Modified poly

Poly(methyl methacrylate) Cast sheet Impact- modified Heat- resistant ... 

SAN modifier [ACRYLONITRILE POLYTffiRS - SURVEY AND SAN (STYRENE-ACRYLONITRHE CO-POLYTffiRS)] (Vol 1) Poly(ethylene-co-vinyl alcohol)... 

Materials that typify thermoresponsive behavior are polyethylene—poly (ethylene glycol) copolymers that are used to functionalize the surfaces of polyethylene films (smart surfaces) (20). When the copolymer is immersed in water, the poly(ethylene glycol) functionaUties at the surfaces have solvation behavior similar to poly(ethylene glycol) itself. The abiUty to design a smart surface in these cases is based on the observed behavior of inverse temperature-dependent solubiUty of poly(alkene oxide)s in water. The behavior is used to produce surface-modified polymers that reversibly change their hydrophilicity and solvation with changes in temperatures. Similar behaviors have been observed as a function of changes in pH (21—24). 

The protonated form of poly(vinyl amine) (PVAm—HCl) has two advantages over many cationic polymers high cationic charge densities are possible and the pendent primary amines have high reactivity. It has been appHed in water treatment, paper making, and textiles (qv). The protonated forms modified with low molecular weight aldehydes are usehil as fines and filler retention agents and are in use with recycled fibers. As with all new products, unexpected appHcations, such as in clear antiperspirants, have been found. It is usehil in many metal complexation appHcations (49). 

HydrophobicaHy Modified, Ethoxylated Urethane. HEUR associative thickeners are in effect poly(oxyethylene) polymers that contain terminal hydrophobe units (66). They can be synthesized via esterification with monoacids, tosylation reactions, or direct reaction with monoisocyanates. There are problems associated with aH of the methods of synthesis. The general commercial procedure for their synthesis is by a step-growth addition of... 

Acrylics. Acetone is converted via the intermediate acetone cyanohydrin to the monomer methyl methacrylate (MMA) [80-62-6]. The MMA is polymerized to poly(methyl methacrylate) (PMMA) to make the familiar clear acryUc sheet. PMMA is also used in mol ding and extmsion powders. Hydrolysis of acetone cyanohydrin gives methacrylic acid (MAA), a monomer which goes direcdy into acryUc latexes, carboxylated styrene—butadiene polymers, or ethylene—MAA ionomers. As part of the methacrylic stmcture, acetone is found in the following major end use products acryUc sheet mol ding resins, impact modifiers and processing aids, acryUc film, ABS and polyester resin modifiers, surface coatings, acryUc lacquers, emulsion polymers, petroleum chemicals, and various copolymers (see METHACRYLIC ACID AND DERIVATIVES METHACRYLIC POLYMERS). 

Cellulosics. CeUulosic adhesives are obtained by modification of cellulose [9004-34-6] (qv) which comes from cotton linters and wood pulp. Cellulose can be nitrated to provide cellulose nitrate [9004-70-0] which is soluble in organic solvents. When cellulose nitrate is dissolved in amyl acetate [628-63-7] for example, a general purpose solvent-based adhesive which is both waterproof and flexible is formed. Cellulose esterification leads to materials such as cellulose acetate [9004-35-7], which has been used as a pressure-sensitive adhesive tape backing. Cellulose can also be ethoxylated, providing hydroxyethylceUulose which is useful as a thickening agent for poly(vinyl acetate) emulsion adhesives. Etherification leads to materials such as methylceUulose [9004-67-5] which are soluble in water and can be modified with glyceral [56-81-5] to produce adhesives used as wallpaper paste (see Cellulose esters Cellulose ethers). 

Emulsion Adhesives. The most widely used emulsion-based adhesive is that based upon poly(vinyl acetate)—poly(vinyl alcohol) copolymers formed by free-radical polymerization in an emulsion system. Poly(vinyl alcohol) is typically formed by hydrolysis of the poly(vinyl acetate). The properties of the emulsion are derived from the polymer employed in the polymerization as weU as from the system used to emulsify the polymer in water. The emulsion is stabilized by a combination of a surfactant plus a coUoid protection system. The protective coUoids are similar to those used paint (qv) to stabilize latex. For poly(vinyl acetate), the protective coUoids are isolated from natural gums and ceUulosic resins (carboxymethylceUulose or hydroxyethjdceUulose). The hydroHzed polymer may also be used. The physical properties of the poly(vinyl acetate) polymer can be modified by changing the co-monomer used in the polymerization. Any material which is free-radically active and participates in an emulsion polymerization can be employed. Plasticizers (qv), tackifiers, viscosity modifiers, solvents (added to coalesce the emulsion particles), fillers, humectants, and other materials are often added to the adhesive to meet specifications for the intended appHcation. Because the presence of foam in the bond line could decrease performance of the adhesion joint, agents that control the amount of air entrapped in an adhesive bond must be added. Biocides are also necessary many of the materials that are used to stabilize poly(vinyl acetate) emulsions are natural products. Poly(vinyl acetate) adhesives known as "white glue" or "carpenter s glue" are available under a number of different trade names. AppHcations are found mosdy in the area of adhesion to paper and wood (see Vinyl polymers). 

The next significant strength improvement followed the 1950 Du Pont (19) discovery of monoamine and quaternary ammonium modifiers, which, when added to the viscose, prolonged the life of the ziac cellulose xanthate gel, and enabled even higher stretch levels to be used. Modifiers have proliferated siace they were first patented and the Hst now iacludes many poly(alkylene oxide) derivatives (20), polyhydroxypolyamines (21—23), and dithiocarbamates (24). 

Fully modified yams had smooth, all-skin cross sections, a stmcture made up of numerous small crystaUites of cellulose, and filament strengths around 0.4 N/tex (4.5 gf/den). They were generally known as the Super tire yams. Improved Super yams (0.44—0.53 N/tex (5—6 gf/den)) were made by mixing modifiers, and one of the best combiaations was found to be dimethylamine with poly-(oxyethylene) glycol of about 1500 mol wt (25). Ethoxjlated fatty acid amines have now largely replaced dimethylamine because they are easier to handle and cost less. 

Polyester sheet products may be produced from amorphous poly(ethylene terephalate) (PET) or partiaHy crystallized PET. Acid-modified (PETA) and glycol modified (PETG) resins are used to make ultraclear sheet for packaging. Poly(butylene terephthalate) (PBT) has also been used in sheet form. Liquid-crystal polyester resins are recent entries into the market for specialty sheet. They exhibit great strength, dimensional stabHity, and inertness at temperatures above 250°C (see Polyesters,thermoplastic). 

Alternative technology for modifying a poly(aLkylene terephthalate) by incorporation of a phosphinate stmcture has been developed by Enichem. Phosphinate units of the stmcture —P(CgH5) (0)CH20— are introduced into a polyester such as PET or PBT by transesterification with an oligomer comprised of the aforementioned units (136). 

Poly(vinyl chloride). To be converted into film, poly(viayl chloride) [9002-86-22] (PVC) must be modified with heat stabilizers and plasticizers, which increase costs. Plasticized PVC film is highly transparent and soft, with a very high gas-permeation rate. Water-vapor transmission rate is relatively low. At present, PVC film is produced by blown-film extmsion, although casting and calendering are employed for heavier gauges (see Vinyl POLYAffiRS). 

The white cell adsorption filter layer is typically of a nonwoven fiber design. The biomaterials of the fiber media are surface modified to obtain an optimal avidity and selectivity for the different blood cells. Materials used include polyesters, eg, poly(ethylene terephthalate) and poly(butylene terephthalate), cellulose acetate, methacrylate, polyamides, and polyacrylonitrile. Filter materials are not cell specific and do not provide for specific filtration of lymphocytes out of the blood product rather than all leukocytes. 

Tetraethylene glycol may be used direcdy as a plasticizer or modified by esterification with fatty acids to produce plasticizers (qv). Tetraethylene glycol is used directly to plasticize separation membranes, such as siHcone mbber, poly(vinyl acetate), and ceUulose triacetate. Ceramic materials utilize tetraethylene glycol as plasticizing agents in resistant refractory plastics and molded ceramics. It is also employed to improve the physical properties of cyanoacrylate and polyacrylonitrile adhesives, and is chemically modified to form polyisocyanate, polymethacrylate, and to contain siHcone compounds used for adhesives. 

Derivatives of hemicellulose components have properties similar to the ceUulosic equivalents but modified by the effects of thek lower molecular weight, more extensive branching, labile constituents, and more heterogeneous nature. Acetates, ethers, carboxymethylxylan (184), and xylan—poly(sodium acrylate) (185) have been prepared. 

The principal classes of high performance fibers are derived from rigid-rod polymers, gel spun fibers, modified carbon fibers, synthetic vitreous fibers, and poly(phenyiene sulfide) fibers. 

Membranes and Osmosis. Membranes based on PEI can be used for the dehydration of organic solvents such as 2-propanol, methyl ethyl ketone, and toluene (451), and for concentrating seawater (452—454). On exposure to ultrasound waves, aqueous PEI salt solutions and brominated poly(2,6-dimethylphenylene oxide) form stable emulsions from which it is possible to cast membranes in which submicrometer capsules of the salt solution ate embedded (455). The rate of release of the salt solution can be altered by surface—active substances. In membranes, PEI can act as a proton source in the generation of a photocurrent (456). The formation of a PEI coating on ion-exchange membranes modifies the transport properties and results in permanent selectivity of the membrane (457). The electrochemical testing of salts (458) is another possible appHcation of PEI. 

CD-modified BPA-polycarbonate (CD 2005, Bayer AG). Poly(methyl methacrylate). 

Three generations of latices as characterized by the type of surfactant used in manufacture have been defined (53). The first generation includes latices made with conventional (/) anionic surfactants like fatty acid soaps, alkyl carboxylates, alkyl sulfates, and alkyl sulfonates (54) (2) nonionic surfactants like poly(ethylene oxide) or poly(vinyl alcohol) used to improve freeze—thaw and shear stabiUty and (J) cationic surfactants like amines, nitriles, and other nitrogen bases, rarely used because of incompatibiUty problems. Portiand cement latex modifiers are one example where cationic surfactants are used. Anionic surfactants yield smaller particles than nonionic surfactants (55). Often a combination of anionic surfactants or anionic and nonionic surfactants are used to provide improved stabiUty. The stabilizing abiUty of anionic fatty acid soaps diminishes at lower pH as the soaps revert to their acids. First-generation latices also suffer from the presence of soap on the polymer particles at the end of the polymerization. Steam and vacuum stripping methods are often used to remove the soap and unreacted monomer from the final product (56). 

Functionalized conducting monomers can be deposited on electrode surfaces aiming for covalent attachment or entrapment of sensor components. Electrically conductive polymers (qv), eg, polypyrrole, polyaniline [25233-30-17, and polythiophene/23 2JJ-J4-j5y, can be formed at the anode by electrochemical polymerization. For integration of bioselective compounds or redox polymers into conductive polymers, functionalization of conductive polymer films, whether before or after polymerization, is essential. In Figure 7, a schematic representation of an amperomethc biosensor where the enzyme is covalendy bound to a functionalized conductive polymer, eg, P-amino (polypyrrole) or poly[A/-(4-aminophenyl)-2,2 -dithienyl]pyrrole, is shown. Entrapment of ferrocene-modified GOD within polypyrrole is shown in Figure 7. 

MBS polymers are prepared by grafting methyl methacrylate and styrene onto a styrene—butadiene mbber in an emulsion process. The product is a two-phase polymer useful as an impact modifier for rigid poly(vinyl chloride). 

Attempts have been made to use cold-set adhesives in the cormgating operation, such as poly(vinyl acetate) and modified, precooked starch formulations, but these have not achieved any appreciable degree of commercial acceptance (20). The use of a polyethylene film appHed to the inside surface of the linerboard facing, which serves as a hot-melt cormgator adhesive, has achieved some commercial usage. However, its use is limited to the small, specialty product niche of fast-food hamburger cartons (see Olefin polymers, polyethylene). 

Heat resistance is an important characteristic of the bond. The strength of typical abrasive stmctures is tested at RT and at 300°C. Flexural strengths are between 24.1 and 34.4 MPa (3500—5000 psi). An unmodified phenoHc resin bond loses about one-third of its room temperature strength at 298°C. Novolak phenoHc resins are used almost exclusively because these offer heat resistance and because the moisture given off during the cure of resole resins results in undesirable porosity. Some novolaks modified with epoxy or poly(vinyl butyral) resin are used for softer grinding action. 

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