Urethane raw materials

The isocyanurate reaction can be both beneficial and troublesome. It can be the bane of production engineers. Low levels of alkaline impurities present in urethane raw materials such as polyols, tackifiers, etc., can cause problems in prepolymer production, resulting in high viscosity products at levels of 5 ppm or less. At higher levels of alkaline impurities, more serious problems can occur, including poor shelf life, poor caulkability, or poor sag resistance. At levels of 15 ppm or higher, the alkalinity can cause an isocyanurate reaction in a prepolymer that can result in a gelled reactor. 

Three classes of urethane raw materials will be described isocyanates, polyols, and chain extenders. The intent is to describe the major types of urethane raw materials used in urethane adhesives, rather than to provide an exhaustive review. The concepts behind the raw materials will be discussed. Once the concepts are understood, it is hoped that the adhesion scientist will then apply the concepts when choosing raw materials for urethane adhesives. 

In order to understand the widely varying physical properties and adhesion properties of urethanes, it is important to understand the different classes of urethane raw materials and their functions in urethane adhesives. In order to... 

ASTM D 4670-87 Standard Test Method for Urethane Raw Materials Determination of Suspanded Matter in Polyols, 1 p (Comm D-20)... 

Polyurethane RIM (PU-RIM) was selected for the Initial RIM application of automotive fascia not only because 1t provides the required damage resistance and other performance requirements, but also because the reactivity of the urethane raw materials, Isocyanate and polyol, provide acceptable productivity. Because the urethane mnomers can be nucleated, high quality sink free surfaces that are suitable for automotive exteriors are produced at the time of demold. Little, 1f any, post mold surface repair 1s needed 1n preparation for painting the RIM part. 

From each of the foregoing topics, It Is quite obvious that the ease by which IMR agents are selected Is greatly curtailed. Finding a compound which can be "dumped" Into any and all systems to provide the property of self-release Is perhaps realistically Impossible. Each and every system must have Its own "right" formulation - a task so far accomplished only by a limited number of suppliers of urethane raw material chemicals. 

During 1976 and 1977 cotton linters for felting enjoyed a low rate of price escalation relative to urethane raw materials (Figure it). However, in the last two years, the price of linters has moved up rapidly to the same range of urethane raw materials. 

Polyurethanes continue to be one of the most versatile of all polymers, finding applications in foams (flexible, rigid, and in-between), elastomers, coatings, sealants, adhesives, paints, textiles, and films. This volume presents some of the major advances in polyurethanes, both from the materials and research side of things as well as processing and applications, and includes studies on foams (additives, vacuum panel applications, blowing and processing), elastomers, adhesion behaviour and new urethane raw materials. 

Mitsui Toatsu Chemicals is now making the urethane raw material directly from 2,4-dinitrotoluene, carbon monoxide and methanol [234. Dimethyl-p-toluene-2,4-carbamate is produced with a catalytic system based on 5V, Pd/C, FeCl3 and pyridine, at 160"C and 70 atm. The carbamate is then heated at 250"C with a paraffin fraction and zinc naphthenate under vacuum. 

URETHANE RAW MATERIAL SUPPLIERS AND CAPACITIES 1976 Estimate (Millions of Pounds)... 

Polyester polyols are an important class of urethane raw materials, with applications in elastomers, adhesives, etc. They are usually made from adipic acid and ethylene glycols (polyethylene adipate) ... 

Another fluorescent pigment class (23) is based on a urethane-type resin the primary raw materials are isocyanates, amines, and hydroxy compounds. 

Crystalline polyesters are highly important as adhesive raw materials. They are normally crystalline waxes and are highly symmetrical in nature, which can aid the crystallization process [26]. Poly(hexamethylene adipate) and poly(caprolactone), shown in Table 2, are only two of the many crystallizable backbones. Poly(ethylene adipate) and poly(letramethylene adipate) are also commonly used in urethane adhesives. The crystalline polyesters are used in curing hot melts, waterborne polyurethanes, thermoplastic polyurethanes, and solvent-borne urethane adhesives. The adipates are available mostly as diols. The poly(caprolactones) are available as diols and triols. 

With the exception of fillers, the raw materials used in two-component urethanes are all liquids. The two components have an isocyanate side and a polyol side. The raw materials are combined in various ways in order to produce with liquids that are combined at a 1 1 volume ratio, preferably, thus keeping the dispensing equipment as simple as possible. Fixed ratios of 3 2 or 1 2 are also commonly used. Ratios other than these are possible, but require the use of a... 

There appear to be conflicting reports regarding the degradation of urethanes. For example, some urethanes are reported to have relatively poor hydrolysis resistance and good biodegradability [77], while other urethanes are reported to be so hydrolytically stable that they have been successfully used as an artificial heart [78]. Both reports are correct. It will be shown that the thermal, oxidative, and hydrolytic stability of urethanes can be controlled, to some degree, by the choice of raw materials used to make the urethane. 

Polyurethane adhesives are formed by the reaction of various types of isoeyanates with polyols. The polar urethane group enables adhesion to various surfaees. Depending on the raw materials, glue lines with rubber-like elastic to brittle-hard behavior ean be aehieved. The presence of reactive terminal groups provides a ehemieally hardened adhesive. When polymerized to a high enough molecular weight, the adhesive ean be physically rather than chemically hardened, i.e. a hot melt. 

Almost all urethane materials are synthesized without the use of solvents or water as diluents or earners and are referred to as being 100% solids. This is true of all foams and elastomers. There are many products, however, which do utilize solvents or water, and these are known as solvent-borne and waterborne systems, respectively. In the past, many coatings, adhesives, and binders were formulated using a solvent to reduce viscosity and/or ease application. However, the use of volatile solvents has been dramatically curtailed in favor of more environmentally friendly water (see Section 4.1.3), and now there are many aqueous coatings, adhesives, and associated raw materials. Hydrophilic raw materials capable of being dispersed in water are called water reducible (or water dispersible), meaning they are sufficiently hydrophilic so as to be readily emulsified in water to form stable colloidal dispersions. 

The raw materials used are common and available from a variety of industrial sources and are always used as-received without further purification. All raw materials must be urethane grade, meaning mainly that the water content is less than about 0.05% by weight. If in doubt, water level should be measured.413,42 Bayer products are used where possible, but a detailed description of each compound is given so that substitutes from other manufacturers may be used. However, it cannot be overemphasized that extreme care must be taken when choosing substitutes because even small differences in these complex materials can cause marked discrepancies in results. Sources for common materials, such as 1,4-butanediol, are not specified as these are readily available... 

Unsaturated polyester resins (UPRs) Uralkyd resins, 202 Urea-methylol reaction, 410 Urethane alkyds, 241 Urethane coatings, 202 Urethane elastomers, implanted, 207 Urethane foams, tests for, 244 Urethane gels, 205 Urethane-grade ATPEs, 223 Urethane-grade polyol types, 212 Urethane-grade raw materials, 246 Urethane hydrogel, preparation of, 250-251... 

---