Mastication of polymers

Table 10. Mechanical synthesis of interpolymers by mastication of polymer blends...

The mechanical degradation and production of macroradicals can also be performed by mastication of polymers brought into a rubbery state by admixture with monomer several monomer-polymer systems were examined (10, 11). This technique was for instance studied for the cold mastication of natural rubber or butadiene copolymers in the presence of a vinyl monomer (13, 31, 52). The polymerization of methyl methacrylate or styrene during the mastication of natural rubber has yielded copolymers which remain soluble up to complete polymerization vinyl acetate, which could not produce graft copolymers by the chain transfer technique, failed also in this mastication procedure. Block and graft copolymers were also prepared by cross-addition of the macroradicals generated by the cold milling and mastication of mixtures of various elastomers and polymers, such as natural rubber/polymethyl methacrylate (74), natural rubber/butadiene-styrene rubbers (76) and even phenol-formaldehyde resin/nitrile rubber (125). 

Mechanical Synthesis of Interpolymers by Mastication of Polymer Blends... 

An entirely new concept was iatroduced iato mbber technology with the idea of "castable" elastomers, ie, the use of Hquid, low molecular-weight polymers that could be linked together (chain-extended) and cross-linked iato mbbery networks. This was an appealing idea because it avoided the use of heavy machinery to masticate and mix a high viscosity mbber prior to mol ding and vulcanization. In this development three types of polymers have played a dominant role, ie, polyurethanes, polysulftdes, and thermoplastic elastomers. 

By rolling on a two-roll mill the molecular weight of the polymer can be greatly reduced by mechanical scission, analogous to that involved in the mastication of natural rubber, and so mouldable materials may be obtained. However, bulk polymerisation is expensive and the additional milling and grinding processes necessary make this process uneconomic in addition to increasing the risk of contamination. 

The resin composition was indeed found to influence the ageing processes in mastic, the polymer fraction was shown to reduce the oxidation of triterpenoids (Figure 5.8). This was found for both natural ageing [33, 36] and artificial ageing. Because the polymer, a polymyrcene, contains many double bonds that can easily be oxidised [42], it might act as a radical stabiliser. The mastic samples shown in Figure 5.8 were obtained from three aliquots of the same mastic solution, the polymer part of the first aliquot was removed and added to the third. 

Figure 5.8 GALDI mass spectra of mastic with variable amounts of polymer, artificially aged for 880 h (36] (a) without polymer (b) normal mastic and (c) with added polymer. Oxidation and decomposition is enhanced with lower amounts of polymer, thus the mastic polymer retards oxidation of the triterpenoids...

Grinding or milling causes degradation of many polymers. The process of mastication of natural rubber involves a mechanically initiated, autoxidative degradation which lowers the molecular weight to a level where the material is easier to process on a commercial scale. 

Graft polymers were obtained by mastication of a 60/40 blend of natural rubber and chlorosulphonated polyethylene (/). From 10-55% natural rubber was obtained as side chains. Grafting presumably proceeds by transfer of chlorine atoms to the rubber radicals to give grafting sites for combination with rubber radicals. Soluble linear polymers were also obtained by mastication for 50-180 min under nitrogen for a blend 50/50 of natural rubber and a polyurethane rubber (Vulcaprene A) (/). 

Mechanical synthesis by cold mastication of rubber and monomers depends on the reaction condition (monomer concentration, temperature, solvent concentration, atmosphere, presence of transfer agents, or catalyst) and on the physical and chemical properties of the rubbers, the monomers and the product interpolymers. A critical factor is the shear stress developed in the system rather than instrumentally-defined shear rates. The degree of reaction of polymer and consequently also the concentration of free macroradicals depends on stress. As a consequence, the influence of the above parameters may be connected to their influence on the viscosity of the reaction medium since an increase in viscosity causes an increase in stress at constant shear rate. 

Fig. 24. Composition during the mastication of initially (a) 24% methyl methacrylate in polystyrene and (b) 38% styrene in polymethyl methacrylate. Curves a, b, and c Free polystyrene, block polymer, and free polymethyl methacrylate, respectively. Curves d, b and c ...

Acrylonitrile monomer when masticated in the presence of polymer leads to the formation of pseudocrosslinked block copolymers by mechanical scission of soluble block copolymers. The aggregation of the polyacrylonitrile chains of the block copolymer fraction results in the formation of swollen gels when the polymerization products are extracted with solvents from the initial polymer (78-80). 

Table 20. Polymerization of vinyl polymers by mastication of cellulose derivatives (80)...

Mastication of rubber. VIII. Preparation of block polymers by... 

Thus, macroradicals have been obtained by stretching fibers (20), deforming plastics by compression (37), ball mill grinding (11), freezing and grinding of polymer solutions (10), ultrasonic irradiation (I), mastication (19), dispersion in a microblender (25), and other mechanical techniques (36). Many reviews on the formation of macroradicals by degradative processes have also been published (5, 12,13,16, 33). 

Polymers are very soft materials which are not easily milled under normal conditions. The mastication of natural rubber is the reduction of molecular weight by milling or cutting, the process being invented by Thomas Hancock as early as 1820. Even today this is a major industrial process in the tire and rubber industry. Other polymers are milled under reduced temperature or even in liquid nitrogen to achieve a controlled molecular mass. The degradation of several polymers has been investigated by Dimitrov et al. [104]. 

Polymer technology is quite old compared to polymer science. For example, natural rubber was first masticated to render it suitable for dissolution or spreading on cloth in 1820. and the first patents on vulcanization appeared some twenty years later. About another one hundred years were to elapse, however, before it was generally accepted that natural rubber and other polymers are composed of giant covalently bonded molecules that differ from ordinary molecules primarily only in size. (The historical development of modern ideas of polymer constitution is traced by Flory in his classical book on polymer chemistry [ I ], while Brydson [2] reviews the history of polymer technology.) Since some of the terms we are going to review derive from technology, they are less precisely defined than those the... 

The role of a peptizer is to enhance the mechanochemical degradation of a polymer, such as the mastication of natural mbber, and known peptizers are thiols and diarylsulfides. The mechanism of action is believed to be the redox decomposition of hydroperoxides (Scott, 1993b), as shown in Scheme 1.70(a) ... 

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