Transitions copolymers

PET (80)/poly(ethylene isophthalate) (20) Melt mixed at 270 °C/mechanical properties/ NMR/DSC/monitoring of block copolymer to random copolymer transition/also used poly (ethylene terephthalate-co-isophthalate) Kint et al. 2003... 

COPOLYMER TRANSITION DATA FOR THE 50 SiO-UNIT SIDE-CHAIN POLYSILOXANE SYSTEM OF FIG. 3(b)... 

Micellar structure has been a subject of much discussion [104]. Early proposals for spherical [159] and lamellar [160] micelles may both have merit. A schematic of a spherical micelle and a unilamellar vesicle is shown in Fig. Xni-11. In addition to the most common spherical micelles, scattering and microscopy experiments have shown the existence of rodlike [161, 162], disklike [163], threadlike [132] and even quadmple-helix [164] structures. Lattice models (see Fig. XIII-12) by Leermakers and Scheutjens have confirmed and characterized the properties of spherical and membrane like micelles [165]. Similar analyses exist for micelles formed by diblock copolymers in a selective solvent [166]. Other shapes proposed include ellipsoidal [167] and a sphere-to-cylinder transition [168]. Fluorescence depolarization and NMR studies both point to a rather fluid micellar core consistent with the disorder implied by Fig. Xm-12. 

It is not the purpose of this book to discuss in detail the contributions of NMR spectroscopy to the determination of molecular structure. This is a specialized field in itself and a great deal has been written on the subject. In this section we shall consider only the application of NMR to the elucidation of stereoregularity in polymers. Numerous other applications of this powerful technique have also been made in polymer chemistry, including the study of positional and geometrical isomerism (Sec. 1.6), copolymers (Sec. 7.7), and helix-coil transitions (Sec. 1.11). We shall also make no attempt to compare the NMR spectra of various different polymers instead, we shall examine only the NMR spectra of different poly (methyl methacrylate) preparations to illustrate the capabilities of the method, using the first system that was investigated by this technique as the example. 

Table 1 shows that most acryflcs have low glass-transition temperatures. Therefore, in copolymers they tend to soften and flexibHize the overall composition. Plasticizers also lower the transition temperature. However, unlike incorporated acryflc comonomers, they can be lost through volatilization or extraction. 

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... 

This type of adhesive is generally useful in the temperature range where the material is either leathery or mbbery, ie, between the glass-transition temperature and the melt temperature. Hot-melt adhesives are based on thermoplastic polymers that may be compounded or uncompounded ethylene—vinyl acetate copolymers, paraffin waxes, polypropylene, phenoxy resins, styrene—butadiene copolymers, ethylene—ethyl acrylate copolymers, and low, and low density polypropylene are used in the compounded state polyesters, polyamides, and polyurethanes are used in the mosdy uncompounded state. 

Improved Hot—Wet Properties. Acryhc fibers tend to lose modulus under hot—wet conditions. Knits and woven fabrics tend to lose their bulk and shape in dyeing and, to a more limited extent, in washing and drying cycles as well as in high humidity weather. Moisture lowers the glass-transition temperature T of acrylonitrile copolymers and, therefore, crimp is lost when the yam is exposed to conditions requited for dyeing and laundering. 

The relaxatioa temperature appears to iacrease with increa sing HFP coateat. Relaxatioa iavolves 5—13 of the chaia carboa atoms. Besides a and y relaxations, one other dielectric relaxation was observed below —150° C, which did not vary ia temperature or ia magnitude with comonomer content or copolymer density (55). The a relaxation (also called Glass 1) is a high temperature transition (157°C) andy relaxation (Glass 11) (internal friction maxima) occurs between —5 and 29°C. 

Mech nic lProperties. Extensive Hsts of the physical properties of FEP copolymers are given in References 58—63. Mechanical properties are shown in Table 3. Most of the important properties of FEP are similar to those of PTFE the main difference is the lower continuous service temperature of 204°C of FEP compared to that of 260°C of PTFE. The flexibiUty at low temperatures and the low coefficients of friction and stabiUty at high temperatures are relatively independent of fabrication conditions. Unlike PTFE, FEP resins do not exhibit a marked change in volume at room temperature, because they do not have a first-order transition at 19°C. They ate usehil above —267°C and are highly flexible above —79°C (64). 

Electronic Properties. What distinguishes polysdanes from virtually ad. other polymers is their backbone CJ-conjugation. This leads to strong electronic absorption in the near-uv from a O —O transition. For most homo- and copolymers the absorption maximum (/-j ) hes between 300 and 400... 

Soluble and weU-characterized polygermane homopolymers, (R Ge), and their copolymers with polysdanes have been prepared by the alkaH metal coupling of diorgano-substituted dihalogermanes (137—139), via electrochemical methods (140), and by transition-metal catalyzed routes (105), as with the synthesis of polysdanes. 

The Ts of methacryhc polymers may be regulated by the copolymerization of two or more monomers as illustrated in Figure 1. The approximate T value for the copolymer can be calculated from the weight fraction of each monomer type and the T (in K) of each homopolymer (15). Acrylates with low transition temperatures are frequently used as permanent plasticizers (qv) for methacrylates. Unlike plasticizer additives, once polymerized into the polymer chain, the acrylate cannot migrate, volatilize, or be extracted from the polymer. 

Measurement of modulus over an extensive temperature range offers more information than T alone (16). Typical modulus—temperature curves are shown in Figure 1. Assuming that the reference temperature is the transition temperature of the copolymer, then curve A of Figure 1 is that of a softer polymer and curve B is that of a harder polymer. Cross-linking of the polymer elevates and extends the mbbery plateau Htde effect on T is noted until extensive cross-linking has been introduced. In practice, cross-linking of methacryhc polymers is used to decrease thermoplasticity and solubihty and to increase residence. 

High density polyethylene (HDPE) is defined by ASTM D1248-84 as a product of ethylene polymerisation with a density of 0.940 g/cm or higher. This range includes both homopolymers of ethylene and its copolymers with small amounts of a-olefins. The first commercial processes for HDPE manufacture were developed in the early 1950s and utilised a variety of transition-metal polymerisation catalysts based on molybdenum (1), chromium (2,3), and titanium (4). Commercial production of HDPE was started in 1956 in the United States by Phillips Petroleum Company and in Europe by Hoechst (5). HDPE is one of the largest volume commodity plastics produced in the world, with a worldwide capacity in 1994 of over 14 x 10 t/yr and a 32% share of the total polyethylene production. 

Most Kaminsky catalysts contain only one type of active center. They produce ethylene—a-olefin copolymers with uniform compositional distributions and quite narrow MWDs which, at their limit, can be characterized by M.Jratios of about 2.0 and MFR of about 15. These features of the catalysts determine their first appHcations in the specialty resin area, to be used in the synthesis of either uniformly branched VLDPE resins or completely amorphous PE plastomers. Kaminsky catalysts have been gradually replacing Ziegler catalysts in the manufacture of certain commodity LLDPE products. They also faciUtate the copolymerization of ethylene with cycHc dienes such as cyclopentene and norhornene (33,34). These copolymers are compositionaHy uniform and can be used as LLDPE resins with special properties. Ethylene—norhornene copolymers are resistant to chemicals and heat, have high glass transitions, and very high transparency which makes them suitable for polymer optical fibers (34). 

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