation to produce, as major scission products, sulfur dioxide and the olefin monomer. Exposure results first in scission of the main chain carbon-sulfur bond, followed by depolymerization of the radical (and cationic) fragments to an extent that is temperature dependent and results in evolution of the volatile monomers species. The mechanism of the radiochemical degradation of polyolefin sulfones has been the subject of detailed studies by O Donnell et. al. (.41). 

The other major class of positive resists is based on polyfolefin sulfones) which are alternating copolymers of sulfur dioxide and the respective olefin having the general structure. 

Since the mid-fifties sulfonated resins based on styrene/divinylbenzene copolymers, initially developed as ion exchangers mainly for water treatment, nave also been used as strongly acidic solid catalysts. Witn few exceptions, industrial application in continuous processes is limited to the manufacture of bulk chemicals, sucn as Disphenol A, (meth)acrylates, metnyl ethers of branched olefins (MTBE, TAME) and secondary alcohols (IPA, SBA). 

Examples are the sulfonating of polyethylene film with chloro-sulfonic acid (60) the sulfonating of sheets of phenolformaldehyde resin (77) the treatment of a film consisting of polystyrene and polyvinylchloride with concentrated sulfuric acid (4) the sulfonating of films consisting of aliphatic vinylpolymers with chlorosulfonic acid (125) the sulfonating of copolymers of a monovinyl- and a polyvinyl compound (30). Also are used copolymers of aromatic monovinyl-compounds and linear aliphatic polyene hydrocarbons (3) copolymers of an unsaturated aromatic compound and an unsaturated aliphatic compound (76), and of reaction products of poly olefines and partially polymerized styrene (173). 

MC MDI MEKP MF MMA MPEG MPF NBR NDI NR OPET OPP OSA PA PAEK PAI PAN PB PBAN PBI PBN PBS PBT PC PCD PCT PCTFE PE PEC PEG PEI PEK PEN PES PET PF PFA PI PIBI PMDI PMMA PMP PO PP PPA PPC PPO PPS PPSU Methyl cellulose Methylene diphenylene diisocyanate Methyl ethyl ketone peroxide Melamine formaldehyde Methyl methacrylate Polyethylene glycol monomethyl ether Melamine-phenol-formaldehyde Nitrile butyl rubber Naphthalene diisocyanate Natural rubber Oriented polyethylene terephthalate Oriented polypropylene Olefin-modified styrene-acrylonitrile Polyamide Poly(aryl ether-ketone) Poly(amide-imide) Polyacrylonitrile Polybutylene Poly(butadiene-acrylonitrile) Polybenzimidazole Polybutylene naphthalate Poly(butadiene-styrene) Poly(butylene terephthalate) Polycarbonate Polycarbodiimide Poly(cyclohexylene-dimethylene terephthalate) Polychlorotrifluoroethylene Polyethylene Chlorinated polyethylene Poly(ethylene glycol) Poly(ether-imide) Poly(ether-ketone) Polyethylene naphthalate Polyether sulfone Polyethylene terephthalate Phenol-formaldehyde copolymer Perfluoroalkoxy resin Polyimide Poly(isobutylene), Butyl rubber Polymeric methylene diphenylene diisocyanate Poly(methyl methacrylate) Poly(methylpentene) Polyolefins Polypropylene Polyphthalamide Chlorinated polypropylene Poly(phenylene oxide) Poly(phenylene sulfide) Poly(phenylene sulfone)... 

Ionomers of practical interest have been prepared by two synthetic routes (a) copolymerization of a low level of functionalized monomer with an olefinically unsaturated monomer or (b) direct functionalization of a preformed polymer. Typically, carboxyl containing ionomers are obtained by direct copolymerization of acrylic or methacrylic acid with ethylene, styrene and similar comonomers by free radical copoly-merization. Rees (22) has described the preparation of a number of such copolymers. The resulting copolymer is generally available as the free acid which can be neutralized to the degree desired with metal hydroxides, acetates and similar salts. Recently, Weiss et al.(23-26) have described the preparation of sulfonated ionomers by copolymerization of sodium styrene sulfonate with butadiene or styrene. 

Marvel reported that propylene and cyclohexene react with sulfiir dioxide to form alternating copolymers of olefin and sulfiir dioxide in a head-to-tail arrangement [2,4], Staudinger reported that 1,3-butadiene reacts with sulfur dioxide to form a cyclic sulfone and an amorphouse linear polysulfone [3,3a, 5]. 

The preparation of ionomers involves either the copolymerization of a functionalized monomer with an olefinic unsaturated monomer or direct functionalization of a preformed polymer. Typically, free-radical copolymerization of ethylene, styrene, or other a-olefins with acrylic acid or methacrylic acid results in carboxyl-containing ionomers. The copolymer, available as a free acid, is then neutralized partially to a desired degree with metal hydroxides, acetates, or similar salts. The second route for the preparation of ionomers involves modification of a preformed polymer. For example, sulfonated polystyrene is obtained by direct sulfonation of polystyrene in a homogeneous solution followed by neutralization of the acid to the desired level. Some commercially available ionomers are listed in Table 15.17. 

PEG cocamine PEG-9 laurate PEG-2 oleamine PEG stearamine Phenol-formaldehyde sulfonate PPG-3-myreth-3 Sodium caprylyl sulfonate Sodium C4-12 olefin/maleic acid copolymer Sodium oleic sulfate Sodium polynaphthalene sulfonate Stearamine oxide Sulfonic acid Tetramethyl decynediol Tetrasodium pyrophosphate Triethanolamine dispersant, dyes acetate... 

Sodium C4-12 olefin/maleic acid copolymer Sodium decyl sulfate Sodium polycarboxylate Sodium polymethacrylate Sodium polynaphthalene sulfonate Sodium tallate Soyamide DEA Stearamide Stearamine Styrene/MA copolymer Tall oil acid Tall oil hydroxyethyl imidazoline Tallow dipropylene triamine TEA-dodecylbenzenesulfonate Tricontanyl PVP Tridecyl neopentanoate Tridecyl trimellitate Triisocetyl citrate Trioctyidodecyl citrate dispersant, pigment dispersions Disodium decyl diphenyl ether disulfonate lsotrideceth-9 Octoxynol-11... 

PVP/dimethylaminoethylmethacrylate copolymer PVP/VA copolymer Quatemium-18 methosulfate Sandarac (Callitris quadrivalvis) gum Scleroglucan Sclerotium gum 3-Sitosterol Sodium acrylate/vinyl alcohol copolymer Sodium carrageenan Sodium cellulose sulfate Sodium C4-12 olefin/maleic acid copolymer Sodium cyclodextrin sulfate Sodium polymethacrylate Sodium polynaphthalene sulfonate Sodium polystyrene sulfonate Sorbitan myristate Soyamide DEA Soybean (Glycine soja) sterol Stearic acid Stearyl alcohol... 

A wide range of dithioester RAFT agents has been reported. Common examples of mono-RAFT agents and their application are provided in Tables 11 (Z = aryl) and 13 (Z = alkyl or aralkyl). RAFT agents can contain various unprotected functionality on the R fragment of dithiobenzoate including hydroxy, carboxylic acid/carboxylate, sulfonic acid/sulfonate, olefin, and siloxane. Examples of bis- and multi-dithioester RAFT agents (Z=aryl) that may be used for triblock or star synthesis are shown in Tables 12 and 22, respectively. Bis-dithioesters can be used to synthesize triblock copolymers in a two-step process. 

Phosphine Sulfonate-Based Catalysts Synthesis of Linear Copolymers of Ethene and Functionalized Olefins 816... 

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