Processing prepolymer

Another approach adopts a two-step process processable prepolymers are synthesized, and then the prepolymers are cured to drive the polymerization reaction to higher conversions, initiating network formation. Chemically, this... 

Catalysts are essential components in the liquid injection moulding (LIM) or reaction injection moulding (RIM) processes. Prepolymer systems for solid polyurethane elastomers usually do not require catalysts, and if long-term hydrolytic stability is required in the final polymer their use is undesirable. 

Another useful approach to attaining good solubility is to start from processable prepolymers. After being processed, these prepolymers can be converted into conductive form through, for example, thermosetting. This method was applied to syntheses of poly(p-phenylene) [46], poly(thienylenevinylene) [47], etc. as final forms. 

Stabilizers and pigments are normally slurried with macroglycol and added to the polymeric glycol charge, prior to diisocyanate addition. Therefore, care must be taken to avoid additives that react significantly with diisocyanates or diamines under processing conditions. Also, stabilizers should be chosen that have no adverse catalytic effect on the prepolymer or chain-extension reactions. 

Interfdci l Composite Membra.nes, A method of making asymmetric membranes involving interfacial polymerization was developed in the 1960s. This technique was used to produce reverse osmosis membranes with dramatically improved salt rejections and water fluxes compared to those prepared by the Loeb-Sourirajan process (28). In the interfacial polymerization method, an aqueous solution of a reactive prepolymer, such as polyamine, is first deposited in the pores of a microporous support membrane, typically a polysulfone ultrafUtration membrane. The amine-loaded support is then immersed in a water-immiscible solvent solution containing a reactant, for example, a diacid chloride in hexane. The amine and acid chloride then react at the interface of the two solutions to form a densely cross-linked, extremely thin membrane layer. This preparation method is shown schematically in Figure 15. The first membrane made was based on polyethylenimine cross-linked with toluene-2,4-diisocyanate (28). The process was later refined at FilmTec Corporation (29,30) and at UOP (31) in the United States, and at Nitto (32) in Japan. 

In the first step of the polymerization process, a prepolymer is prepared as a slurry in water. Excess diamine is added to control the degree of polymerization, eg, degree of polymerization = 6-14 (158). This prepolymerization step is conducted at approximately 200°C under autogenous pressure for less than 90 min. 

Reaction Injection Molding. RIM uses the anionic polymeri2ation of nylon-6 to carry out polymeri2ation in the mold. A commercial process involves the production of block copolymers of nylon-6 and a polyether by mixing molten caprolactam, catalyst, and polyether prepolymer, and reacting in a mold (27,28). 

Polymerization of the dianhydride and diamine proceeds through an intermediate poly(amide acid) stage before ring closure converts the adjacent acid and amide groups to the polyetherimide (94). The polymerization can be carried directiy to the polyetherimide as a single-step process, or first to an ainide—acid-containing prepolymer, which can be isolated, and then to the polyetherimide. 

Fig. 3. The key steps of the Kureha process, as disclosed in the patent Hterature (48), are (/) dehydration of aqueous feedstocks (sodium sulfide or its functional equivalent) in the presence of A/-methyl-2-pyrrohdinone (2) polymerization of the dehydrated sodium sulfide with -dichlorobenzene at alow temperature to form a prepolymer (J) addition of water to the prepolymer (4) a second, higher temperature polymerization step and (5) polymer recovery.

Urethanes are processed as mbber-like elastomers, cast systems, or thermoplastic elastomers. The elastomer form is mixed and processed on conventional mbber mills and internal mixers, and can be compression, transfer, or injection molded. The Hquid prepolymers are cast using automatic metered casting machines, and the thermoplastic peUets are processed like aU thermoplastic materials on traditional plastic equipment. The unique property of the urethanes is ultrahigh abrasion resistance in moderately high Shore A (75—95) durometers. In addition, tear, tensUe, and resistance to many oUs is very high. The main deficiencies of the urethanes are their resistance to heat over 100°C and that shear and sliding abrasion tend to make the polymers soft and gummy. 

There are many suppHers of urethane systems in the United States. The TSE Company suppHes the mbber form many companies supply the prepolymer forms. It is estimated that close to 68,000 t of these mbbers are used in the United States if aU forms are included. Uses include sport wheels (roUer blades, ski wheels) printing, paper, and steel processing roUs gears pump liners appHance components and soHd industrial tires. 

In the CSIRO process, a reactive polyurethane prepolymer is appHed to a garment from perchloroethylene. The garment is then pressed and subsequendy steamed in an oven. A second polymer may sometimes be used in conjunction with the prepolymer. When this is employed, the process is termed the Serolan BAP Process (178). A number of alternative treatments are being investigated to achieve finishes that are more environmentally friendly (179). 

The reaction product of 4,4 -bismaleimidodiphenylmethane and 4,4 -diaminophenylmethane, known as Kerimide 601 [9063-71-2] is prepolymerized to such an extent that the resulting prepolymer is soluble in aprotic solvents such as /V-methy1pyrro1idinone [872-50-4] dimethylformamide [68-12-2] and the like, and therefore can be processed via solution techniques to prepreg. Kerim ide 601 is mainly used in glass fabric laminates for electrical appHcations and became the industry standard for polyimide-based printed circuit boards (32). 

The Michael addition reaction of amines and thiols with bismaleimides or functionalized monomaleimides is a versatile tool ia the synthesis of chain-extended maleimide-terroinated prepolymers. These prepolymers generally are soluble ia organic solvents from which they can be processed to prepreg and molded to high quaUty, void-free laminates. 

Step-Growth Gopolymerization. A sample of a block copolymer prepared by condensation polymerisation is shown in equation 30 (37). In this process, a prepolymer diol (HO—Z—OH) is capped with isocyanate end groups and chain extended with a low molecular-weight diol (HO—E—OH) to give a so-called segmented block copolymer, containing polyurethane hard blocks and O—Z—O soft blocks. 

Polyurethane foams may be rigid, semi-rigid or flexible. They may be made from polyesters, polyethers or natural polyols such as castor oil (which contains approximately three hydroxyl groups in each molecule). Three general processes are available known as one-shot, prepolymer or quasi-prepolymer processes. These variations lead to 27 basic types of product or process, all of which have been used commercially. This section deals only with flexible foams (which are made only from polyesters and polyethers). Since prepolymers and... 

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