Copolymers commercially important

Acrylamide copolymerizes with many vinyl comonomers readily. The copolymerization parameters ia the Alfrey-Price scheme are Q = 0.23 and e = 0.54 (74). The effect of temperature on reactivity ratios is small (75). Solvents can produce apparent reactivity ratio differences ia copolymerizations of acrylamide with polar monomers (76). Copolymers obtained from acrylamide and weak acids such as acryUc acid have compositions that are sensitive to polymerization pH. Reactivity ratios for acrylamide and many comonomers can be found ia reference 77. Reactivity ratios of acrylamide with commercially important cationic monomers are given ia Table 3. 

Other Polymers. Besides polycarbonates, poly(methyl methacrylate)s, cycfic polyolefins, and uv-curable cross-linked polymers, a host of other polymers have been examined for their suitabiUty as substrate materials for optical data storage, preferably compact disks, in the last years. These polymers have not gained commercial importance polystyrene (PS), poly(vinyl chloride) (PVC), cellulose acetobutyrate (CAB), bis(diallylpolycarbonate) (BDPC), poly(ethylene terephthalate) (PET), styrene—acrylonitrile copolymers (SAN), poly(vinyl acetate) (PVAC), and for substrates with high resistance to heat softening, polysulfones (PSU) and polyimides (PI). 

Copolymers. Although many copolymers of ethylene can be made, only a few have been commercially produced. These commercially important copolymers are Hsted in Table 4, along with their respective reactivity coefficient (see Co polymers. The basic equation governing the composition of the copolymer is as follows, where and M2 are the monomer feed compositions, and r2 ate the reactivity ratios (6). 

A commercially important example of the special case where one monomer is the same in both copolymers is blends of styrene—acrylonitrile, 1 + 2, or SAN copolymers with styrene—maleic anhydride, 1 + 3, or SMA copolymers. The SAN and SMA copolymers are miscible (128,133,144) so long as the fractions of AN and MA are neatly matched, as shown in Figure 4. This suggests that miscibility is caused by a weak exothermic interaction between AN and MA units (128,133) since miscibility by intramolecular repulsion occurs in regions where 02 7 can be shown (143) by equation 11. 

Vinylidene chloride copolymers were among the first synthetic polymers to be commercialized. Their most valuable property is low permeabiUty to a wide range of gases and vapors. From the beginning in 1939, the word Saran has been used for polymers with high vinylidene chloride content, and it is still a trademark of The Dow Chemical Company in some countries. Sometimes Saran and poly (vinylidene chloride) are used interchangeably in the Hterature. This can lead to confusion because, although Saran includes the homopolymer, only copolymers have commercial importance. The homopolymer, ie, poly (vinylidene chloride), is not commonly used because it is difficult to fabricate. 

The principal solution to fabrication difficulties is copolymerization. Three types of comonomers are commercially important vinyl chloride acrylates, including alkyl acrylates and alkyimethacrylates and acrylonitrile. When extmsion is the method of fabrication, other solutions include formulation with plasticizers, stabilizers, and extmsion aids plus applying improved extmsion techniques. The Hterature on vinyHdene chloride copolymers through 1972 has been reviewed (1). 

GopolymeriZation. The importance of VDC as a monomer results from its abiHty to copolymerize with other vinyl monomers. Its Rvalue equals 0.22 and its e value equals 0.36. It most easily copolymerizes with acrylates, but it also reacts, more slowly, with other monomers, eg, styrene, that form highly resonance-stabiHzed radicals. Reactivity ratios (r and r, with various monomers are Hsted in Table 2. Many other copolymers have been prepared from monomers for which the reactivity ratios are not known. The commercially important copolymers include those with vinyl chloride (VC),... 

Although they lack commercial importance, many other poly(vinyl acetal)s have been synthesized. These include acetals made from vinyl acetate copolymerized with ethylene (43—46), propjiene (47), isobutjiene (47), acrylonitrile (48), acrolein (49), acrylates (50,47), aHyl ether (51), divinyl ether (52), maleates (53,54), vinyl chloride (55), diaHyl phthalate (56), and starch (graft copolymer) (47). 

Copolymers of acrylonitrile [107-13-1] are used in extmsion and molding appHcations. Commercially important comonomers for barrier appHcations include styrene and methyl acrylate. As the comonomer content is increased, the permeabiUties increase as shown in Figure 3. These copolymers are not moisture-sensitive. Table 7 contains descriptions of three high nitrile barrier polymers. Barex and Cycopac resins are mbber-modified to improve the mechanical properties. 

A polymer blend is a physical or mechanical blend (alloy) of two or more homopolymers or copolymers. Although a polymer blend is not a copolymer according to the above definition, it is mentioned here because of its commercial importance and the frequency with which blends are compared with chemically bonded copolymers. Another technologically significant material relative to the copolymer is the composite, a physical or mechanical combination of a polymer with some unlike material, eg, reinforcing materials such as carbon black, graphite fiber, and glass (see Composite materials). 

Copolymers extend the number and range of available materials, enabling the polymer scientist to achieve combinations of material properties (eg, tensile strength, solubiHty, solvent resistance, low temperature flexibiHty, etc) unattainable from the simple constituent homopolymers. As a result, a large number of copolymers have become commercially important. Table 1 Hsts some of them. 

In 1957, it was discovered that organometaUic catalysts gave high mol wt polymers from epoxides (3). The commercially important, largely amorphous polyether elastomers developed as a result of this early work are polyepichlorohydrin (ECH) (4,5), ECH—ethylene oxide (EO) copolymer (6), ECH—aUyl glycidyl ether (AGE) copolymer (7,8), ECH—EO—AGE terpolymer (8), ECH—propylene oxide (PO)—AGE terpolymer (8,9), and PO—AGE copolymer (10,11). The American Society for Testing and Materials (ASTM) has designated these polymers as follows ... 

Information on the synthesis of the polyetherimide—polysiloxane block copolymers has not been disclosed. Many other synthetic methods for preparing block copolymers have been described (19,20,25) but are currendy not beheved to be commercially important. 

Until the mid-1950s the only polyolefins (polyalkenes) of commercial importance were polyethylene, polyisobutylene and isobutylene-isoprene copolymers (butyl rubber). Attempts to produce polymers from other olefins had, at best, resulted only in the preparation of low molecular weight material of no apparent commercial value. 

Polyacrylic acid (pAA) homopolymers and related copolymers have become a commercially important class of water-soluble polymers. Acrylic acid polymers can range in molecular mass from less than 1000 Da to greater than 1,000,000 Da. A representative set of analysis conditions is... 

Certain commercially important crosslinking reactions are carried out with unsaturated polymers. For example, as will be described later in this chapter, polyesters can be made using bifunctional acids which contain a double bond. The resulting polymers have such double bonds at regular intervals along the backbone. These sites of unsaturation are then crosslinked by reaction with styrene monomer in a free-radical chain (addition) process to give a material consisting of polymer backbones and poly(styrene) copolymer crosslinks. 

Many commercially important polymers are actually mixtures of two or more polymer components that differ from one another in composition (for copolymers) or in microstructure (for homopolymers). Such mixtures may be the deliberate result of polymer blending, polymer synthesis, or the presence of different types of initiators or catalytic sites that produce different polymer chains. The ung spectral data of the whole polymer in such systems would include contributions from all its components, and as such should be treated with care. 

The crystallization kinetics of commercial polyolefins is to a large extent determined by the chain microstructure [58-60]. The kinetics and the regime [60] of the crystallization process determine not only the crystalline content, but also the structure of the interfaces of the polymer crystals (see also Chapter 7). This has a direct bearing on the mechanical properties like the modulus, toughness, and other end use properties of the polymer in fabricated items such as impact resistance and tear resistance. Such structure-property relationships are particularly important for polymers with high commercial importance in terms of the shear tonnage of polymer produced globally, like polyethylene and polyethylene-based copolymers. It is seen that in the case of LLDPE, which is... 

Copolymerisation can be brought about by many types of polymerisation reactions. The majority of the commercially important copolymers, however, are made by free-radical, ionic or polycondensation polymerisation. 

Other polyesters of commercial importance are polycarbonates, liquid crystal polyesters, unsaturated polyesters, and copolymers (Secs. 2-8e, 2-14g, 2-12, 2-13). 

Many other copolymers of commercial importance have been discussed previously see Secs. 3-14c (vinyl acetate, vinylidene chloride), 3-14d (acrylic and methacrylic acids and esters,... 

Copolymerization. The copolymerization of butadiene-styrene with alkyllithium initiator has drawn considerable attention in the last decade because of the inversion phenomenon (12) and commercial importance (13). It has been known that the rate of styrene homopolymerization with alkyllithium is more rapid than butadiene homopolymerization in hydrocarbon solvent. However, the story is different when a mixture of butadiene and styrene is used. The propagating polymer chains are rich in butadiene until late in reaction when styrene content suddenly increases. This phenomenon is called inversion because of the rate of butadiene polymerization is now faster than the styrene. As a result, a block copolymer is obtained in this system. However, the copolymerization characteristic is changed if a small amount of polar solvent... 

Because P1VN and P2VN do not have the same commercial importance as PS, less data are available for the UV absorbance of the vinylnaphthalene polymers and copolymers. Laitinen and co-workers 26) were the first to report the absorbance spectrum between 240 and 300 nm of P2VN in chloroform solution. They found... 

However, often it is difficult to produce suitable graft or block copolymers for important commercial applications. Alternatively, these compatibilizing copolymers can be generated in situ during the blend preparation through polymer-polymer grafting reactions using functionalized polymers (38). 

Stearamidomethylpyridinium chloride is used in waterproofing textiles. It is made by reacting pyridine hydrochloride with stearamide and formaldehyde. Vmylpyridines are used as components of acrylonitrile copolymers to improve the dyeability of polyacrylonitrile fibers. Tile commercially important products are 2-vinylpyndine 4-vinylpyndine and 2-methyl-5-vinylpyridine. Formulas are shown below. 

When polymerization occurs in a mixture of monomers there will be competition between the different kinds of monomers to add to the growing chain and produce a copolymer. Such a polymer will be expected to have physical properties quite different from those of a mixture of the separate homopolymers. Many copolymers, such as GRS, ethene-propene, Viton rubbers, and Vinyon plastics are of considerable commercial importance. 

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