As chain transfer agents

The thiol ( -dodecyl mercaptan) used ia this recipe played a prominent role ia the quaUty control of the product. Such thiols are known as chain-transfer agents and help control the molecular weight of the SBR by means of the foUowiag reaction where M = monomer, eg, butadiene or styrene R(M) = growing free-radical chain k = propagation-rate constant = transfer-rate constant and k = initiation-rate constant. 

Other additives that may be incorporated include sodium hydrogen phosphates as buffering agents to stabilise that pH of the reaction medium, lauryl mercaptan or trichlorethylene as chain transfer agents to control molecular weight, a lubricant such as stearic acid and small amounts of an emulsifier such as sodium lauryl sulphate. 

Peroxyacetals 58106 and peresters such as 61107 are also effective transfer agents, however, at typical polymerization temperatures ( 60 CC) they are thermally unstable and also act as initiators. Compounds such as 62 which may give addition and 1,5-intramolecular substitution with fragmentation have also been examined for their potential as chain transfer agents (l,5-SHi mechanism).108... 

The values of k" and E are highly dependent on the initiator types and their effects on the solvent types are less overwhelming. The types of solvent used as chain transfer agent are usually fixed... 

Morton and Salatiello have deduced the ratio kpp/kp for radical polymerization of butadiene by applying the above described procedure, appropriately modified for the emulsion system they used. The primary molecular weight was controlled by a mercaptan acting as chain transfer agent, as in the experiments of Bardwell and Winkler cited above. Measurement of the mercaptan concentration over the course of the reaction provided the necessary information for calculating % at any stage of the process, and in particular at the critical conversion 6c for the initial appearance of gel. The velocity constant ratios which they obtained from their results through the use of Eq. 

Complexes of tetravalent zirconium with organic acids, such as citric, tartaric, malic, and lactic acids, and a complex of aluminum and citric acid have been claimed to be active as dispersants. The dispersant is especially useful in dispersing bentonite suspensions [288]. Polymers with amine sulfide terminal moieties are synthesized by using aminethiols as chain transfer agents in aqueous addition polymerizations. The polymers are useful as mineral dispersants [1182]. 

Monofunctional and difunctional xanthates, shown in Scheme 30, were employed as chain transfer agents in the synthesis of block and triblock copolymers of acrylic acid, AA and acrylamide, AAm PAA-fr-PAAm, PAAm-fr-PAA-fo-PAAm and P(AA-sfaf-AAm)-fr-PAAm [81]. The polymerizations were conducted in aqueous solutions at 70 °C with 4,4 -azobis(4-cyanopentanoic acid) as the initiator. The yields were almost quantitative,... 

A number of different materials were used as chain transfer agents to control molecular weight. These results are shown in Table 6.1. The effect of varying concentration of t-butyl alcohol and reaction temperature is shown in Figure 6.1. The results are consistent with normal free radical polymerizations. Polymer output was characterized by inherent viscosity and ZST tests. 

Semitelechelic HPMA polymers were synthesized by free radical polymerization of HPMA using 2,2 -azobis(isobutyronitrile) (AIBN) as the initiator and alkyl mercaptans as chain transfer agents. Alkyl mercaptans with different functional groups, namely, 2-mercaptoethylamine, 3-mercapto-propionic acid, 3-mercaptopropionic hydrazide, and methyl 3-mercapto-propionate, were used as the chain transfer agents ST HPMA polymers... 

Termination may also occur by chain transfer with the initiator (e.g., water or alcohol) or a deliberately added chain-transfer agent. Deliberate termination of growth is carried out to produce polymers with specific molecular weights or, more often, telechelic polymers with specific end groups. Hydroxyl and amine end groups are obtained by using water and ammonia as chain-transfer agents. Carboxyl-ended telechelics can be obtained by termination with ketene silyl acetal followed by hydrolysis with base [Kobayashi et al., 1989]. 

Polymers prepared by current industrial processes have been compared with this new process in the dispersion of GCC and PCCs (Tables 1-3). These current processes use as chain transfer agent inorganic salts processes A and B) or alcohol process D). 

Secondary aromatic amines, such as phenyl beta-naphthylamine. have been used as antioxidants in elastomers, but the preferred antioxidants for plastics have been 2,6-disubstituted and 2,4,6-trisubstituted phenols. These hindered phenols serve as chain transfer agents with the macroradicals which are produced by the degradation of polymers. 

A novel procedure [5] is exemplified in the preparation of polystyryl aluminium derivatives by thermal polymerization of styrene in the presence of AlEt3 acting as chain transfer agent. 

In order to synthesize telechelic polymers, the ROMP reaction is carried out in the presence of acyclic olefins that act as chain transfer agents to regulate the molecular weight of the polymers produced. 

To lower the molecular weight, either hydrogen can be used as chain transfer agent or the polymerization temperature can be increased. In contrast, the molecular weight can only be increased by lowering the temperature (21). 

For the control of the molecular weight, mercaptans are used as chain transfer agents. The use of a solvent, such as ethylbenzene or toluene may be helpful for viscosity control of the polymer solution. However, the rate of production may decreased as the load of the devolatizing unit increases. 

Finally, the ASA graft copolymer is prepared. To the alkyl acrylate rubber polymer obtained as described just above, styrene and acrylonitrile are added in the desired quantities. Dodecylmercaptan and potassium persulfate are added as chain transfer agent and radical initiator, respectively. An ASA copolymer with a mean diameter of 550 nm is obtained. 

The effect of water is to be explained. Cationic polymerization of VCZ is generally not inhibited by water. The monomer is very basic and can well compete for the carbonium ion with water. Since the polymerization is readily initiated by a proton, water acts as chain transfer agent rather than inhibitor. Although the reactivity of the carbonium ion depends certainly on the nature of the counter-ion, as will be discussed later, water seems to act as an efficient chain transfer agent, at least in the present system. The Ion-radical might consequently be converted to a proton so that the cationic propagation could even be promoted in the presence of water. 

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