Second monomer

As with polyesters, the amidation reaction of acid chlorides may be carried out in solution because of the enhanced reactivity of acid chlorides compared with carboxylic acids. A technique known as interfacial polymerization has been employed for the formation of polyamides and other step-growth polymers, including polyesters, polyurethanes, and polycarbonates. In this method the polymerization is carried out at the interface between two immiscible solutions, one of which contains one of the dissolved reactants, while the second monomer is dissolved in the other. Figure 5.7 shows a polyamide film forming at the interface between an aqueous solution of a diamine layered on a solution of a diacid chloride in an organic solvent. In this form interfacial polymerization is part of the standard repertoire of chemical demonstrations. It is sometimes called the nylon rope trick because of the filament of nylon produced by withdrawing the collapsed film. 

When monomers of drastically different solubiUty (39) or hydrophobicity are used or when staged polymerizations (40,41) are carried out, core—shell morphologies are possible. A wide variety of core—shell latices have found appHcation ia paints, impact modifiers, and as carriers for biomolecules. In staged polymerizations, spherical core—shell particles are made when polymer made from the first monomer is more hydrophobic than polymer made from the second monomer (42). When the first polymer made is less hydrophobic then the second, complex morphologies are possible including voids and half-moons (43), although spherical particles stiU occur (44). 

In the most common production method, the semibatch process, about 10% of the preemulsified monomer is added to the deionised water in the reactor. A shot of initiator is added to the reactor to create the seed. Some manufacturers use master batches of seed to avoid variation in this step. Having set the number of particles in the pot, the remaining monomer and, in some cases, additional initiator are added over time. Typical feed times ate 1—4 h. Lengthening the feeds tempers heat generation and provides for uniform comonomer sequence distributions (67). Sometimes skewed monomer feeds are used to offset differences in monomer reactivity ratios. In some cases a second monomer charge is made to produce core—shell latices. At the end of the process pH adjustments are often made. The product is then pumped to a prefilter tank, filtered, and pumped to a post-filter tank where additional processing can occur. When the feed rate of monomer during semibatch production is very low, the reactor is said to be monomer starved. Under these... 

When the initial monomer supply is exhausted, the anionic chain ends retain their activity. Thus, these anionic chains have been termed living polymers. If more monomer is added, they resume propagation. If it is a second monomer, the result is a block copolymer. 

Anionic polymerization, if carried out properly, can be truly a living polymerization (160). Addition of a second monomer to polystyryl anion results in the formation of a block polymer with no detectable free PS. This technique is of considerable importance in the commercial preparation of styrene—butadiene block copolymers, which are used either alone or blended with PS as thermoplastics. 

Vinyhdene chloride copolymerizes randomly with methyl acrylate and nearly so with other acrylates. Very severe composition drift occurs, however, in copolymerizations with vinyl chloride or methacrylates. Several methods have been developed to produce homogeneous copolymers regardless of the reactivity ratio (43). These methods are appHcable mainly to emulsion and suspension processes where adequate stirring can be maintained. Copolymerization rates of VDC with small amounts of a second monomer are normally lower than its rate of homopolymerization. The kinetics of the copolymerization of VDC and VC have been studied (45—48). 

A tapered block is an impure block of one monomer that has an increasing amount of a second monomer at one end. 

The addition—reaction product of bisphenol A [80-05-07] and glycidyl methacrylate [106-91-2] is a compromise between epoxy and methacrylate resins (245). This BSI—GMA resin polymerizes through a free-radical induced covalent bonding of methacrylate rather than the epoxide reaction of epoxy resins (246). Mineral fillers coated with a silane coupling agent, which bond the powdered inorganic fillers chemically to the resin matrix, are incorporated into BSI—GMA monomer diluted with other methacrylate monomers to make it less viscous (245). A second monomer commonly used to make composites is urethane dimethacrylate [69766-88-7]. 

In order to enhance the reactivity of the chlorine atom, a second reactive monomer can be adopted giving dual cure sites. According to the Hterature, the second monomer can contain carboxyl (22—24), cyanoalkyl (25), hydroxypropyl (26), or epoxy groups (27,28). 

The product, referred to here as S LB, is able to initiate further polymerization. Similar products have been termed living polymers (48). Addition of a second monomer, such as butadiene [106-99-0] gives... 

By copolymerising with a small amount of second monomer which acts as an obstruction to the unzipping reaction, in the event of this being allowed to start. On the industrial scale methyl methacrylate is sometimes copolymerised with a small amount of ethyl acrylate, and formaldehyde copolymerised with ethylene oxide or 1,3-dioxolane for this very reason. 

As with other rigid amorphous thermoplastic polymers such as PVC and polystyrene (see the next chapter) poly(methyl methacrylate) is somewhat brittle and, as with PVC and polystrene, efforts have been made to improve the toughness by molecular modification. Two main approaches have been used, both of which have achieved a measure of success. They are copolymerisation of methyl methacrylate with a second monomer and the blending of poly(methyl methacrylate) with a rubber. The latter approach may also involve some graft copolymerisation. 

Over the years many attempts have been made to produce commercial acrylic polymers with a higher softening point than PMMA. The usual approach was to copolymerise MMA with a second monomer such as maleic anhydride or an N-substituted maleimide which gave homopolymers with a higher Tg than PMMA. In this way copolymers with Vicat softening points as high as 135°C could be obtained. 

The common feature of these materials was that all contained a high proportion of acrylonitrile or methacrylonitrile. The Vistron product, Barex 210, for example was said to be produced by radical graft copolymerisation of 73-77 parts acrylonitrile and 23-27 parts by weight of methyl acrylate in the presence of a 8-10 parts of a butadiene-acrylonitrile rubber (Nitrile rubber). The Du Pont product NR-16 was prepared by graft polymerisation of styrene and acrylonitrile in the presence of styrene-butadiene copolymer. The Monsanto polymer Lopac was a copolymer of 28-34 parts styrene and 66-72 parts of a second monomer variously reported as acrylonitrile and methacrylonitrile. This polymer contained no rubbery component. 

An alternative approach to the production of thermally stable polyoxy-methylenes was made by chemists of the Celanese Corporation of America and the commercial products were marketed as Celcon. Hostaform and Duracon. The principle of thermal stability in this case is the copolymerisation of formaldehyde with a second monomer which is a cyclic ether of the general form shown in Figure 19.3 (I). 

Polymers can also be produced by combining two or more different monomers in the polymerisation process. If two monomers are used the product is called a copolymer and the second monomer is usually included in the reaction to enhance the properties of the polymer produced by the first monomer alone. It is possible to control the way in which the monomers (A and B) link up and there are four main configurations which are considered useful. These are ... 

In a third type of block copolymer formation. Scheme (3), the initiator s azo group is decomposed in the presence of monomer A in a first step. The polymer formed contains active sites different from azo functions. These sites may, after a necessary activation step, start the polymerization of the second monomer B. Actually, route (3) of block copolymer formation is a vice versa version of type (1). It has been shown in a number of examples that one starting bifunctional azo compound can be used for block copolymer synthesis following either path. Reactions of type (3) are tackled in detail in Section III of this chapter. 

Furthermore, photochemically induced homolytical bond cleavage can also be applied when the prepolymer itself does not contain suitable chromophoric groups [113-115]. Upon thermolysis of ACPA in the presence of styrene, a carboxyl-terminated polystyrene is formed. This styrene-based prepolymer was reacted with lead tetraacetate and irradiated with UV light yielding free radicals capable of initiating the polymerization of a second monomer (Scheme 33) [113]. 

Hexamethylenediamine (1,6-hexanediamine) is a colorless solid, soluble in both water and alcohol. It is the second monomer used to produce nylon 6/6 with adipic acid or its esters. 

HO(CH2)eOH + 2NH3 H2N(CH2)eNH2 + 2H2O Hexamethylenediamine is the second monomer for nylon 6/6. 

Numbers that follow the word nylon denote the number of carbons present within a repeating unit and whether one or two monomers are being used in polymer formation. For nylons using a single monomer such as nylon 6 or nylon 12, the numbers 6 and 12 denote the number of carbons in caprolactam and laurolactam, respectively. For nylons using two monomers such as nylon 610, the first number, 6, indicates the number of carbons in the hexamethylene diamine and the other number, 10, is for the second monomer sebacic acid. 

As it is known at present in all countries producing PAN fibres, AN copolymers containing 5—10% of a second monomer are used to increase the elasticity and, in most cases, a third monomer (1-25%) is added to improve the dyeability. 

Of substantial interest for the synthesis of fibre-forming reactive AN copolymers is the use of methacrolein 4 as second monomer, which affords copolymers of type 5, containing aldehyde groups. 

One of the earliest examples of this methodology involves the reaction of a polymeric anion (formed by living anionic polymerization) with molecular oxygen to form a polymeric hydroperoxide which can be decomposed either thermally or, preferably, in a redox reaction to initiate block polymer formation with a second monomer (Scheme 7.25). However, the usual complications associated with initiation by hydroperoxides apply (Section 3.3.2.5). 

The same conditions of initiator efficiency are to be observed when the living carban-ionic end of a polymer chain is used to initiate the polymerization of a second monomer 6,7,26.27) for tjjg synthesis of a block copolymer, the monomers are to be added... 

Sequential addition of monomers 6 7-26-27-114) is the most obvious procedure. Once the first monomer has been polymerized, the resulting living species is used as a polymeric initiator for the polymerization of the second one. The monomers are to be added in the order of increasing electron affinity to provide efficient and fast initiation 26 U4). This condition is rather restrictive, and the number of monomer systems that can be used is limited (Table 5). Moreover, when the second monomer contains an electrophilic function (e.g. ester) which could lead to side reactions, it is necessary to first lower the nucleophilicity of the living site. This is best done by intermediate addition of 1.1-diphenylethylene25). The stabilized diphenylmethyl anions do not get involved in side reactions with ester functions, while initiation is still quantitative and fast. 

Grafting from methods involve creation of metalated sites on a polymer backbone, and subsequent use of these sites to initiate the polymerization of a second monomer. Several examples of such grafting processes have been described 135 ,39>. However, no control of the number and length of the grafts is provided, since some sites may be inaccessible to the incoming monomer. As no accurate characterization... 

Seymour and coworkers (27,28,29,30) actually used these composition gradients to prepare block copolymers by swelling particles containing occluded (i.e., living) macroradicals with a second monomer. Such block copolymers were prepared from occluded vinylacetate, methyl methacrylate, and acrylonitrile macroradicals, and the yield of block copolymers was studied as a function of the solubility and rate of diffusion of the swelling monomer in the particles. 

The chains share the same chemical environment and grow at the same average rate. If the final chain length is large, all the molecules will have more or less the same size and the resulting pol5Tner will be approximately monodisperse. Furthermore, if a second monomer is added to the system after the first has been depleted, a block copol5Tner can be formed. 

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