Polyethersulfon

Possible tape materials include polyimide, polyester, polyethersulfone (PES), and polyparabanic acid (PPA) (18). Of these, polyimide is the most widely used material because its high melting point allows it to survive at temperatures up to 365°C. Although polyester is much cheaper than other materials, its use is limited to temperatures less than 160°C. PES and PPA, on the other hand, are half as cosdy as polyimide, and can survive maximum short-term temperatures of 220 and 275°C, respectively. PES has better dimensional stabiUty than polyimide, absorbs less moisture, and does not tear as easily however, it is inflammable and can be attacked by certain common solvents. Table 7 Hsts various plastic tapes and their properties. Common bump materials are gold, copper, and 95% Pb/5% Sn solder (see Tables 6 and 8 for properties see also References 2 and 21). 

The aromatic sulfone polymers are a group of high performance plastics, many of which have relatively closely related stmctures and similar properties (see Polymers containing sulfur, polysulfones). Chemically, all are polyethersulfones, ie, they have both aryl ether (ArOAr) and aryl sulfone (ArS02Ar) linkages in the polymer backbone. The simplest polyethersulfone (5) consists of aromatic rings linked alternately by ether and sulfone groups. 

Reaction of bis (sulfonyl chloride)s with diaryl ether produces polyethersulfones. For example, condensation of diphenyl ether with the disulfonylchloride of diphenyl ether yields polyethersulfone (5) ... 

The diphenylsulfone group is suppHed to the repeat unit of aU polysulfones by DCDPS the differentiating species between various polysulfones comes from the choice of bisphenol. There are three commercially important polysulfones referred to genericaHy by the common names polysulfone (PSF), polyethersulfone (PES), and polyphenylsulfone (PPSF). The repeat units of these polymers are shown in Table 1. 

PES repeat unit stmcture can alternatively be drawn as Victrex polyethersulfone [25667 2-9]. 

The polymerizations of polyethersulfone (PES) and polyphenylsulfone (PPSE) are analogous to that of PSE, except that in the case of these two polymers, solvents which are higher boiling than DMSO are needed due to the higher reaction temperatures required. Diphenyl sulfone, sulfolane, and... 

Other Synthesis Routes. Several alternative routes to the nucleopbilic substitution synthesis of polysulfones are possible. Polyethersulfone can be synthesized by the electrophilic Eriedel-Crafts reaction of bis(4-chlorosulfonylphen5l)ether [121 -63-1] with diphenyl ether [101-84-8] (11—13). 

The tensile and flexural properties as well as resistance to cracking in chemical environments can be substantially enhanced by the addition of fibrous reinforcements such as chopped glass fiber. Mechanical properties at room temperature for glass fiber-reinforced polysulfone and polyethersulfone are shown in Table 5. 

Fig. 5. Flexural modulus—temperature curves of C, polysulfone and B, polyethersulfone compared to the moduli curves of A, polyacetal D, heat-resistant...

Table 5. Properties of Glass Fiber-Reinforced (GR) Polysulfone and Polyethersulfone...

Property ASTM test method Polysulfone, % GR Polyethersulfone, % GR ... 

These solvents include tetrahydrofuran (THF), 1,4-dioxane, chloroform, dichioromethane, and chloroben2ene. The relatively broad solubiHty characteristics of PSF have been key in the development of solution-based hoUow-fiber spinning processes in the manufacture of polysulfone asymmetric membranes (see Hollow-fibermembranes). The solvent Hst for PES and PPSF is short because of the propensity of these polymers to undergo solvent-induced crysta11i2ation in many solvents. When the PES stmcture contains a small proportion of a second bisphenol comonomer, as in the case of RADEL A (Amoco Corp.) polyethersulfone, solution stabiHtyis much improved over that of PES homopolymer. 

Fig. 6. Melt viscosity dependence on shear rate for various polymers A, low density polyethylene at 210°C B, polystyrene at 200°C C, UDEL P-1700 polysulfone at 360°C D, LEXAN 104 polycarbonate at 315°C and E, RADEL A-300 polyethersulfone at 380°C.

Proprietary blend formulations based on polysulfone, polyethersulfone, and polyphenylsulfone are sold commercially by Amoco Corporation to meet various end use requirements. The blends based on polysulfone are sold under the MINDEL trademark. A glass fiber-reinforced blend based on PES is offered under the trade name RADEL AG-360. This offers most of the performance characteristics of 30% glass fiber-reinforced polyethersulfone but at a lower cost. Two blend product lines are offered based on PPSF. These are designated as the RADEL R-4000 and R-7000 series of products. The former is a lower cost alternative to RADEL R PPSF homopolymer offering most of the performance attributes unique to PPSF. The R-7000 series of resins have been formulated for use in aircraft interiors for civil air transport. They exhibit a very high degree of resistance to flammabihty and smoke release. 

There are three commercial suppHers that manufacture polysulfones Amoco Corporation ia the United States, BASF Corporation ia Germany, and Sumitomo Chemical Company ia Japan. A listing of the resias suppHed by each of these companies along with the trade names particular to each of these suppHers is shown ia Table 9. AH three companies supply a polyethersulfone-type product. Polysulfone, on the other hand, is suppHed by Amoco and BASF, and Amoco is the sole suppHer of polyphenylsulfone. 

As of November 1, 1995, the price range of UDEL polysulfone resias ia large quantities was 9.10— 12.03/kg depending on grade and color. RADEL A polyethersulfone grades sold for 10.46— 13.26/kg and the prices of RADEL R polyphenylsulfone resias were ia the range 15.75— 25.95/kg. MINDEL resias based oa polysulfoae had Hst prices betweea 6.72— 7.42/kg. 

A number of amorphous thermoplastics are presently employed as matrices in long fiber composites, including polyethersulfone (PES), polysulfone (PSU), and polyetherimide (PEI). AH offer superior resistance to impact loading and higher interlaminar fracture toughnesses than do most epoxies. However, the amorphous nature of such polymers results in a lower solvent resistance, clearly a limitation if composites based on such polymers are to be used in aggressive environments. 

Polysulfones. The most common polysulfone is actually a sulfone ether, polyethersulfone [25135-51-7] (PES), and has the following stmcture. 

Newer resins include polysulfone, polyethersulfone, polyetherimide, and polyetherketone. Some of these newer materials are high temperature thermoplastic, not thermoset, resins. They are being promoted for the design of injection-molded printed circuit boards in three-dimensional shapes for functional appHcations as an alternative to standard flat printed circuit boards. Only semiadditive or fully additive processing can be used with these devices. 

Amorphous Thermoplastics. Polysulfone, polyethersulfone, and polyarylsulfone are examples of amorphous thermoplastics. These materials have high Ts and can stand temperatures up to 200°C for a long period of time. Amoco and ICI are principal suppHers of this class of material. 

Polysulfone Resins. Commercially important polysulfones are aromatic, ie, in the generalized formula for the repeating unit R and R both contain aromatic rings (see Polymers containing sulfur, polysulfone resins). They all possess ether linkages as weU, so that use of the designations polysulfone, polyarylsulfone (PAS), and polyethersulfone (PES) is somewhat arbitrary. 

Amoco Performance Products (Atlanta, Ga.), is the sole supplier of polysulfone, Udel, polyarylsulfone, Radel A, and polyphenylsulfone, Radel R. ICI Advanced Materials (Exton, Pa.), is the sole domestic supplier of the polyethersulfone, Victrex PES, but announced ia 1991 it was withdrawing from the business. 

In 1989 BASE announced its intention to market in the United States a polysulfone, Ultrason S, and a polyethersulfone, Ultrason E. Both materials would likely be made in Germany. World consumption and prices of polysulfones are given in Table 12. 

Ultem PEI resins are amber and amorphous, with heat-distortion temperatures similar to polyethersulfone resins. Ultem resins exhibit high modulus and ate stiff yet ductile. Light transmission is low. In spite of the high use temperature, they are processible by injection mol ding, stmctural foam mol ding, or extmsion techniques at moderate pressures between 340 and 425°C. They are inherently flame retardant and generate Httie smoke dimensional stabiUties are excellent. Large flat parts such as circuit boards or hard disks for computers can be injection-molded to maintain critical dimensions. 

The PEEK resia is marketed as aeat or filled pellets for iajectioa mol ding, as powder for coatiags, or as preimpregaated fiber sheet and tapes. Apphcations iaclude parts that are exposed to high temperature, radiation, or aggressive chemical environments. Aerospace and military uses are prominent. At present, polyamideimide (PAl) resia and poly(arylene sulfides) are the main competitors for apphcations requiring service temperatures of 280°C. At lower temperatures, polyethersulfones, amorphous nylons, and polyetherimides (PEI) can be considered. 

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