Prepolymer solvents

To produce a spandex fiber by reaction spinning, a 1000—3500 molecular weight polyester or polyether glycol reacts with a diisocyanate at a molar ratio of about 1 2. The viscosity of this isocyanate-terrninated prepolymer may be adjusted by adding small amounts of an inert solvent, and then extmded into a coagulating bath that contains a diamine so that filament and polymer formation occur simultaneously. Reactions are completed as the filaments are cured and solvent evaporated on a belt dryer. After appHcation of a finish, the fibers are wound on tubes or bobbins and rewound if necessary to reduce interfiber cohesion. 

Titrations with dibutylamine [111-92-2] can also be used to determine the NCO content of isocyanates and prepolymers. Generally, an excess of amine in a suitable solvent such as chlorobenzene [108-90-7] is added to the sample. The resulting solution is allowed to react and the unreacted amine is back- titrated with dilute hydrochloric acid. For low NCO content levels, a colorimetric method is often used. The isocyanate-containing species is titrated with amine and the unreacted amine is deterrnined using malachite green [569-64-2]. 

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. 

Most general-purpose release agents have been developed for this market in part because of their low toxicity and chemical inertness and do not usually present health and safety problems. Some of the solvent dispersions require appropriate care in handling volatile solvents, and many supphers are offering water-based alternatives. Some of the sohds, particularly finely divided hydrophobic sohds, can also present inhalation problems. Some of the metallic soaps are toxic, although there is a trend away from the heavier, more toxic metals such as lead. The reactive type of release coating with monomers, prepolymers, and catalysts often presents specific handling difficulties. The potential user with health and safety questions is advised to consult the manufacturer directly. 

Water-borne adhesives are preferred because of restrictions on the use of solvents. Low viscosity prepolymers are emulsified in water, followed by chain extension with water-soluble glycols or diamines. As cross-linker PMDI can be used, which has a shelf life of 5 to 6 h in water. Water-borne polyurethane coatings are used for vacuum forming of PVC sheeting to ABS shells in automotive interior door panels, for the lamination of ABS/PVC film to treated polypropylene foam for use in automotive instmment panels, as metal primers for steering wheels, in flexible packaging lamination, as shoe sole adhesive, and as tie coats for polyurethane-coated fabrics. PMDI is also used as a binder for reconstituted wood products and as a foundry core binder. 

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. 

For convenience of application it is usual to utilise the two-stage preparation shown above. Initially the soluble polymer (I) is formed which is then converted into the insoluble thermally stable polyimide (II) Figure 18.35). Suitable solvents for the high molecular weight prepolymer (I) include dimethylformamide and dimethylacetamide. 

Monomeric MDI Pure 4,4 -MDI 2.0 Solid (MP = 37 C) Flexible prepolymers Liquid 1-K adhesive Thermoplastic adhesives Curing hot melts Solvent-borne adhesives... 

A variety of applications exist for liquid, 100% solid adhesives, (An adhesive is considered 100% solid if there is no solvent in the adhesive.) Some of the largest uses include structural wood adhesives and adhesives used for the transportation industry, such as windshield adhesives and those used for bonding composite sidewalls of a recreational vehicle (RV). Structural wood adhesives are often made of a polymeric MDI with functionality of approximately 2.7 or higher. Rigid assemblies often utilize polymeric MDI, whereas flexible adhesive assemblies will more often utilize pure MDI, a solid waxy material that melts at around 37°C, or a modified MDI , i.e., MDI that has been modified to make it a liquid at room temperature. Prepolymers are made with ratios of anywhere from NCO/OH = 1.6 to 3.0 or higher. 

Polyester polyurethanes are usually based on a blend of a quasi-prepolymer (polyester/MDl) and a diol/polyester suitable for spray-up operation. An alternative is to use a solvent-containing system using blocked curatives to give an extended pot-life of 2 to 3 hours enabling them to be brush, roller or spray applied. 

The polyurethane lining systems in use today are normally of the 100% solids type without solvents. The individual components, prepolymer and isocyanate are preheated and pumped to the mix/dispenser for metering and mixing. After mixing, the material is pumped through an orifice where it is... 

The PGS obtained by Wang and coworkers was a kind of thermoset elastomer with the Young s modulus of 0.282 0.025 MPa, a tensile strain of at least 267 zE 59.4%, and a tensUe strength was at least 0.5 MPa. The mechanical properties of PGS were well consisted with that of some common soft tissues. Although PGS is a thermoset polymer, its prepolymer can be processed into various shapes by solving it in common organic solvents such as 1,3-dioxolane, tetrahydrofuran, isopropanol, ethanol, and iV,M-dimethylformamide. Porous scaffolds can be fabricated by salt leaching. 

The predominant RO membranes used in water applications include cellulose polymers, thin film oomposites (TFCs) consisting of aromatic polyamides, and crosslinked polyetherurea. Cellulosic membranes are formed by immersion casting of 30 to 40 percent polymer lacquers on a web immersed in water. These lacquers include cellulose acetate, triacetate, and acetate-butyrate. TFCs are formed by interfacial polymerization that involves coating a microporous membrane substrate with an aqueous prepolymer solution and immersing in a water-immiscible solvent containing a reactant [Petersen, J. Memhr. Sol., 83, 81 (1993)]. The Dow FilmTec FT-30 membrane developed by Cadotte uses 1-3 diaminobenzene prepolymer crosslinked with 1-3 and 1-4 benzenedicarboxylic acid chlorides. These membranes have NaCl retention and water permeability claims. 

Applications Van der Maeden et al. [646] first used GE-HPLC for the qualitative and quantitative analysis of oligomeric mixtures, such as low-MW resins (epoxy up to 16-mer, o-cresol novolak up to 16-mer, p-cresol novolak up to 13-mer), prepolymers (poly-(2,6-diphenyl-p-phenylene oxide) up to 20-mer), PET (up to 14-mer) and ethoxylated octaphenol surfactants (up to 19-mer). In many GE-HPLC separations of oligomeric mixtures, a compromise has to be found between sample loading, injection volume and compatibility of the sample solvent and the initial phase system. Therefore,... 

Acetylene terminated polyimide prepolymers have many advantages over conventional polyimides in the areas of processing and solvent resistance. In addition, the presence of the isoimide structure further extends the the utility of these systems by modification of the solubility properties and glass transition temperature. 

For the solubility of TPA in prepolymer, no data are available and the polymer-solvent interaction parameter X of the Flory-Huggins relationship is not accurately known. No experimental data are available for the vapour pressures of dimer or trimer. The published values for the diffusion coefficient of EG in solid and molten PET vary by orders of magnitude. For the diffusion of water, acetaldehyde and DEG in polymer, no reliable data are available. It is not even agreed upon if the mutual diffusion coefficients depend on the polymer molecular weight or on the melt viscosity, and if they are linear or exponential functions of temperature. Molecular modelling, accompanied by the rapid growth of computer performance, will hopefully help to solve this problem in the near future. The mass-transfer mechanisms for by-products in solid PET are not established, and the dependency of the solid-state polycondensation rate on crystallinity is still a matter of assumptions. 

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