Application Data: 1,4 Butanediol in Polyurethanes

One of the most important fields of application for 1,4butanediol are the manufacture of polyurethanes. The main polyurethanes produced from it are cellular and solid elastomers. Polyurethanes Polyurethanes, in which butanediol is the diol component (chain extender) in the hard segment, contain the following structural unit: -NH-CO-O-CH2CH2CH2CH2-O-CO-NH Polyurethanes possess unique properties such as abrasion resistance, elasticity, strength, toughness, low temperature flexibility, and paintability. The most important fields of application are soft and rigid foams, microcellular elastomers (soft integral skin foams), laminates, surface coatings, adhesives, thermoplastic elastomers, fibers, and dispersions. Polyurethane raw materials The raw materials required for the production of polyurethanes are polyols and isocyanates. The former are primarily polyether or polyester polyols. The main isocyanates used are 2,4-toluenediisocyanate (TDI) and methylenedi-pphenylenediisocyanate (MDI) and their higher homologues. A chain extender is also included in the starting materials for certain groups of polyurethanes. These are compounds that have a low molecular weight and contain two hydrogen atoms that can react with isocyanates. Examples are water, glycols, and diamines. The primary interest that 1,4-butanediol receives in the manufacture of polyurethanes is as an ingredient of

polyester polyols and as a chain extender. In other words, 1,4-butanediol is primarily used in thermoplastic polyurethane elastomers for injection molding and both extrusion processes and cellular elastomers for soft integral skin foams. Adhesives and surface coatings require much less 1,4-butanediol. Production of pour-in-place, foamed and unfoamed polyurethanes Long-chain polyols with terminal hydroxyl groups react with the previously mentioned aromatic diisocyanates and with a chain extender to yield flexible polyurethanes with a high molecular weight that can be molded in the molten state. The preferred chain extender is 1,4-butanediol. The polyols are either of the polyester type, e.g., polyethylene adipate or polybutylene adipate, or they are polyether polyols, e.g., polybutylene ether glycol, which is produced from tetrahydrofuran, or polypropylene ether glycol. The molecular weight of the compounds is between 500 and 6000. Foams are obtained by adding a blowing agent to the mixture. They may be hard, semi-hard, or soft, depending on the constituents of the mixture. There are two different techniques for molding polyurethanes of the polyether or polyester types. Prepolymers with terminal isocyanate groups are produced from the polyols and excess diisocyanate. In the second phase, shortly before molding, the chain extender (usually 1,4butanediol) and any other auxiliaries, e.g., blowing agents, catalysts, or stabilizers, are added to the prepolymers. The entire mixture is then poured in place. The second method, referred to as the one-shot technique, is technically simpler. Long-chain, liquid polyether polyols or polyester polyols are mixed with the liquefied diisocyanate, the chain extender, catalyst, and blowing agent in one operation at room temperature. The mixture is then molded in single shots

at temperatures of 45-50 C. The physical and chemical properties of polyurethanes can be varied within very wide limits according to the raw materials selected and the processing conditions. In fact, the products can be custom tailored to a wide range of applications. 1,4-butanediol as chain extender in the production of TP polyurethane elastomers The typical mechanical characteristics of thermoplastic polyurethane elastomers are: 1. Excellent abrasion resistance 2. High strength and toughness 3. High elasticity & low compression set 4. Excellent low-temperature flexibility For instance, a linear, thermoplastic, semicrystalline polyurethane is obtained in the reaction among 1,4-butanediol, polyol, and diphenylinethane diisocyanate. If linear, highmelting, crystalline sections of a macromolecule (1,4butanediol and MDI) are connected together by soft, lowmelting segments (polyol and MDI), the resultant thermoplastic polyurethane elastomer has pronounced elastic properties, and the ultimate elongation may be as much as several hundred percent. Hydrogen interaction between the urethane and urea groups and Van Der Waals forces are responsible for the crystallinity of the hard segment. Interactions between the molecules are improved if the molecular chains are very close together. For this reason, the first demand imposed on a diol chain extender is linearity; the second is that it must contain an even number of carbon atoms.

Measurements of the heat distortion temperature, elongation at break, tensile strength, modulus of elasticity, etc. of polyurethanes in which the chain extender was a homologous aliphatic diol have revealed that these properties oscillate. If the measured values are plotted against the number of carbon atoms, maximum values occur at the even figures and minimum values at the odd. X-ray investigations have confirmed the effect of the number of carbon atoms in the chain extender on the crystallinity of the hard segments. If the linear diols are arranged in the sequence of decreasing number of carbon atoms, it will be seen that the crystallinity of the hard segment increases, i.e. 1,8-octanediol < 1,6-hexanediol < 1,4-butanediol < ethylene glycol. Thus, 1,4-butanediol is superior to the higher diols for technical reasons. Other powerful arguments in its favor are its price and availability. If the mechanical properties of the products obtained from it are taken as a measure, ethylene glycol is an outstanding chain extender. However, there are two important arguments against its use. It incurs difficulties in processing, owing to its inadequate miscibility with most other polyols, and polyurethanes derived from ethylene glycol as the chain extender have poor resistance to hydrolysis.

Application Data: 1,4-butanediol in polyester polyols

The demands placed on the polyols and their constituents are not as easily defined as those of the chain extender. The polyol chains should remain amorphous at as low temperatures as possible, yet display a certain orderly arrangement to ensure that a given level of cohesive forces is retained and that the polyurethane has satisfactory mechanical properties.

In view of the mechanical properties desired, the focus is on linear diols and dicarboxylic acids. Adipic acid is the predominant acid. The diols almost exclusively used are ethylene glycol, 1,4-butanediol and 1,6-hexanediol, owing to their availability and their price. When hydrolysis resistance is relatively less important, blends of 1,4-butanediol and ethylene glycol are frequently used. When it is critical, 1,6-hexanediol is used. In some individual cases, mixtures with special diol compounds are used to improve flexibility at low temperatures.

Soft integral skin foams MDI, a polyol, and a chain extender are usually required for the manufacture of an integral skin foam. Since the chemical constitution of integral skin foam is similar to that of other elastomers, the designation cellular elastomers is also used. Soft foams can be achieved by reduction. Polyesters and polyethers can be used as the polyol component. For many fields of application, polyurethanes produced with polyester polyols have superior mechanical properties and higher resistance to atmospheric influences, e.g., ultra-violet radiation and oxygen. On the other hand, polyether polyols increase the resistance to hydrolysis and improve flexibility at low temperatures. These differences can be easily understood in light of the chemical structure. Due to the presence of the oxygen atom in the molecule, a polyether is not resistant to ultra-violet radiation and atmospheric oxygen but is more resistant to hydrolysis than an ester. On the other hand, the cohesive forces in a polyester chain are greater than those in a polyether due to the polar carbonyl

groups. The greater intermolecular forces ensure better elastic properties but entail lower flexibility at low temperatures. Main fields of application for soft integral foams Shoe soles The use of polyurethanes in shoe soles was influenced by the dictates of changing fashions, e.g., platform soles. Polyurethane soles can be produced easily in any desired shape, can be readily coated, and have a low specific gravity. Thus, quite independent of fashion trends, they have established a firm position in shoe soles, particularly since their quality is superior to that of the two other synthetic soles derived from polyvinylchloride or diene copolymers. The extent to which leather will be replaced by synthetic products depends on the price and availability of sole leather.

Solid elastomers In general, higher physical property requirements are imposed on unfoamed polyurethanes than on foamed. Factors important to the use of solid elastomers in laminates are their resistance to wear, tensile strength, resistance to tear propagation, resistance to breaking, and resistance to folding. Laminates There is no doubt that polyurethanes are considered to be the best for the production of leather substitutes for outerwear, handbags, upholstery, etc. A less significant field of application is poromeric microporous materials. In contrast to the demands made on conventional synthetic leather substitutes, not only the impermeability to water but also the permeability to water vapor are required.

Frequently, both of these properties are classified under one heading and are referred to as good breathing properties. Poromers of this nature are primarily intended for shoe upper leather. Adhesives Polyurethane adhesives are produced mainly from polyester polyols, including butanediol polyester polyols. However, the structure of the adhesives as a whole differs considerably from that of the previously discussed elastomers . For instance, polyurethane adhesives are branched, and a chain extender is not usually required for their manufacture. 1,4-butanediol polyester plasticizers are readily compatible with vinyl polymers and improve their resistance to oxidation. They are less volatile, have less tendency than monomeric esters to migrate into other plastics with which they come in contact, and increase the impact strength at subzero temperatures. Since they are not extracted by soapy water, tetrachloroethylene, or gasoline and oils, they can be used in the manufacture of vinyl coated fabrics that can be drycleaned. The proportion of polyester determines whether the plasticized polymer will be flexible, soft, or rubbery. The polyesters produced from 1,4-butanediol have better flexibility at low temperatures than those produced from 2, 2-dimethyl-1,3propanediol (neopentylglycol). In practice, blends of polyesters derived from 1,4-butanediol and 1,3-butanediol are used for the production of liquid products that can be easily handled. The efficiency of these plasticizers at subzero temperatures is exceeded only by that of di-2-ethylhexyl-terephthalate. Polyvinyl derivatives plasticized with 1,4- butanediol polyesters are processed into adhesive films for oil tank linings, roof

coverings, refrigerator gaskets, gasoline lines, and oil-resistant cables. Compounds obtained when some of the butanediol in the polyester is replaced by methyldiethanolamine may become basic as a result of the nitrogen content. When these compounds are polymerized until they are quite viscous, they are suitable plasticizers for leather substitutes.

Application Data: 1,4-Butanediol in Polyester Plasticizers 1,4-butanediol polyester plasticizers are readily compatible with vinyl polymers and improve their resistance to oxidation. They are less volatile, have less tendency than monomeric esters to migrate into other plastics with which they come in contact, and increase the impact strength at subzero temperatures. Since they are not extracted by soapy water, tetrachloroethylene, or gasoline and oils, they can be used in the manufacture of vinyl coated fabrics that can be drycleaned. The proportion of polyester determines whether the plasticized polymer will be flexible, soft, or rubbery. The polyesters produced from 1,4-butanediol have better flexibility at low temperatures than those produced from 2, 2-dimethyl-1,3propanediol (neopentylglycol). In practice, blends of polyesters derived from 1,4-butanediol and 1,3-butanediol are used for the production of liquid products that can be easily handled. The efficiency of these plasticizers at subzero temperatures is exceeded only by that of di-2-ethylhexyl-terephthalate. Polyvinyl derivatives plasticized with 1,4-butanediol polyesters

are processed into adhesive films for oil tank linings, roof coverings, refrigerator gaskets, gasoline lines, and oil-resistant cables. Compounds obtained when some of the butanediol in the polyester is replaced by methyldiethanolamine may become basic as a result of the nitrogen content. When these compounds are polymerized until they are quite viscous, they are suitable plasticizers for leather substitutes.