Chain retardive

Synthetic and mechanistic aspects of iatramolecular cycli2ation in the tricycHc diterpenoid area have been studied in detail. In general, the presence of electron withdrawing groups such as carbonyl in the side chain retard the rates of cycli2ation (61). 

Phenols are antioxidants (see Chapter 12) and terminate chains retarding oxidation. 

In the photodecomposition of polystyrene-bound cobaloximes, the polymer chain decreases the mobility of bis(dimethylglyoximato)pyridinecobalt(L) and increases the probability of recombination of L and a radical fixed on the polymer chain. Retardation of the dissociation resulted in a larger equilibrium constant for the polymeric system than that for the analogous monomeric system.130... 

The hydrogenation rate under pressure decreases in the series benzene, mono- di-, tri-, tetra-, penta-, and hexamethylbenzenes on Ni/ALOa but increases on WS2 (420, 421). In the hydrogenation of ketones on Pt, the branching of the carbon chain retards the reaction (422). If the reaction rate after the substitution decreases this means that SQab > SQak ... 

Antioxidants markedly retard the rate of autoxidation throughout the useful life of the polymer. Chain-terminating antioxidants have a reactive —NH or —OH functional group and include compounds such as secondary aryl amines or hindered phenols. They function by transfer of hydrogen to free radicals, principally to peroxy radicals. Butylated hydroxytoluene is a widely used example. 

We conclude this section by noting an extreme case of chain transfer, a reaction which produces radicals of such low reactivity that polymerization is effectively suppressed. Reagents that accomplish this are added to commercial monomers to prevent their premature polymerization during storage. These substances are called either retarders or inhibitors, depending on the degree of protection they afford. Such chemicals must be removed from monomers prior to use, and failure to achieve complete purification can considerably affect the polymerization reaction. 

An example of a commercial semibatch polymerization process is the early Union Carbide process for Dynel, one of the first flame-retardant modacryhc fibers (23,24). Dynel, a staple fiber that was wet spun from acetone, was introduced in 1951. The polymer is made up of 40% acrylonitrile and 60% vinyl chloride. The reactivity ratios for this monomer pair are 3.7 and 0.074 for acrylonitrile and vinyl chloride in solution at 60°C. Thus acrylonitrile is much more reactive than vinyl chloride in this copolymerization. In addition, vinyl chloride is a strong chain-transfer agent. To make the Dynel composition of 60% vinyl chloride, the monomer composition must be maintained at 82% vinyl chloride. Since acrylonitrile is consumed much more rapidly than vinyl chloride, if no control is exercised over the monomer composition, the acrylonitrile content of the monomer decreases to approximately 1% after only 25% conversion. The low acrylonitrile content of the monomer required for this process introduces yet another problem. That is, with an acrylonitrile weight fraction of only 0.18 in the unreacted monomer mixture, the low concentration of acrylonitrile becomes a rate-limiting reaction step. Therefore, the overall rate of chain growth is low and under normal conditions, with chain transfer and radical recombination, the molecular weight of the polymer is very low. 

In order for a soHd to bum it must be volatilized, because combustion is almost exclusively a gas-phase phenomenon. In the case of a polymer, this means that decomposition must occur. The decomposition begins in the soHd phase and may continue in the Hquid (melt) and gas phases. Decomposition produces low molecular weight chemical compounds that eventually enter the gas phase. Heat from combustion causes further decomposition and volatilization and, therefore, further combustion. Thus the burning of a soHd is like a chain reaction. For a compound to function as a flame retardant it must intermpt this cycle in some way. There are several mechanistic descriptions by which flame retardants modify flammabiUty. Each flame retardant actually functions by a combination of mechanisms. For example, metal hydroxides such as Al(OH)2 decompose endothermically (thermal quenching) to give water (inert gas dilution). In addition, in cases where up to 60 wt % of Al(OH)2 may be used, such as in polyolefins, the physical dilution effect cannot be ignored. 

Chemical Interaction. Halogens and some phosphoms flame retardants act by chemical interaction. The flame retardant dissociates into radical species that compete with chain propagating and branching steps in the combustion process. 

The majority of secondary plasticizers ia use are chlotinated paraffins, which are hydrocarbons chlotinated to a level of 30—70%. Eor a given hydrocarbon chain, viscosity iacreases with chlorine content, as does the fire retardancy imparted to the formulation. These materials aid fire retardancy due to thein chlorine content. Chlotinated paraffins of the same chlorine content may, however, have different volatiHties and viscosities if they are based on different hydrocarbon chaias (see Cm OROCARBONS and cm OROHYDROCARBONS, cm.ORiNATDD paraffins). 

Because of the low reactivity and tendency to undergo chain transfer, small additions of most aHyl compounds retard polymerization of typical vinyl monomers ia free-radical systems (1,3) and may be useful ia controlling molecular weight and stmcture ia polymers. 

In the case of hyperphenylalaninaemia, which occurs ia phenylketonuria because of a congenital absence of phenylalanine hydroxylase, the observed phenylalanine inhibition of proteia synthesis may result from competition between T.-phenylalanine and L-methionine for methionyl-/RNA. Patients sufferiag from maple symp urine disease, an inborn lack of branched chain oxo acid decarboxylase, are mentally retarded unless the condition is treated early enough. It is possible that the high level of branched-chain amino acids inhibits uptake of L-tryptophan and L-tyrosiae iato the brain. Brain iajury of mice within ten days after thek bkth was reported as a result of hypodermic kijections of monosodium glutamate (MSG) (0.5—4 g/kg). However, the FDA concluded that MSG is a safe kigredient, because mice are bom with underdeveloped brains regardless of MSG kijections (106). 

Rubber Chemicals. Sodium nitrite is an important raw material in the manufacture of mbber processing chemicals. Accelerators, retarders, antioxidants (qv), and antiozonants (qv) are the types of compounds made using sodium nitrite. Accelerators, eg, thiuram [137-26-8J, greatly increase the rate of vulcaniza tion and lead to marked improvement in mbber quaUty. Retarders, on the other hand (eg, /V-nitrosodiphenylamine [156-10-5]) delay the onset of vulcanization but do not inhibit the subsequent process rate. Antioxidants and antiozonants, sometimes referred to as antidegradants, serve to slow the rate of oxidation by acting as chain stoppers, transfer agents, and peroxide decomposers. A commonly used antioxidant is A/,AT-disubstituted Nphenylenediamine which can employ sodium nitrite in its manufacture (see Rubber chemicals). 

J) At position 1, an acidic side chain two or three carbons long should be present. The natural L-alanyl side chain reduces receptor binding but enhances in vivo activity by increasing access to the receptor and by retarding metaboHsm and excretion. The enantiomeric D-analogues retain considerable activity in contrast to other bioactive substances (17). 

Amines can also swell the polymer, lea ding to very rapid reactions. Pyridine, for example, would be a fairly good solvent for a VDC copolymer if it did not attack the polymer chemically. However, when pyridine is part of a solvent mixture that does not dissolve the polymer, pyridine does not penetrate into the polymer phase (108). Studies of single crystals indicate that pyridine removes hydrogen chloride only from the surface. Kinetic studies and product characterizations suggest that the reaction of two units in each chain-fold can easily take place further reaction is greatiy retarded either by the inabiUty of pyridine to diffuse into the crystal or by steric factors. 

Mini-emulsion processes have been developed where the monomer is emulsified under high energy with either a long-chain alcohol or a polymer producing very small droplets. The long-chain alcohol retards the diffusion of the monomer out of the droplets (65). Polymerization takes place primarily... 

Chain transfer also occurs to the emulsifying agents, leading to their permanent iacorporation iato the product. Chain transfer to aldehydes, which may be formed as a result of the hydrolysis of the vinyl acetate monomer, tends to lower the molecular weight and slow the polymerisation rate because of the lower activity of the radical that is formed. Thus, the presence of acetaldehyde condensates as a poly(vinyl alcohol) impurity strongly retards polymerisation (91). Some of the initiators such as lauryl peroxide are also chain-transfer agents and lower the molecular weight of the product. 

Oil Repellent. Fluorochemicals are the only class of material that can provide oil repeUency without altering the porosity of the paper or paperboard. Physical barriers to oil penetration are used primarily for their moisture- or gas-barrier properties, with retarded oil penetration as a secondary benefit. The most common od-repeUent additives are long-chain perfluoroalkyl phosphate salts of ammonia or diethanol amine. Commercial sources include Scotchban (3M), Zonyl (DuPont), and Lodyne (Ciba Specialties). There are also a fluorochemical carboxylate salt, Lodyne (Ciba Specialties), and fluorochemical copolymers, eg, Scotchban (3M). The widest range of oily fluid holdout is provided by the fluorochemical copolymers. 

Flame Retardants. Bromine compounds make up an important segment of the market for flame retardants used in polymers. Additive flame retardants are added to polymers during processing reactive flame retardants react chemically to become part of the polymer chain itself. In addition to the compounds Hsted in Table 3, a number of proprietary mixtures and phosphoms—bromine-containing flame retardants are also sold (see Elame RETARDANTS, HALOGENATED, FLAAffi RETARDANTS). 

A/-substituted, long-chain alkyl monomethylol cycHc ureas have also been used to waterproof cotton through etherification. Other water repellent finishes for cotton are produced by cross-linked siHcone films (56). In addition to the polymeri2ation of the phosphoms-containing polymers on cotton to impart flame retardancy and of siHcone to impart water repeUency, polyduorinated polymers have been successfuUy appHed to cotton to impart oil repeUency. Chemical attachment to the cotton is not necessary for durabUity oU repeUency occurs because of the low surface energy of the duorinated surface (57). 

Thus the thiol 0 2 25511 is capable of terminating a growiug chain and also initiating a new chain. If the initiation-rate constant, k is not much slower than the propagation-rate constant, the net result is the growth of a new chain without any effect on the overall polymerization rate (retardation). That represents a tme chain transfer, ie, no effect on the rate but a substantial decrease iu molecular weight (12). 

Monomer conversion (79) is followed by measuring the specific gravity of the emulsion. The polymerization is stopped at 91% conversion (sp gr 1.069) by adding a xylene solution of tetraethylthiuram disulfide. The emulsion is cooled to 20°C and aged at this temperature for about 8 hours to peptize the polymer. During this process, the disulfide reacts with and cleaves polysulfide chain segments. Thiuram disulfide also serves to retard formation of gel polymer in the finished dry product. After aging, the alkaline latex is acidified to pH 5.5—5.8 with 10% acetic acid. This effectively stops the peptization reaction and neutralizes the rosin soap (80). 

In addition, other additives may exist which react with R and RO2, introducing new propagation reactions which lead to a slower chain reaction. Such materials would be referred to as oxidation retarders. 

In the past the greatest attention has been paid to the chain-breaking antioxidants and oxidation retarders of general structure AH, which may function in the following ways. 

It will be noticed that with chain-breaking antioxidants the additive will be consumed whilst if we assume that the AO2H molecule will regenerate A radicals the oxidation retarder is not effectively consumed. The difference between the two is illustrated schematically in Figure 7.4. 

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