Copolymer, free radical

Other useful modifications include acetylation, hydroxyethylation, hydro-xypropylation, cationic starches, succinate, and substituted succinate derivatives of starch. In starch-grafted copolymers, free radicals are initiated on the starch that then act as macroinitiators for the acryl or vinyl monomers. These products are used in firefighting fluids, electrolyte solutions for alkaline batteries, wound dressing, and so on. 

Another approach for the preparation of organic polymers with cyclophos-phazene side groups involves the Staudinger reaction of an azido- substituted cyclophosphazene with a phosphine residue in an organic copolymer. Free-radical copolymerization of styrene with diphenyl-p-styrylphosphine yields... 

Free-radical polymerization is used to produce graft copolymers. Free-radical sites on the macromolecule provide sites for an unsaturated copolymer to graft, a method commonly used for polyolefins [9, 14]. 

Synthetic copolymers Free radical copolymerization of 2-p-nitrobenz.oxvethyi methacrylate and methoxydiethoxyethyl methacrylate. Chemical hydrolysis of polymer backbone. Drug delivery system. Pitt and Shah, 1995... 

Dyads and triads in copolymers Free radical polymerization Geometric distribution Dyads and triads in terpolymers Nncleotide sequences in DNA Amino acid sequences in protein Sequence alignment... 

Polymeric vinylidene chloride generally produced by free radical polymerization of CH2 = CCl2. Homopolymers and copolymers are used. A thermoplastic used in moulding, coatings and fibres. The polymers have high thermal stability and low permeability to gases, and are self extinguishing. 

The elastomer produced in greatest amount is styrene-butadiene rubber (SBR) Annually just under 10 lb of SBR IS produced in the United States and al most all of it IS used in automobile tires As its name suggests SBR is prepared from styrene and 1 3 buta diene It is an example of a copolymer a polymer as sembled from two or more different monomers Free radical polymerization of a mixture of styrene and 1 3 butadiene gives SBR... 

Styrene-butadiene rubber is prepared from the free-radical copolymerization of one part by weight of styrene and three parts by weight of 1,3-butadiene. The butadiene is incorporated by both 1,4-addition (80%) and 1,2-addition (20%). The configuration around the double bond of the 1,4-adduct is about 80% trans. The product is a random copolymer with these general features ... 

Remember from Sec. 1.3 that graft copolymers have polymeric side chains which differ in the nature of the repeat unit from the backbone. These can be prepared by introducing a prepolymerized sample of the backbone polymer into a reactive mixture—i.e., one containing a source of free radicals—of the side-chain monomer. As an example, consider introducing polybutadiene into a reactive mixture of styrene ... 

We begin our discussion of copolymers by considering the free-radical polymerization of a mixture of two monomers. Mi and M2. This is already a narrow view of the entire field of copolymers, since more than two repeat units can be present in copolymers and, in addition, mechanisms other than free-radical chain growth can be responsible for copolymer formation. The essential features of the problem are introduced by this simpler special case, so we shall restrict our attention to this system. 

Note that this inquiry into copolymer propagation rates also increases our understanding of the differences in free-radical homopolymerization rates. It will be recalled that in Sec. 6.1 a discussion of this aspect of homopolymerization was deferred until copolymerization was introduced. The trends under consideration enable us to make some sense out of the rate constants for propagation in free-radical homopolymerization as well. For example, in Table 6.4 we see that kp values at 60°C for vinyl acetate and styrene are 2300 and 165 liter mol sec respectively. The relative magnitude of these constants can be understod in terms of the sequence above. 

In resists of this class, the imaging layer contains a multifunctional monomer that can form an intercormected network upon polymerization, and a photosensitizer to generate a flux of initiating free radicals. Although not stricdy required for imaging, the composition usually includes a polymeric binder (typically an acryhc copolymer) to modify the layer s physical properties. Figure 7b shows the chemical stmctures of typical components. 

Butenediol does not undergo free-radical polymerization. A copolymer with vinyl acetate can be prepared with a low proportion of butenediol (110). 

Thermal Oxidative Stability. ABS undergoes autoxidation and the kinetic features of the oxygen consumption reaction are consistent with an autocatalytic free-radical chain mechanism. Comparisons of the rate of oxidation of ABS with that of polybutadiene and styrene—acrylonitrile copolymer indicate that the polybutadiene component is significantly more sensitive to oxidation than the thermoplastic component (31—33). Oxidation of polybutadiene under these conditions results in embrittlement of the mbber because of cross-linking such embrittlement of the elastomer in ABS results in the loss of impact resistance. Studies have also indicated that oxidation causes detachment of the grafted styrene—acrylonitrile copolymer from the elastomer which contributes to impact deterioration (34). 

In all manufacturing processes, grafting is achieved by the free-radical copolymerization of styrene and acrylonitrile monomers in the presence of an elastomer. Ungrafted styrene—acrylonitrile copolymer is formed during graft polymerization and/or added afterward. 

Emulsion Adhesives. The most widely used emulsion-based adhesive is that based upon poly(vinyl acetate)—poly(vinyl alcohol) copolymers formed by free-radical polymerization in an emulsion system. Poly(vinyl alcohol) is typically formed by hydrolysis of the poly(vinyl acetate). The properties of the emulsion are derived from the polymer employed in the polymerization as weU as from the system used to emulsify the polymer in water. The emulsion is stabilized by a combination of a surfactant plus a coUoid protection system. The protective coUoids are similar to those used paint (qv) to stabilize latex. For poly(vinyl acetate), the protective coUoids are isolated from natural gums and ceUulosic resins (carboxymethylceUulose or hydroxyethjdceUulose). The hydroHzed polymer may also be used. The physical properties of the poly(vinyl acetate) polymer can be modified by changing the co-monomer used in the polymerization. Any material which is free-radically active and participates in an emulsion polymerization can be employed. Plasticizers (qv), tackifiers, viscosity modifiers, solvents (added to coalesce the emulsion particles), fillers, humectants, and other materials are often added to the adhesive to meet specifications for the intended appHcation. Because the presence of foam in the bond line could decrease performance of the adhesion joint, agents that control the amount of air entrapped in an adhesive bond must be added. Biocides are also necessary many of the materials that are used to stabilize poly(vinyl acetate) emulsions are natural products. Poly(vinyl acetate) adhesives known as "white glue" or "carpenter s glue" are available under a number of different trade names. AppHcations are found mosdy in the area of adhesion to paper and wood (see Vinyl polymers). 

Copolymers of VF and a wide variety of other monomers have been prepared (6,41—48). The high energy of the propagating vinyl fluoride radical strongly influences the course of these polymerizations. VF incorporates well with other monomers that do not produce stable free radicals, such as ethylene and vinyl acetate, but is sparingly incorporated with more stable radicals such as acrylonitrile [107-13-1] and vinyl chloride. An Alfrey-Price value of 0.010 0.005 and an e value of 0.8 0.2 have been determined (49). The low value of is consistent with titde resonance stability and the e value is suggestive of an electron-rich monomer. 

Most commercial processes involve copolymerization of ethylene with the acid comonomer followed by partial neutralization, using appropriate metal compounds. The copolymerization step is best carried out in a weU-stirred autoclave with continuous feeds of all ingredients and the free-radical initiator, under substantially constant environment conditions (22—24). Owing to the relatively high reactivity of the acid comonomer, it is desirable to provide rapid end-over-end mixing, and the comonomer content of the feed is much lower than that of the copolymer product. Temperatures of 150—280°C and pressures well in excess of 100 MPa (1000 atm) are maintained. Modifications on the basic process described above have been described (25,26). When specific properties such as increased stiffness are required, nonrandom copolymers may be preferred. An additional comonomer, however, may be introduced to decrease crystallinity (10,27). 

Polymerization of methacrylates is also possible via what is known as group-transfer polymerization. Although only limited commercial use has been made of this technique, it does provide a route to block copolymers that is not available from ordinary free-radical polymerizations. In a prototypical group-transfer polymerization the fluoride-ion-catalyzed reaction of a methacrylate (or acrylate) in the presence of a silyl ketene acetal gives a high molecular weight polymer (45—50). 

Density. The density (crystallinity) of catalyticaHy produced PE is primarily determined by the amount of comonomer ( a-olefin) in ethylene copolymer. This amount is easily controlled by varying the relative amounts of ethylene and the comonomer in a polymerization reactor. In contrast, the density of PE produced in free-radical processes is usually controlled by temperature. 

Polymerization using oxygen is not well understood it is known that oxygen copolymerizes with ethylene to form peroxidic copolymers (10). Other free-radical generators such as azo compounds and carbon—carbon compounds have found only limited use in the synthesis of LDPE. 

The second type of solution polymerization concept uses mixtures of supercritical ethylene and molten PE as the medium for ethylene polymerization. Some reactors previously used for free-radical ethylene polymerization in supercritical ethylene at high pressure (see Olefin POLYMERS,LOW DENSITY polyethylene) were converted for the catalytic synthesis of LLDPE. Both stirred and tubular autoclaves operating at 30—200 MPa (4,500—30,000 psig) and 170—350°C can also be used for this purpose. Residence times in these reactors are short, from 1 to 5 minutes. Three types of catalysts are used in these processes. The first type includes pseudo-homogeneous Ziegler catalysts. In this case, all catalyst components are introduced into a reactor as hquids or solutions but form soHd catalysts when combined in the reactor. Examples of such catalysts include titanium tetrachloride as well as its mixtures with vanadium oxytrichloride and a trialkyl aluminum compound (53,54). The second type of catalysts are soHd Ziegler catalysts (55). Both of these catalysts produce compositionaHy nonuniform LLDPE resins. Exxon Chemical Company uses a third type of catalysts, metallocene catalysts, in a similar solution process to produce uniformly branched ethylene copolymers with 1-butene and 1-hexene called Exact resins (56). 

Olig omerization and Polymerization. Siace an aHyl radical is stable, linear a-olefins are not readily polymerized by free-radical processes such as those employed ia the polymerization of styrene. However, ia the presence of Ziegler-Natta catalysts, these a-olefins can be smoothly converted to copolymers of various descriptions. Addition of higher olefins during polymerization of ethylene is commonly practiced to yield finished polymers with improved physical characteristics. 

Organic peroxides are used in the polymer industry as thermal sources of free radicals. They are used primarily to initiate the polymerisation and copolymerisation of vinyl and diene monomers, eg, ethylene, vinyl chloride, styrene, acryUc acid and esters, methacrylic acid and esters, vinyl acetate, acrylonitrile, and butadiene (see Initiators). They ate also used to cute or cross-link resins, eg, unsaturated polyester—styrene blends, thermoplastics such as polyethylene, elastomers such as ethylene—propylene copolymers and terpolymers and ethylene—vinyl acetate copolymer, and mbbets such as siUcone mbbet and styrene-butadiene mbbet. 

Etherification and esterification of hydroxyl groups produce derivatives, some of which are produced commercially. Derivatives may also be obtained by graft polymerization wherein free radicals, initiated on the starch backbone by ceric ion or irradiation, react with monomers such as vinyl or acrylyl derivatives. A number of such copolymers have been prepared and evaluated in extmsion processing (49). A starch—acrylonitrile graft copolymer has been patented (50) which rapidly absorbs many hundred times its weight in water and has potential appHcations in disposable diapers and medical suppHes. 

Styrene is a colorless Hquid with an aromatic odor. Important physical properties of styrene are shown in Table 1 (1). Styrene is infinitely soluble in acetone, carbon tetrachloride, benzene, ether, / -heptane, and ethanol. Nearly all of the commercial styrene is consumed in polymerization and copolymerization processes. Common methods in plastics technology such as mass, suspension, solution, and emulsion polymerization can be used to manufacture polystyrene and styrene copolymers with different physical characteristics, but processes relating to the first two methods account for most of the styrene polymers currendy (ca 1996) being manufactured (2—8). Polymerization generally takes place by free-radical reactions initiated thermally or catalyticaHy. Polymerization occurs slowly even at ambient temperatures. It can be retarded by inhibitors. 

Eree-radical initiation of emulsion copolymers produces a random polymerisation in which the trans/cis ratio caimot be controlled. The nature of ESBR free-radical polymerisation results in the polymer being heterogeneous, with a broad molecular weight distribution and random copolymer composition. The microstmcture is not amenable to manipulation, although the temperature of the polymerisation affects the ratio of trans to cis somewhat. 

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