Polymer mastication

Tabrel9. Polymerization of methyl methacrylate by natural polymer mastication (82)... 

Guns are used to apply cartridges of sealants (polyurethanes, silicones) and also adhesives in mastics form such as polychloroprene or MS polymer mastics. The cartridges are made of plastic (polyethylene), metal or cardboard, the bottom of the cartridge is a piston, so that when the trigger of the gun is actuated the piston will push the sealant to extrude it through a tip cut to the proper diameter (Fig. 11). 

Fig. 2. Change in Wallace rapid plasticity with time during open mill polymer mastication (mill friction ratio 1 1 2, starting temperature 40°C).

Other Uses. Large quantities of hydrocarbon resins are used in mastics, caulks, and sealants (qv). Polymers for these adhesive products include neoprene, butyl mbber, polyisoprene, NR, SBR, polyisobutylene, acryHcs, polyesters, polyamides, amorphous polypropylene, and block copolymers. These adhesives may be solvent or water-borne and usually contain inorganic fillers. 

A review covers the preparation and properties of both MABS and MBS polymers (75). Literature is available on the grafting of methacrylates onto a wide variety of other substrates (76,77). Typical examples include the grafting of methyl methacrylate onto mbbers by a variety of methods chemical (78,79), photochemical (80), radiation (80,81), and mastication (82). Methyl methacrylate has been grafted onto such substrates as cellulose (83), poly(vinyl alcohol) (84), polyester fibers (85), polyethylene (86), poly(styrene) (87), poly(vinyl chloride) (88), and other alkyl methacrylates (89). 

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. 

Another major area of use is in the field of adhesives. The main attractions of the material are the absence of a need for mastication, easy solvation of the polymer, which is supplied in a crumb form, the production of low-viscosity solutions and high joint strength. In conjunction with aromatic resins they are used for contact adhesives whilst with aliphatic resin additives they are used for permanently tacky pressure-sensitive adhesives. In addition to being applied from solution they may be applied as a hot melt. 

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. 

By reduction in the degree of polymerisation. To produce processable rubbers the original polymers are masticated with substances such as benzothiazole disulphide and tetramethylthiuram disulphide. The more severe degradation techniques to produce liquid polysulphides are mentioned below. 

These polymers are very sensitive to mastication. Mastication decreases the solution viscosity and increases the ease of solution. Because the reactive sulphur linkages, rapid vulcanizing properties are obtained. On the other hand, the presence of thiuram disulphide improves the resistance of CR to dehydrochlorination. 

Polymer chains with sulphur atoms, improving breakdown of polychloroprene during mastication, increasing tear resistance and dynamic behaviour. 

Polychloroprene elastomer. Neoprene AC and AD are the most commonly used, mainly Neoprene AD because of its superior viscosity stability. For difficult-to-bond substrates, graft polymers Neoprene AD-G or AF) show better performance. For sprayable adhesives or high-viscosity mastics, the Neoprene AG offers excellent results. When specific properties (e.g. increase tack, improve wetting, increase peel strength) need to be met, blends of Neoprene AC or AD with Neoprene AG provide adequate performance. 

Low-molecular weight chains do not experience enough shear force to induce scission. Watson et al." demonstrated (by the intrinsic viscosity characterization of masticated NR) that the limiting molecular weight for the shear-induced degradation is in the order of 0.7-1.0 X 10 Frenkel independently speculated that shear-induced cleavage occurs near the midpoint of the polymer chain. 

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...

UV-filtered light, as in a museum, effectively reduces the amount of oxidation to almost the same level that occurs in darkness. The polymer fraction of mastic was found to reduce the degree of oxidation in the material, possibly by acting as a radical scavenger. 

Rubber-like materials now superseding the traditional mastics and putties used in the building industry. Such sealants (also termed mastics) are based on butyl rubber, liquid polysulphides, silicone rubbers, polybutylene, nitrile rubbers and plasticised vinyl polymers. SEBS... 

The LP grades are liquid polymers used in sealant and mastic applications, and are formed by breaking down a high molecular weight polymer in a controlled manner. The liquid polymer again has mercaptan end groups. 

Block copolymers have been obtained from polymeric radicals, which—unlike those employed for graft polymerization—have the radical centers at the ends of the polymer chains. This can be achieved by breaking chemical bonds in the polymer backbone by mastication (mixing) of the polymer [Ceresa, 1973, 1976, 1978 Sakaguchi and Sohma, 1978]. If... 

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. 

Mechanochemical Degradation. Mechanochemical degradation occurs in polymers as the result of an applied mechanical force. This type of degradation is quite common in machining processes such as grinding, ball milling, and mastication. 

---