Hardness copolymers

The polymer is available as a soft material with Mw = 264,000 and as a hard material with Mw = 237,000, depending on the proportion of the two copolymers. The pyrogram for the soft copolymer is shown in Figure 11.1.6, and the pyrogram for the hard copolymer is shown in Figure 11.1.7. The pyrolysis and pyrolysate separation were done in the same conditions as those for other examples previously discussed (see Table 4.2.2). 

Figure 11.1.7. Result for a Py-GC/MS analysis of a carbonate urethane hard copolymer, M = 237,000. Pyrolysis done on 0.4 mg material at 60

The degree of swelling of this copolymer in organic solvents is controlled by means of the amount of divinylbenzene. Hard copolymers of this type take up metal complexes only on the surface. The physical properties of the support can be varied by means of the polymerization method the metal loading can also be controlled well. 

Styrene-Butadiene-Styrene Block Copolymers. Styrene blocks associate into domains that form hard regions. The midblock, which is normally butadiene, ethylene-butene, or isoprene blocks, forms the soft domains. Polystyrene domains serve as cross-links. 

Much more information can be obtained by examining the mechanical properties of a viscoelastic material over an extensive temperature range. A convenient nondestmctive method is the measurement of torsional modulus. A number of instmments are available (13—18). More details on use and interpretation of these measurements may be found in references 8 and 19—25. An increase in modulus value means an increase in polymer hardness or stiffness. The various regions of elastic behavior are shown in Figure 1. Curve A of Figure 1 is that of a soft polymer, curve B of a hard polymer. To a close approximation both are transpositions of each other on the temperature scale. A copolymer curve would fall between those of the homopolymers, with the displacement depending on the amount of hard monomer in the copolymer (26—28). 

Acrylonitrile (AN), C H N, first became an important polymeric building block in the 1940s. Although it had been discovered in 1893 (1), its unique properties were not realized until the development of nitrile mbbers during World War II (see Elastomers, synthetic, nitrile rubber) and the discovery of solvents for the homopolymer with resultant fiber appHcations (see Fibers, acrylic) for textiles and carbon fibers. As a comonomer, acrylonitrile (qv) contributes hardness, rigidity, solvent and light resistance, gas impermeabiUty, and the abiUty to orient. These properties have led to many copolymer apphcation developments since 1950. 

The properties of SAN resins depend on their acrylonittile content. Both melt viscosity and hardness increase with increasing acrylonittile level. Unnotched impact and flexural strengths depict dramatic maxima at ca 87.5 mol % (78 wt %) acrylonitrile (8). With increasing acrylonitrile content, copolymers show continuous improvements in barrier properties and chemical and uv resistance, but thermal stabiUty deteriorates (9). The glass-transition... 

A substantial fraction of commercially prepared methacrylic polymers are copolymers. Monomeric acryUc or methacrylic esters are often copolymerized with one another and possibly several other monomers. Copolymerization greatiy increases the range of available polymer properties. The aH-acryhc polymers tend to be soft and tacky the aH-methacryhc polymers tend to be hard and brittie. By judicious adjustment of the amount of each type of monomer, polymers can be prepared at essentially any desired hardness or flexibiUty. Small amounts of specially functionalized monomers are often copolymerized with methacrylic monomers to modify or improve the properties of the polymer directiy or by providing sites for further reactions. Table 9 lists some of the more common functional monomers used for the preparation of methacrylic copolymers. 

Organic cross-linkers, which include glyoxal (48) and formaldehyde (qv), have also been used. Use of hypohaUte salts (49) and epichlorohydrin (50) promotes gel stabiUty. Phenol—formaldehyde cross-linking systems have been used to produce stable acrylamide copolymer gels at temperatures above 75°C and brine hardness levels above 2000 ppm (51). 

Many lens casters use the term hard-resin lenses for DADC products companies and trade names include American Optical (Aoflte ), Cobum (Supremacy I), Optical Radiation (Orcoflte), and Silor Optical (Orma 1000). Additional information can be obtained from the Optical Manufacturers Association, Falls Church, Va. Cast sheets of homopolymer and copolymers are suppHed by the SGL Homalite Company, Foster Grant, and others. 

Diallyl Isophthalate. DAIP polymerizes faster than DAP, undergoes less cyclization, and yields cured polymers of better heat resistance, eg, up to ca 200°C. Prepolymer molding materials such as Dapon M of EMC, are not sticky. Maleic anhydride accelerates polymerization, whereas vinyl isobutyl ether retards it and delays gelation in castings. Copolymers with maleic anhydride are exceptionally hard and tough and may scratch homopolymer surfaces. 

Copolymers of diallyl itaconate [2767-99-9] with AJ-vinylpyrrolidinone and styrene have been proposed as oxygen-permeable contact lenses (qv) (77). Reactivity ratios have been studied ia the copolymerization of diallyl tartrate (78). A lens of a high refractive iadex n- = 1.63) and a heat distortion above 280°C has been reported for diallyl 2,6-naphthalene dicarboxylate [51223-57-5] (79). Diallyl chlorendate [3232-62-0] polymerized ia the presence of di-/-butyl peroxide gives a lens with a refractive iadex of n = 1.57 (80). Hardness as high as Rockwell 150 is obtained by polymerization of triaHyl trimeUitate [2694-54-4] initiated by benzoyl peroxide (81). 

The most successful of these products contain high ratios of VP to DMAEMA and are partially quatemized with diethyl sulfate (Polyquaternium 11) (142—144). They afford very hard, clear, lustrous, nonflaking films on the hair that are easily removed by shampooing. More recendy, copolymers with methyl vinyl imidazoliiim chloride (Polyquaternium 16) (145) or MAPTAC (methacrylamidopropyltrimethyl ammonium chloride) (Polyquaternium 28) have been introduced. Replacement of the ester group in DMAEMA with an amide analog as in Polyquaternium 28 results in a resin resistant to alkaline hydrolysis and hence greater utility in alkaline permanent-wave and bleach formulations (see Quaternary ammonium compounds). 

The case is the largest portion of the container. The case is divided into compartments which hold the cell elements. The cores normally have a mud-rest area used to collect shed soHds from the battery plates and supply support to the element. Typical materials of constmction for the battery container are polypropylene, polycarbonate, SAN, ABS, and to a much lesser extent, hard mbber. The material used in fabrication depends on the battery s appHcation. Typical material selections include a polypropylene—ethylene copolymer for SLI batteries polystyrene for stationary batteries polycarbonate for large, single ceU standby power batteries and ABS for certain sealed lead—acid batteries. 

Step-Growth Gopolymerization. A sample of a block copolymer prepared by condensation polymerisation is shown in equation 30 (37). In this process, a prepolymer diol (HO—Z—OH) is capped with isocyanate end groups and chain extended with a low molecular-weight diol (HO—E—OH) to give a so-called segmented block copolymer, containing polyurethane hard blocks and O—Z—O soft blocks. 

Several cleaning formulations for specific uses contain unreacted polyamines. Examples include mixtures of ammonium alkylbenzenesulfonate, solvents, and PIP which give good cleaning and shine performance on mirrors and other hard surfaces without rinsing (305), and a hard-surface cleaner composed of a water-soluble vinyl acetate—vinyl alcohol copolymer, EDA, cyclohexanone [108-94-1] dimethyl sulfoxide [67-68-5] a surfactant, and water (306). TEPA, to which an average of 17 moles of ethylene oxide are added, improves the clay sod removal and sod antiredeposition properties of certain hquid laundry detergents (307). 

The excellent low temperature properties of FZ have been iadicated ia Table 1. Modulus curves were obtained usiag dynamic mechanical spectroscopy to compare several elastomer types at a constant 75 durometer hardness. These curves iadicate the low temperature flexibiUty of FZ is similar to fluorosihcone and ia great contrast to that of a fluorocarbon elastomer (vinyUdene fluoride copolymer) (Fig. 3) (15). 

The crystalliza tion resistance of vulcaniza tes can be measured by following hardness or compression set at low temperature over a period of time. The stress in a compression set test accelerates crystallization. Often the curve of compression set with time has an S shape, exhibiting a period of nucleation followed by rapid crystallization (Fig. 3). The mercaptan modified homopolymer, Du Pont Type W, is the fastest crystallizing, a sulfur modified homopolymer, GN, somewhat slower, and a sulfur modified low 2,3-dichlorobutadiene copolymer, GRT, and a mercaptan modified high dichlorobutadiene copolymer, WRT, are the slowest. The test is often mn near the temperature of maximum crystallization rate of —12° C (99). Crystallization is accelerated by polyester plasticizers and delayed with hydrocarbon oil plasticizers. Blending with hydrocarbon diene mbbers may retard crystallization and improve low temperature britdeness (100). 

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