Majority copolymers

Graft Copolymer FIGURE 6-1 Major copolymer types. 

As simple example, MALDI-tof-ms has been used to study the number of a-methyl styrene (a-MeSty) repeat units in SRM1487, a narrow MMD PMMA NIST standard reference material of about 6300 g/mol (62). Here, the major copolymer component is MMA and a-MeSty is the minor component. The a-MeSty is, in fact, part of the initiator for this polymer and the material is either a MMA styrene MMA triblock copolymer or a styrene MMA diblock copolymer, with the a-MeSty block length containing 0-6 a-MeSty. 

In this chapter the overall crystallization kinetics and spherulite growth rates of the major copolymer types will be presented and analyzed. It should be recalled from the point of view of polymer crystallization that chains containing structurally different repeating units, although chemically identical, are also treated as copolymers. These include branch points and regio defects as well as stereo and geometric isomers. As a matter of convenience, the influence of cross-links will also be included in this chapter. 

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). 

The major use of vinylpyrrohdinone is as a monomer in manufacture of poly(vinylpyrrohdinone) (PVP) homopolymer and in various copolymers, where it frequendy imparts hydrophilic properties. When PVP was first produced, its principal use was as a blood plasma substitute and extender, a use no longer sanctioned. These polymers are used in pharmaceutical and cosmetic appHcations, soft contact lenses, and viscosity index improvers. The monomer serves as a component in radiation-cured polymer compositions, serving as a reactive diluent that reduces viscosity and increases cross-linking rates (see... 

In this article the term acrylamide polymer refers to all polymers which contain acrylamide as a major constituent. Consequendy, acrylamide polymers include functionalized polymers prepared from polyacrylamide by postreaction and copolymers prepared by polymerizing acrylamide (2-propenamide, C H NO) with one or more comonomers. 

The vast majority of all commercially prepared acryUc polymers are copolymers of an acryUc ester monomer with one or more different monomers. Copolymerization gready increases the range of available polymer properties and has led to the development of many different resins suitable for a broad variety of appHcations. Several review articles are available (84,85). 

Synthetic emulsion polymers account for approximately 70% of the U.S. consumption of acrylate monomers. Major end uses for these latex polymers are coatings (32%), textiles (17%), adhesives (7%), paper (5%), and floor poHshes (3%). The U.S. producers of acryflc copolymer emulsions include Rohm and Haas, Reichhold, National Starch, Union Carbide, Air Products, Unocal, B. F. Goodrich, and H. B. Fuller. 

Solution polymers are the second most important use for acryflc monomers, accounting for about 12% of the monomer consumption. The major end use for these polymers is in coatings, primarily industrial finishes. Other uses of acryflc monomers include graft copolymers, suspension polymers, and radiation curable inks and coatings. 

The principal monomer is acrylamide [79-06-17, where R = H and R = NH2, made by the hydrolysis of acrylonitrile. The homopolymer [9003-05-8] of acrylamide, which in theory has no electrical charge, has some use as a flocculant however, the majority of acrylamide-based flocculants are copolymers with acryHc monomers containing charged functional groups, such as those shown in Figure 1, or polymers containing functional groups formed by modification of acrylamide homopolymers or copolymers (Fig. 2). The chemistry of polyacrylamides has been reviewed by several authors (18—20) (see... 

Vinyl chloride has gained worldwide importance because of its industrial use as the precursor to PVC. It is also used in a wide variety of copolymers. The inherent flame-retardant properties, wide range of plastici2ed compounds, and low cost of polymers from vinyl chloride have made it a major industrial chemical. About 95% of current vinyl chloride production worldwide ends up in polymer or copolymer appHcations (83). Vinyl chloride also serves as a starting material for the synthesis of a variety of industrial compounds, as suggested by the number of reactions in which it can participate, although none of these appHcations will likely ever come anywhere near PVC in terms of volume. The primary nonpolymeric uses of vinyl chloride are in the manufacture of vinyHdene chloride and tri- and tetrachloroethylene [127-18-4] (83). 

Miscellaneous Copolymers. VP has been employed as a termonomer with various acryUc monomer—monomer combinations, especially to afford resins usehil as hair fixatives. Because of major differences in reactivity, VP can be copolymerized with alpha-olefins, but the products are actually PVP grafted with olefin or olefin oligomers (151,152). Likewise styrene can be polymerized in the presence of PVP and the resulting dispersion is unusually stable, suggesting that this added resistance to separation is caused by some grafting of styrene onto PVP (153). The Hterature contains innumerable references to other copolymers but at present (ca 1997), those reviewed in this article are the only ones known to have commercial significance. 

With the current prevalence of computer Hterature searching, it is relatively easy to accomplish patent searches, especiaUy in Chemicaly hstracts (CAS). In heu of what would be an extensive Ust of patent references to the many appHcations for VP homo- and copolymers, a Ust of the major categories and the number of patents granted in each of them during the period 1989—1995 is given in Table 17. More detail concerning the patents is provided in Reference 27. 

Some commercial durable antistatic finishes have been Hsted in Table 3 (98). Early patents suggest that amino resins (qv) can impart both antisHp and antistatic properties to nylon, acryUc, and polyester fabrics. CycHc polyurethanes, water-soluble amine salts cross-linked with styrene, and water-soluble amine salts of sulfonated polystyrene have been claimed to confer durable antistatic protection. Later patents included dibydroxyethyl sulfone [2580-77-0] hydroxyalkylated cellulose or starch, poly(vinyl alcohol) [9002-86-2] cross-linked with dimethylolethylene urea, chlorotria2ine derivatives, and epoxy-based products. Other patents claim the use of various acryUc polymers and copolymers. Essentially, durable antistats are polyelectrolytes, and the majority of usehil products involve variations of cross-linked polyamines containing polyethoxy segments (92,99—101). 

Aliphatic Polyolefins other than Polyethylene, and Diene Rubbers Table 11.11 Comparison of major propenies of ethylene-based copolymers with polyethylene ... 

This chapter has so far dealt with the major fields of use of vinyl chloride polymers, namely plasticised PVC homopolymer, unplasticised PVC, including impact-modified grades, and copolymers particular based on vinyl acetate. There are, however, five particular special forms of vinyl chloride polymer which merit separate consideration, namely crystalline PVC, after-chlorinated PVC (often known as CPVC) and certain graft copolymers and two vinyl-chloride-based copolymers. 

A number of other copolymers with vinylidene chloride as the major component have been marketed. Prominent in the patent literature are methyl methacrylate, methyl acrylate and ethyl acrylate. 

Neoprene latex 115 contains a copolymer of chloroprene and methacrylic acid, stabilized with polyvinyl alcohol [15], With respect to other polychloroprene latices, this latex has two major advantages (1) excellent colloidal stability, which gives high resistance to shear and a broad tolerance to several materials ... 

Of the amorphous block copolymers, styrenic block copolymers are the vast majority. These are synthesized anionically in solution, with butyl lithium commonly employed as the initiator [4]. There are three processes for this polymerization ... 

A major development in fluoroplastks is the recent small scale production of Teflon AF, a noncrystaUme (amorphous) fluorocarbon polymer with a high glass transition temperature (240 °C) This optically transparent TFE copolymer is soluble m certan fluorocabons and has the same chemical and oxidative stability as crystallme TFE homopolymers [5]... 

Eor a long time there have been discussions about which type of sorbent is the best for SEC separations in various mobile phases. In principle, organic (copolymer) and inorganic packings can be used. Each type of packing has its benefits and drawbacks. Table 9.3 summarizes major sorbent properties and reveals some interesting aspects of SEC separations and its requirements on packings. 

In the preceding sections, our discussion has been limited to softer grade elastomer-plastic vulcanizates. Commercial interest, however, also centers on another major family of polymer blends, semi-rigid impact resistant polyolefins. Thus, we report some of our findings on PRP triblock copolymer and EVA rubber blends without... 

In addition to the abovementioned parameters, various factors such as viscosity of the copolymer and its interaction with the homopolymers also play a major role in the compatibilization process. 

Acrylic fibers are a major synthetic fiber class developed about the same time as polyesters. Modacrylic fibers are copolymers containing between 35-85% acrylonitrile. Acrylic fibers contain at least 85% acrylonitrile. Orion is an acrylic fiber developed by DuPont in 1949 Dynel is a modacrylic fiber developed by Union Carbide in 1951. 

Polyolefin copolymers Although there is a wide variety of these available, the only one currently commercially available as a compounded powder is saponified EVA. This is reported to have good weatherability and will not suffer from ESC. One major advantage this coating has is that it can be applied by the fluidised bed process at low temperatures and this offers the possibility of coating temperature-sensitive metals such as galvanised steel. 

Figures 12-12 and 12-13 document that trap-free SCL-conduction can, in fact, also be observed in the case of electron transport. Data in Figure 12-12 were obtained for a single layer of polystyrene with a CF -substituted vinylquateiphenyl chain copolymer, sandwiched between an ITO anode and a calcium cathode and given that oxidation and reduction potentials of the material majority curriers can only be electrons. Data analysis in terms of Eq. (12.5) yields an electron mobility of 8xl0 ycm2 V 1 s . The rather low value is due to the dilution of the charge carrying moiety. The obvious reason why in this case no trap-limited SCL conduction is observed is that the ClVquatciphenyl. substituent is not susceptible to chemical oxidation.

One of the major drawbacks to many promising copolymers is their unsatisfactory electrochemical stability. Carbonyl groups which feature in many of the back-bone/chain linking groups are likely to cause stability concerns. Likewise, urethane, alcohol, and siloxane functions are sensitive to lithium metal. With this in mind, a recent trend has been to find synthetic routes to amorphous structures with... 

The majority of hydrophilic and water-soluble polymers are manufactured on the commercial level. Their list includes PAAm, copolymers of AAm, PAAc, PEO, PVA, poly(jY-vinylpyrrolidone), some polyamines etc. So, it seems practically highly attractive to produce hydrogels based on these polymers using various crosslinking techniques. 

It has been argued that for a majority of copolymerizations, composition data can be adequately predicted by the terminal model copolymer composition equation (eqs. 5-9). However, in that composition data are not particularly good for model discrimination, any conclusion regarding the widespread applicability of the implicit penultimate model on this basis is premature. 

One of the major advantages of radical polymerization over most other forms of polymerization, (anionic, cationic, coordination) is that statistical copolymers can be prepared from a very wide range of monomer types that can contain various unprotected functionalities. Radical copolymerization and the factors that influence copolymer structure have been discussed in Chapter 7. Copolymerization of macromonomers by NMP, ATRP and RAFT is discussed in Section 9.10.1. 

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