Prepolymer heating/cooling

The reaction mixture is dehydrated at temperatures as high as 160°C (higher temperatures can be tolerated than with resoles). The prepolymer is cooled, crushed, blended with 5-15% hexamethylenetetramine, (CH2)6N4, and sold to the fabricator. Hexamethylenetetramine, referred to as hexa, is the product of the reaction of 6 mol of formaldehyde and 4 mol of ammonia. Curring occurs rapidly on heating with the formation of both methylene and ben-zylamine crosslinking bridges between benzene rings. The crosslinked network is pictured as... 

PA-4,6 salt is prepared from adipic acid and 1,4-tetramethylenediamine as described for the PA-6,6 salt (Example la). PA-4,6 salt (20 g), 2 mL water, and 0.2 mL 1,4-tetramethylenediamine (2.1 mol % excess) are added to a 100-mL glass container in an autoclave. The autoclave is flushed with nitrogen, closed, and given a starting nitrogen pressure of 5 bar. The autoclave is heated over a period of 60 min to 180° C and maintained at that temperature for 100 min, when the pressure is increased to about 8 bar. The pressure is then gradually released, the reaction mass cooled, and the material removed from the autoclave. The prepolymer is crushed into small particles (0.1—0.2 mm) (see Example lb). This prepolymer has a relative viscosity (r]rd) of 1.3 as measured in 96% sulfuric acid (1% solution at 25° C). 

A prepolymer is made first by charging Pluracol E2000 [1000.0 g, 1.0 eq., poly(ethylene oxide), 56 OH, BASF] to a suitable container equipped with a mechanical stirrer and a nitrogen gas inlet. Flush the container with dry nitrogen and add Desmodur W (264.0 g, 2.0 eq., 4,4 -methylene-bis(cyclohexyl isocyanate), 31.8% NCO, Bayer). While maintaining a positive N2 pressure on the reaction mixture, stir and heat at 80°C for 2 h. Cool the product to room temperature and check the NCO content (theory = 3.32 %). It might be necessary to warm the highly viscous prepolymer to take samples for titration. To a portion of this prepolymer (250.0 g, 0.2 eq.), add Dabco T-12 (0.25 g, dibutyltin dilaurate,... 

The amino resins or plastics, closely related to the phenolics in both synthesis and applications, are obtained by the polymerization of formaldehyde with urea (XXXVII) (/ = 4) or melamine (XXXVIII) (f — 6). Synthesis of the amino plastics can be carried out either in alkaline or acidic conditions [Drumm and LeBlanc, 1972 Nair and Francis, 1983 Updegraff, 1985]. Control of the extent of reaction is achieved by pH and temperature control. The prepolymer can be made at various pH levels depending on the reaction temperature chosen. Polymerization is stopped by cooling and bringing the pH close to neutral. Curing of the prepolymer involves heating, usually in the presence of an added acid catalyst. 

THERMOPLASTIC. A high polymer that softens when exposed to heat and returns to its original condition when cooled to room temperature. Natural substances that exhibit this behavior are crude rubber and a number of waxes however, the term is usually applied to synthetics such as polyvinyl chloride, nylons, fluorocarbons, linear polyethylene, polyurethane prepolymer, polystyrene, polypropylene, and cellulosic and acrylic resins. See also Plastics. 

Random Prepolymers. These prepolymers are built up from polyfunctional monomers reacting statistically according to the theories of Flory. Reaction is stopped at a desired prepolymer molecular weight, usually by cooling. Final polymerization is achieved by heating therefore the term thermoset is used for them. 

Adhesives wet, flow, and set to a solid during bond formation. The transformation from liquid adhesive to solid bond can be achieved in a number of ways. Where the adhesive is a polymer, the initial starting material is a liquid monomer or prepolymer that, under the conditions of bonding with heat, pressure, and/or catalyst, polymerizes to the solid polymer in the glue line. It is also usual to apply solutions of preformed polymers in suitable solvents to the faces of adherends, and allow bond formation to take place with evaporation of solvent. Alternatively, polymers that can be melted or softened to flow at elevated temperatures can be applied as hot melt adhesives to form the bond on cooling. With porous adherends like wood, penetration of the pores by liquid or molten adhesives is an important factor in bond formation. 

The experimental setup, as shown in Fig. 8.6 can also be used for reactive extrusion with prepolymerization (3). In a stirred tank reaetor that can be heated and cooled the mixture is allowed to prepolymerize thermally (without the addition of initiator). This prepolymerization oeeurred batchwise. The contents of the reactor were heated to 135°C, and onee the thermal polymerization started, it was eooled to maintain this temperature. At a conversion of 25% the reactor was cooled to 60°C to stop the reaction. The tubing from this reactor vessel to the extruder was heated to avoid viscosity problems. In another vessel the initiators were dissolved in a small amount of monomer mixture at room temperature. The prepolymer and the monomer-initiator mixture were pumped to the extruder in a ratio of 10 to 1 and mixed in a small statie mixer at the feed port. The volume of the static mixer was chosen such that the residence time in this mixer was in the order of one second to prevent polymerization inside the mixer. 

Plastic is a material that can be plasticized into certain shapes under certain conditions (temperature, pressure, etc.) and can keep its shape unchanged at room temperature and normal atmosphere pressure. According to their performance after heat treatment, plastics can be divided into thermoplastic and thermosetting plastics. A thermoplastic plastic is generally a linear or branched polymer. It melts when heated and solidifies when cooled, and this kind of behavior can be repeated, so the plastic can be used multiple times. The main varieties are polyethylene, polypropylene, polyvinyl chloride, polystyrene, and acrylonitrile-butadiene-styrene terpolymer. Thermosetting plastic is a space network polymer, which is formed by direct polymerization of monomers or by cross-linking of linear prepolymers. Once the solidification is finished, the polymer cannot be heated back to the plasticizing state. The main varieties are phenolic resin, epoxy resin, amino resin, and unsaturated polyester. 

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