Patent Publication Number: US-10323117-B2

Title: Polyols derived from farnesene for polyurethanes

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
     This application is a divisional of U.S. patent application Ser. No. 14/989,140, filed on Jan. 6, 2016, which are incorporated herein by reference in its entirety for all purposes. 
    
    
     FIELD OF THE INVENTION 
     The invention relates to polyurethanes that may be used as insulating glass sealants, electric potting compounds, construction coating/sealants, and water membranes, for example. More specifically, the invention relates to polyurethanes and their compositions that are derived or include polyols derived from farnesene. 
     BACKGROUND 
     It is well known to prepare isocyanate terminated polyurethane prepolymers from polyether and/or polyester polyols and aromatic diisocyanates. Polyurethane prepolymers are formed by combining an excess of diisocyanate with polyol. One of the —NCO groups of a diisocyanate reacts with one of the OH groups of the polyol, and the other end of the polyol reacts with another diisocyanate. The result is a prepolymer having an isocyanate group on both ends. The prepolymer is therefore a diisocyanate itself, but unlike the original diisocyanate, the prepolymer has a greater molecular weight, a higher viscosity, a lower isocyanate content by weight (% NCO), and a lower vapor pressure. 
     Furthermore, it is also well known to prepare polyurethane elastomers by chain extending these prepolymers with low molecular weight diols. The resulting polyurethanes have excellent mechanical properties, but are rather hydrophilic, which can limit their utility in certain moisture sensitive applications. 
     Hydroxyl terminated polyols with very non-polar backbones (e.g., hydroxyl functional polybutadiene) can be used to introduce hydrophobicity into polyurethane elastomers. However, polyols having a polybutadiene backbone, for example, usually have a much higher viscosity than those based on polyether backbone. To reduce the viscosity of hydroxyl-terminated polybutadienes, one can either blend polyether polyols into the polyol mixture or make prepolymers with increased —NCO percentage. The approach is in general not ideal because the final polyurethane products tend to have inferior hydrophobicity. 
     Thus, there is a need for improved polyurethanes having relatively low viscosity for easier application that are hydrophobic for moisture-sensitive applications. 
     SUMMARY OF THE INVENTION 
     According to one embodiment, a composition is provided for making a polyurethane. The composition comprises one or more polyols, one or more isocyanate-group containing compounds having an isocyanate group functionality of at least two, and optionally one or more chain extenders. At least one of the polyols is a farnesene-based polyol having a number average molecular weight less than or equal to 100,000 g/mol, more desirably a number average molecular weight less than or equal to 25,000 g/mol, and a viscosity at 25° C. less than 10,000 cP. The farnesene-based polyol may be a polyol of a farnesene homopolymer or a copolymer of farnesene and, optionally, one or more dienes and/or vinyl aromatics. Examples of dienes include butadiene and isoprene. The chain extender may include one or more monomeric polyols and/or polyamines. The composition may also comprise additional polyols, such as a polyol of a homopolymer or copolymer of a polydiene. The NCO/OH ratio of the composition may be about 2:1 to 1:2. 
     According to another embodiment, a method of preparing a polyurethane is provided comprising combining one or more polyols with one or more isocyanate-containing compounds having a isocyanate functionality of at least two, and optionally, a chain extender, to form a mixture and curing the mixture. At least one of the one or more polyols is a farnesene-based polyol. The chain extender may be one or more monomeric polyols and/or polyamines, such as 1,4-butanediol, 1,6-hexanediol, ethylene glycol, 2-ethyl-1,3-hexanediol (EHD), 2-butyl-2-ethyl-1,3-propanediol (BEPG), 2,2,4-trimethyl-1,3-pentanediol (TMPD), 2,4-deithyl-1,5-pentanediol (PD-9), N,N-diisopropanol aniline, dimethylolpropionic acid, hydroquinone dihydroxyethyl ether (HQEE), diethylene glycol, propylene glycol, trimethylolpropane, glycerol, diethyltoluenediamine (DETDA), 4,4′-methylene bis(2-chloroaniline) (MBCA), ethylenediamine (EDA), dimethylthiotoluene-diamine (DMTTDA), 4,4′-methylenedianiline (MDA), complex of methylenediamine with NaCl (MDA complex), trimethyleneglycol di-p-aminobenzoate (TMGDAB), 4,4′-methylene-bis(3-chloro-2,6-diethylaniline) (M-CDEA), and N,N′-bis(sec-butyl)methylene-dianiline (SBMDA). The one or more isocyanate-group containing compounds include 4,4′-diphenylmethane diisocyanate (MDI), cyclohexanediisocyanate, p-phenylene diisocyanate, 1,5-naphthalene diisocyanate, toluene diisocyanate (TDI), p-xylene diisocyanate, hexamethylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,4-bis(isocyanomethyl)-cyclohexane, p-tetramethylxylene diisocyanate, m-tetramethylxylene diisocyanate, isophorone diisocyanate, and combinations thereof. 
     According to yet another embodiment, a polyurethane is provided prepared according to the methods disclosed herein. An elastomeric product is also provided comprising the polyurethane that may be in the form of a sealant, a coating, a caulk, an electric potting compound, a membrane, a sponge, a foam, an adhesives, and a propellant binder. 
     These and other aspects of the various embodiments of the disclosed methods and compositions will be understood from the following detailed description. 
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     According to various embodiments of the disclosed methods and compositions, a farnesene-based polyol is provided, as well as a composition for making a polyurethane comprising a diisocyanate and the farnesene-based polyol. The composition may further include chain extenders, such as monomeric polyols and polyamines. Therefore, as used herein “polyurethane” refers to a polymer containing one or more urethane bonds and may also include one or more urea bonds. 
     The farnesene-based polyols according to the disclosed methods and compositions exhibit lower viscosities compared to polydiene-based polyols, such as polybutadiene, of similar molecular weight. Therefore, farnesene-based polyols may be handled favorably in polyurethane formulations and applications without significant dilution with other components. In addition, the farnesene-based polyols can be combined with oligomers based on hydroxyl-terminated polybutadiene and polyisoprene to provide polyol mixtures that may be combined with one or more diisocyanates to form the compositions for making the polyurethanes. The viscosity of polyfarnesene may be controlled by copolymerization with other monomers, such as dienes and vinyl aromatics. Examples include butadiene, isoprene, and styrene. The resulting polyurethanes derived from polyfarnesene polyols, having excellent hydrophobicity, are excellent in a variety of applications, such as insulating glass sealants, caulks, electric potting compounds, construction coating/sealants, water membranes, sponges, foams, adhesives, coatings, propellant binders, encapsulating compounds, as well as other rubber-fabricated materials. 
     The farnesene-based polyol may be obtained by polymerizing a monomer feed that primarily includes farnesene followed by hydroxyl-functionalization of the terminal end(s) of the polymer. As used herein “polyol” is an organic compound having more than one hydroxyl group. The farnesene-based polymers have a lower viscosity compared to polybutadienes, but comparable hydrophobicity. Therefore, the polyols may be used to manufacture polyurethanes used in moisture sensitive coating applications, for example, without significant dilution with other additives for the purpose of lowering its viscosity. 
     Any methods known by those having skill in the art may be used to polymerize the farnesene monomers. Anionic polymerization may be desirable because anionic polymerization allows greater control over the final molecular weight of the polymer. The living terminal ends of the polymer may also be easily quenched using an epoxide followed by contact with a protic source providing a polyol. The low viscosity farnesene-based polymers may be derived by polymerizing farnesene monomer alone or with at least one other monomer, such as butadiene or isoprene, for example. It is preferred that the polymers made according to various embodiments of the disclosed methods and compositions are derived from a monomer feed that is primarily composed of farnesene. 
     Farnesene exists in isomer forms, such as α-farnesene ((E,E)-3,7,11-trimethyl-1,3,6,10-dodecatetraene) and β-farnesene (7,11-dimethyl-3-methylene-1,6,10-dodecatriene). As used in the specification and in the claims, “farnesene” means (E)-β-farnesene having the following structure: 
                         
as well (E)-β-farnesene in which one or more hydrogen atoms have been replaced by another atom or group of atoms (i.e. substituted).
 
     The farnesene monomer used to produce various embodiments of the polymer according to the disclosed methods and compositions may be prepared by chemical synthesis from petroleum resources, extracted from insects, such as Aphididae, or plants. Therefore, an advantage of the disclosed methods and compositions is that the polymer may be derived from a monomer obtained via a renewable resource. The monomer may be prepared by culturing a microorganism using a carbon source derived from a saccharide. The farnesene-based polymer according to the disclosed methods and compositions may be efficiently prepared from the farnesene monomer obtained via these sources. 
     The saccharide used may be any of monosaccharides, disaccharides, and polysaccharides, or may be a combination thereof. Examples of monosaccharides include, without limitation, glucose, galactose, mannose, fructose, and ribose. Examples of disaccharides include, without limitation, sucrose, lactose, maltose, trehalose, and cellobiose. Examples of polysaccharides include, without limitation, starch, glycogen, and cellulose. 
     The cultured microorganism that consumes the carbon source may be any microorganism capable of producing farnesene through culturing. Examples thereof include eukaryotes, bacteria, and archaebacteria. Examples of eukaryotes include yeast and plants. The microorganism may be a transformant obtained by introducing a foreign gene into a host microorganism. The foreign gene is not particularly limited, and may be a foreign gene involved in the production of farnesene because it can improve the efficiency of producing farnesene. 
     In the case of recovering farnesene from the cultured microorganism, the microorganism may be collected by centrifugation and disrupted, and then farnesene can be extracted from the disrupted solution with a solvent. Such solvent extraction may appropriately be combined with any known purification process such as distillation. 
     The farnesene-based polymers described herein may be prepared by a continuous solution polymerization process wherein an initiator, monomers, and a suitable solvent are continuously added to a reactor vessel to form the desired homo-polymer or co-polymer. Alternatively, the farnesene-based polymers may be prepared by a batch process in which all of the initiator, monomers, and solvent are combined in the reactor together substantially simultaneously. Alternatively, the farnesene-based polymers may be prepared by a semi-batch process in which all of the initiator and solvent are combined in the reactor together before a monomer feed is continuously metered into the reactor. 
     Preferred initiators for providing a polymer with living terminal chain ends include, but are not limited to organic salts of alkali metals. The polymerization reaction temperature of the mixture in the reactor vessel may be maintained at a temperature of about −80 to 80° C. 
     As understood by those having skill in the art, anionic polymerization may continue, as long as monomer is fed to the reaction. The farnesene-based polyols may be obtained by polymerization of farnesene and one or more comonomers. Examples of comonomers include, but are not limited to, dienes, such as butadiene, isoprene, and myrcene, or vinyl aromatics, such as styrene and alpha methyl styrene, in which butadiene, isoprene, and styrene are preferred. In one embodiment of the disclosed methods and compositions, a method of manufacturing a farnesene-based polyol may comprise polymerizing a monomer feed, wherein the monomer feed comprises farnesene monomer and a comonomer in which the comonomer content of the monomer feed is ≤75 mol. %, alternatively ≤50 mol. %, or alternatively ≤25 mol. %, based on the total moles of the monomer in the monomer feed. Examples of comonomers include, but are not limited to, dienes, vinyl aromatics, and combinations thereof. 
     The hydroxy functionalized low viscosity farnesene-based homo-polymers or co-polymers according to embodiments of the disclosed methods and compositions may have a number average molecular weight less than or equal to 100,000 g/mol, alternatively less than or equal to 25,000 g/mol, as measured through a gel permeation chromatograph and converted using polystyrene calibration. The weight of the polyol can be from about 0.5 wt. % to about 99.5 wt. % of the resulting polyurethane. The farnesene-based homopolymers or copolymers may have a viscosity less than or equal to 100,000 cP, alternatively less than 50,000 cP, or alternatively less than or equal to 25,000 cP, at 25° C. 
     The quenching step to end polymerization is accomplished by reacting the a living terminal end(s) of the living polymer with an alkylene oxide, such as propylene oxide, and a protic source, such as an acid, resulting in a diol or polyol, i.e. a hydroxyl group on the terminal ends of the polymer. 
     Following polymerization, the hydroxyl-terminated polymer may be hydrogenated to decrease the degree of unsaturation of the polymer to at most 50%, alternatively at most 10%. Hydrogenation of the hydroxyl-terminated polymer will modify the glass transition temperature (Tg) of the polymer and improve the thermostability and UV-stability of the polymer. Hydrogenation may be carried out by a variety of processes familiar to those of ordinary skill in the art including, but not limited to, hydrogenation in the presence of catalysts, such as Raney Nickel, nobel metals, soluble transition metal catalysts, and titanium catalysts, for example. Degree of unsaturation is determined by analytical methods known in the art, such as iodine value. 
     According to certain embodiments, a composition for making a polyurethane is provided that comprises one or more polyols, wherein at least one polyol is a farnesene-based polyol, one or more isocyanate-group containing compounds having a functionality of at least 2, and optionally, a chain extender selected from the group consisting of monomeric polyols, polyamines, and combinations thereof. The amount of at least one polyol and one or more isocyanate-group containing compounds in the composition may be such that the ratio of —NCO groups to —OH groups is about 2:1 to 1:2. The use of NCO/OH ratios lower than unity results in softer, lower modulus materials. At NCO/OH ratio levels above 1.0 lower modulus material may also be prepared. However, these materials will gradually increase in hardness with time since the free NCO groups can undergo further reaction with moisture to give urea structures, or can form allophanate crosslinks (especially at elevated temperatures). 
     The physical properties of the polyurethane, such as viscosity, may be tailored depending on the desired application for the polyurethane by selection of the molecular weight of the polyols, as well as the ratio of farnesene-based polyols to non-farnesene-based polyols in the compositions described herein. Additional polyols that may also be included in the composition with the farnesene-based polyol include, but are not limited to, poly(oxypropylene)glycol, poly(oxyethylene)glycol, poly(oxypropylene-oxyethylene)glycol, poly(oxytetramethylene)glycol, poly(oxybutylene)glycol, poly(caprolactone)glycol, poly(ethyleneadipate)glycol, poly(butyleneadipate)glycol, aromatic polyester glycols, polybutadiene polyol, hydrogenated polybutadiene polyol, polyisoprene polyol, hydrogenated polyisoprene polyol, and mixtures thereof. 
     The one or more isocyanate-group containing compounds having a functionality of at least 2 may exhibit several or all of the following characteristics: bulk, symmetry around the isocyanate functional groups, rigid, aromatic, crystalline and high purity. The one or more isocyanate-group containing compounds having a functionality of at least 2 include, but are not limited to, 4,4′-diphenylmethane diisocyanate (MDI), cyclohexanediisocyanate, p-phenylene diisocyanate, 1,5-naphthalene diisocyanate, toluene diisocyanate (TDI), p-xylene diisocyanate, hexamethylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,4-bis(isocyanomethyl)-cyclohexane, p-tetramethylxylene diisocyanate, m-tetramethylxylene diisocyanate, isophorone diisocyanate, and mixtures thereof. 
     The one or more chain extenders included in the composition may include monomeric polyols and polyamines, for example. The molecular weight of each of the one or more chain extenders may be about 50 to 700. As understood by those of skill in the art, the type and amount of chain extender will affect the elastomeric properties of the polyurethane, such as tensile strength, elongation, and tear resistance values. When the compositions as described herein react to form a polyurethane, the chain extenders contribute to the hard segment of the polyurethane that serve as physical cross-links between the amorphous soft segment domains. The hard segments, which are formed by the reaction between an isocyanate group and either the hydroxyl or amine group of the chain extenders, inhibit plastic flow of softer segments of the polyurethane provided by the long chain polyols. The choice and amount of chain extender may also affect flexural, heat, and chemical resistance properties of the polyurethane. The chain extenders may include, but are not limited to, 1,4-butanediol, 1,6-hexanediol, ethylene glycol, 2-ethyl-1,3-hexanediol (EHD), 2-butyl-2-ethyl-1,3-propanediol (BEPG), 2,2,4-trimethyl-1,3-pentanediol (TMPD), 2,4-deithyl-1,5-pentanediol (PD-9), N,N-diisopropanol aniline, dimethylolpropionic acid, hydroquinone dihydroxyethyl ether (HQEE), diethylene glycol, propylene glycol, trimethylolpropane, glycerol, diethyltoluenediamine (DETDA), 4,4′-methylene bis(2-chloroaniline) (MBCA), ethylenediamine (EDA), dimethylthiotoluene-diamine (DMTTDA), 4,4′-methylenedianiline (MDA), complex of methylenediamine with NaCl (MDA complex), trimethyleneglycol di-p-aminobenzoate (TMGDAB), 4,4′-methylene-bis(3-chloro-2,6-diethylaniline) (M-CDEA), N,N′-bis(sec-butyl)methylene-dianiline (SBMDA), and mixtures thereof. 
     The polyurethanes made according to the methods disclosed herein may be manufactured by a batch procedure or a continuous procedure. The mixing of the reactants can be accomplished by any of the procedures and apparatus conventional in the art. The individual components are urethane grade and, as such, have low moisture content or are rendered substantially free from the presence of water using conventional procedures, for example, by azeotropic distillation, or by heating under reduced pressure at a temperature in excess of the boiling point of water at the pressure employed. The later procedure is desirable to accomplish degassing of the components. 
     Preparation of polyurethanes according to the various embodiments disclosed herein may be achieved by procedures conventional in the art for synthesis of polyurethanes. Such procedures include the casting procedure in which the reactants (one or more polyols, one or more diisocyanates, and one or more optional chain extenders) are mixed in the liquid state, either by the one-shot route or the two-step route, also known as the prepolymer technique, and then, the reacting mixture is fabricated into its final form by an appropriate technique such as casting or molding, while the reaction continues by chain extension and/or cross-linking. Final cure is typically achieved by a hot air post-cure for up to twenty-four hours at 25° C. to about 200° C. In general, the reaction of the components limits the subsequent pot life to several minutes, and subsequent casting or molding immediately thereafter. Vacuum degassing may also be used to prepare castings which are bubble free. In the one-shot route, the polyurethane is made by combining all of the components of the composition for making a polyurethane as described herein generally simultaneously into a common reaction vessel. One-shot systems offer the advantages of versatility, simplicity, and low cost fabrication techniques for preparing urethanes having a wide range of physical properties. Such applications as caulks, sealants, elastomers and foams are possible via these systems. 
     Two-shot systems are based upon the intermediate formulation of a prepolymer which can be further chain-extended with additional polyols and polyamines to form the final polyurethane. These systems may provide higher performance urethanes and have the advantages of lowering the overall toxicity of the system. 
     In the prepolymer procedure, the one or more isocyanate-group containing compounds are first reacted with the one or more polyols to form a prepolymer. The one or more polyols include at least one farnesene-based polyol. Therefore, the resulting prepolymer is a polymer having a chain derived from farnesene monomer and terminal ends functionalized with one or more isocyanate groups. Additional isocyanate-group containing compounds, polyols, and chain extenders may then be added to the prepolymer to complete formation of the polyurethane. 
     The methods described herein may be either solventless or include a solvent. In the solventless embodiment, the one or more polyols are heated to 70° to 100° C., for example, and then thoroughly mixed with the desired amount of chain extender for at least two hours under nitrogen flow to eliminate moisture. Isocyanate containing compounds are then added to the mixture immediately prior to pouring the mixture into a heated mold, desirably treated with a mold release compound. The polyurethane composition is formed by curing into the mold for several hours and then postcuring above 110° C. for at least 2 hours. In the solvent method, the one or more polyols are dissolved in a solvent, such as dry toluene, heated to about 70° to 100° C., for example, and then mixed with the desired type and amount of the one or more isocyanate-containing compounds and chain extenders for at least 2 hours under nitrogen flow. The solvent is then removed by evaporation, for example, and then the composition is postcured for at least 2 hours at 110° C. while under vacuum. The thermoplastic polyurethane composition can then be heat pressed above the elastomer melting point to form an elastomeric polyurethane article. 
     The compositions for making a polyurethane, in addition to including one or more polyols, isocyanate-containing compounds, and chain extenders may also include reinforcing additives, asphalt, and process oils to alter the physical characteristics of the polyurethane composition and/or reduce costs. 
     Plasticizers may be included as extenders that also increase the softness and flexibility of the cured material in various embodiments of the disclosed methods and compositions. One or more plasticizers may be selected from the group consisting of vegetable oil, mineral oil, soybean oil, terpene resins, aromatic esters (e.g. dioctyl phthalate, diundecyl phthalate, tricresyl phosphate, and triisononyl mellitate), linear esters (e.g. di-tridecyl adipate), chlorinated Paraffin, aromatic and napthenic process oils, alkyl naphthalenes, and low molecular weight polyisoprene, polybutadiene, or polybutylene resins. The amounts of plasticizer employed in the invention composition can vary from 0 to about 500 phr (per hundred parts of polyurethane), between about 0 to about 100 phr, and most between about 0 and about 60 phr. 
     Because of their hydrocarbon backbones, the polyurethanes made according to the methods and compositions described herein are compatible with conventional hydrocarbon oils, chlorinated oils, asphalts and other related low cost extending materials. The quantity of asphalt or process oil which may be incorporated depends on the type of oils, the amount of isocyanate groups present, and the type of fillers, if present. Cured polyurethanes may be formulated which incorporate in excess of 100 parts extending material per 100 parts of polyurethane and do not “bleed” oil from the final product. The cured polyurethanes may also exhibit a moderate decrease in tensile strength and modulus and improved elongation with the addition of an extending material. Oil extension may also improve hydrolytic stability, control of premix viscosities, pot life, gel time, cure time, and the ability to attain higher filler loading. The use of materials such as chlorinated waxes and oils also provides fire retardant properties to the finished product. 
     Suitable fillers include, but are not limited to, carbon black, calcium carbonate, clays, talcs, zinc oxide, titanium dioxide, silica and the like. Calcium carbonates are relatively soft and may be used at rather high levels to enhance the extrusion properties of the polyurethane compositions described herein. Elastomers prepared using calcium carbonates are suitable for many caulk and sealant applications where high elongation and moderate tensile properties are required. Clays may provide a moderate degree of reinforcement, fair abrasion resistance, but a relatively high stiffening effect. Clays are used as fillers in stocks requiring hardness and high modulus; e.g., shoe soles and heels, mats, and floor tiles. Zinc oxide may also provide resilience and heat conductivity, but its use as a reinforcing filler may be limited due to high density and cost. Zinc oxide may be effectively employed as a reinforcing filler in conjunction with carbon black to increase tensile, modulus, tear, and hardness, and abrasion resistance. It is important to note that at a constant carbon black level, increasing the concentration of zinc oxide may decrease the workable pot life of the compositions described herein after the isocyanate component is added; i.e., gelation occurs more rapidly. Silicas contribute a greater increase in tensile strength than other non-carbon black fillers. Silicas also have a profound stiffening effect on the compositions described herein. The amount of filler usually is in the range of 0 to about 800 phr, depending on the type of filler used and on the application for which the formulation is intended. Preferred fillers are silica and titanium dioxide. The filler should be thoroughly dried in order that adsorbed moisture will not interfere with the reaction between the isocyanate-containing compounds and the one or more polyols. 
     Stabilizers known in the art may also be incorporated into the composition. For example, adhesive formulations that utilize the polyurethanes of the disclosed methods and compositions may include stabilizers for protection during the life of the sealant or adhesive against, for example, oxygen, ozone and ultra-violet radiation. The stabilizers may also prevent thermo-oxidative degradation during elevated temperature processing. Antioxidants and UV inhibitors which interfere with the urethane curing reaction should be avoided. Preferred antioxidants are sterically hindered phenolic compounds, like butylated hydroxy toluene. Preferred UV inhibitors are UV absorbers such as benzotriazole compounds. The amount of stabilizer in the formulation will depend greatly on the intended application of the product. If processing and durability requirements are modest, the amount of stabilizer in the formulation will be less than about 1 phr. However depending on the intended use of the polyurethane, the stabilizer concentration may be as much as about 10 phr. 
     The polyurethane according to the embodiments of the disclosed methods and compositions may be cured by procedures known by those having ordinary skill in the art for the curing of isocyanate terminated polymers. Curing mechanisms include, but are not limited to, the use of moisture, blocked amines, oxazolidines, epoxies, triisocyanurate ring formation, allophonate and biruet crosslinking and the like. Unfilled urethane systems may be cured at ambient temperatures, but cure rates may be accelerated by using either typical urethane catalysts and/or elevated temperatures. Catalysts include, but are not limited to, dibutyltin dilaurate and 1,4-diazo [2.2.2] bicyclooctane. The amount and type of catalyst that may be included in the compositions described herein may be selected based on the desired cure rate. Dependent upon the curing technology employed, the resulting polyurethanes may be either a thermoset polyurethane or a higher melt temperature thermoplastic polyurethane once curing is accomplished. 
     The polyurethanes obtained according to the various embodiments of the disclosed methods and compositions exhibit excellent chemical and physical properties. 
     EXAMPLES 
     Embodiments of the disclosed methods and compositions are further described using the following non-limiting examples. 
     Table 1 provides a list of the materials used for preparing the formulations of the following examples and comparative examples. 
                             TABLE 1               Material   Description   Eq. Wt                                            Krasol ® LBH 2000 LO (polybutadiene   0.812 meq/g OH value   1232       diol)   (27-74)       Krasol ® HLBH P-2000 (hydrogenated   0.83 meq/g OH value       polybutadiene diol)       Poly bd ® R45-HTLO (polybutadiene   0.84 meq/g OH value       diol)       Polyfarnesene diol (Mw = 2000)   1.019 meq/g OH value   981           (27-74)       2-ethyl-1,3-hexanediol   EHD,   73.12       2,4′ Diphenylmethane Diisocyanate   33.5% NCO content   125.4       (Lupranate ® MI)       Dibutyltin dilaurate   T-12       Dibutyl phthalate   DBP                    
Evaluation of Effect of Polyol Blends and Isocyanate Content
 
     The effect of blending a polyfarnesene diol and polybutadiene diol and reacting the various blends with increasing amounts of a diisocyanate were evaluated. In Comparative Examples 1-3, only polybutadiene diols was used. In Examples 1-6, blends of polybutadiene diol and polyfarnese diols were used. Viscosity of the polyurethane prepolymers was measured at 25° C., and NCO group content was monitored by identifying the intensity of NCO group absorbance peaks at 2265 cm −1  on IR during prepolymer preparation at 60° C. for 3 hours. The results are provided in Tables 2, 3, and 4. 
     
       
         
           
               
               
               
               
             
               
                   
                 TABLE 2 
               
               
                   
                   
               
               
                   
                 Comp. 
                   
                   
               
               
                   
                 Ex. 1 
                 Ex. 1 
                 Ex. 2 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
            
               
                 Krasol ® LBH 2000 LO 
                 100 
                 75 
                 50 
               
               
                 Polyfarnesene diol 
                 0 
                 25 
                 50 
               
               
                 2,4′ Diphenylmethane Diiso- 
                 19.95 
                 20.09 
                 20.24 
               
               
                 cyanate 
               
               
                 Free NCO % in final prepolymer 
                 2.72 
                 2.58 
                 2.43 
               
               
                 by wt % 
               
               
                 Viscosity of prepolymer at 25° 
               
               
                 C., cps 
               
               
                 At initial time of prepolymeriza- 
                 3437 
                 2230 
                 1398 
               
               
                 tion 
               
               
                 At reacted 3 hrs of polymeriza- 
                 Off 
                 241000 
                 131000 
               
               
                 tion 
                 scale 
               
               
                 NCO content from intensity at 
               
               
                 2265/cm on FTIR 
               
               
                 At initial time of prepolymeriza- 
                 0.1978 
                 0.2074 
                 0.2137 
               
               
                 tion 
               
               
                 At reacted 3 hrs of polymeriza- 
                 0.0950 
                 0.0927 
                 0.0911 
               
               
                 tion 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
             
               
                   
                 TABLE 3 
               
               
                   
                   
               
               
                   
                 Comp. 
                   
                   
               
               
                   
                 Ex. 2 
                 Ex. 3 
                 Ex. 4 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
            
               
                 Krasol ® LBH 2000 LO 
                 100 
                 75 
                 50 
               
               
                 Polyfarnesene diol 
                 0 
                 25 
                 50 
               
               
                 2,4′ Diphenylmethane Diiso- 
                 31.49 
                 31.63 
                 31.79 
               
               
                 cyanate 
               
               
                 Free NCO % in final prepoly- 
                 5.42 
                 5.28 
                 5.15 
               
               
                 mer by wt % 
               
               
                 Viscosity of prepolymer at 
               
               
                 25° C., cps 
               
               
                 At initial time of prepolymer- 
                 2007 
                 1299 
                 870 
               
               
                 ization 
               
               
                 At reacted 3 hrs of polymer- 
                 69360 
                 39492 
                 22620 
               
               
                 ization 
               
               
                 NCO content from intensity at 
               
               
                 2265/cm on FTIR 
               
               
                 At initial time of prepolymer- 
                 0.2976 
                 0.2962 
                 0.2982 
               
               
                 ization 
               
               
                 At reacted 3 hrs of polymer- 
                 0.2001 
                 0.1985 
                 0.1969 
               
               
                 ization 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
             
               
                   
                 TABLE 4 
               
               
                   
                   
               
               
                   
                 Comp. 
                   
                   
               
               
                   
                 Ex. 3 
                 Ex. 5 
                 Ex. 6 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
            
               
                 Krasol ® LBH 2000 LO 
                 100 
                 75 
                 50 
               
               
                 Polyfarnesene diol 
                 0 
                 25 
                 50 
               
               
                 2,4′ Diphenylmethane Diiso- 
                 46.19 
                 46.33 
                 46.48 
               
               
                 cyanate 
               
               
                 Free NCO % in final prepolymer 
                 8.24 
                 8.12 
                 7.99 
               
               
                 by wt % 
               
               
                 Viscosity of prepolymer at 25° 
               
               
                 C., cps 
               
               
                 At initial time of prepolymeriza- 
                 1119 
                 721 
                 545 
               
               
                 tion 
               
               
                 At reacted 3 hrs of polymeriza- 
                 19371 
                 10685 
                 7264 
               
               
                 tion 
               
               
                 NCO content from intensity at 
               
               
                 2265/cm on FTIR 
               
               
                 At initial time of prepolymeriza- 
                 0.3821 
                 0.3827 
                 0.3852 
               
               
                 tion 
               
               
                 At reacted 3 hrs of polymeriza- 
                 0.3048 
                 0.3057 
                 0.3063 
               
               
                 tion 
               
               
                   
               
            
           
         
       
     
     Based on the results in Tables 2-4, increased polyfarnesene diol in the polyol blends resulted in a lower viscosity of the resulting polyurethane prepolymer. 
     Similar viscosity results, provided in Tables 5, 6, and 7 were exhibited by various blends of polyfarnesene diols with polybutadiene diols. The viscosity of the blends decreases with the increased amount of polyfarnesene diol in the blends. 
     
       
         
           
               
               
               
               
               
               
               
             
               
                 TABLE 5 
               
               
                   
               
             
            
               
                 Polyfarnesene diol 
                   
                 100 
                 75 
                 50 
                 25 
                 0 
               
               
                 Polybd R45HTLO 
                   
                 0 
                 25 
                 50 
                 75 
                 100 
               
               
                 Brookfield 
                 25° C. 
                 1289 
                 1828 
                 2757 
                 4187 
                 6467 
               
               
                 viscosity, cps 
                 40° C. 
                 427 
                 666 
                 1060 
                 1687 
                 2663 
               
               
                   
                 60° C. 
                 142 
                 236 
                 398 
                 652 
                 1045 
               
               
                   
                   
                   
                 miscible 
                 miscible 
                 miscible 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
               
               
               
             
               
                 TABLE 6 
               
               
                   
               
             
            
               
                 Polyfarnesene 
                   
                 100 
                 75 
                 50 
                 25 
                 0 
               
               
                 diol 
               
               
                 Krasol LBH 2000 
                   
                 0 
                 25 
                 50 
                 75 
                 100 
               
               
                 Brookfield 
                 25° C. 
                 1289 
                 2128 
                 3609 
                 6186 
                 10623 
               
               
                 viscosity, cps 
                 40° C. 
                 427 
                 668 
                 1035 
                 1629 
                 2605 
               
               
                   
                 60° C. 
                 142 
                 205 
                 299 
                 434 
                 631 
               
               
                   
                   
                   
                 miscible 
                 miscible 
                 miscible 
               
               
                   
               
            
           
         
       
     
                                             TABLE 7                  Polyfarnesene       100   75   50   25   0       diol       Krasol HLBH       0   25   50   75   100       2000       Brookfield   25° C.   1289   2820   6452   15216   36492       viscosity, cps   40° C.   427   863   1804   3819   8748           60° C.   142   254   473   892   1831                   miscible   miscible   miscible                    
Evaluation of Physical Properties
 
     The polyfarnesene diol (Mw=2000) was used, either by itself or blended with polybutadiene polyol, to prepare various samples of cured polyurethane plaques for evaluation. The polyurethanes were prepared from blends that also used various concentrations of a chain extender, ethyl hexanediol (EHD), and a diisocyanate 2,4′ Diphenylmethane Diisocyanate (Lupranate® MI). 
     The polyurethanes were prepared by the one shot procedure. Polyols and chain extenders were combined in a flask and mixed under nitrogen at ambient temperature followed by the addition of isocyanate and immediately pouring the mixture into a heated mold. The final curing was performed in an oven and held at 85° C. for 5 hours and overnight at 60° C. Each sample sheet was post cured for one week at room temperature before testing of its physical properties. Relative parameters were tested by referring to ASTM D412, ASTM D624 Die C, and using DSC, Shore type Durometers, a Brookfield viscometer, and an EJA Vantage-10 tensile tester and the results provided in Tables 8, 9, and 10. 
     
       
         
           
               
               
               
               
               
             
               
                   
                 TABLE 8 
               
               
                   
                   
               
               
                   
                 Comp. 
                   
                   
                   
               
               
                   
                 Ex. A1 
                 A2 
                 A3 
                 A4 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
            
               
                 Krasol LBH 2000 LO 
                 100 
                 75 
                 50 
                 0   
               
               
                 Polyfarnesene diol 
                 0 
                 25 
                 50 
                 100    
               
               
                 2-ethyl-1,3-hexanediol 
                 5.34 
                 5.05 
                 4.75 
                  4.10 
               
               
                 2,4′ Diphenylmethane 
                 19.95 
                 20.09 
                 20.24 
                 20.42 
               
               
                 Diisocyanate 
               
               
                 20% T-12 solution in DBP, 
                 4 
                 4 
                 4 
                 4   
               
               
                 drops 
               
               
                 Hard segment content, 
                 20.19 
                 20.09 
                 19.99 
                 19.69 
               
               
                 wt % 
               
               
                 Hardness of PU, Shore A 
                 54 
                 47 
                 38 
                 55*   
               
               
                 Tensile strength, psi 
                 337 
                 267 
                 No data** 
                 No data*** 
               
               
                 Elongation at break, % 
                 885 
                 680 
                 &gt;1250 
                 No data*** 
               
               
                 Modulus, psi 
                 109 
                 95 
                 41 
                 No data*** 
               
               
                 Tear strength, Ibf/in 
                 98 
                 74 
                 33 
                 No data*** 
               
               
                 Tg of polyurethane 
                 −28.3 
                 −33.4 
                 −39.8 
                 −51.2  
               
               
                 product, ° C. 
               
               
                   
               
               
                 55* the hardness was tested by type Shore 00 Durometer 
               
               
                 No data** data could not be obtained due to specimen were not broken after strain was over 1200% 
               
               
                 No data*** for sample A4, it is too soft and tacky to be tested 
               
            
           
         
       
     
     
       
         
           
               
               
               
               
               
             
               
                   
                 TABLE 9 
               
               
                   
                   
               
               
                   
                 Comp. 
                   
                   
                   
               
               
                   
                 Ex. B1 
                 B2 
                 B3 
                 B4 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
            
               
                 Krasol LBH 2000 LO 
                 100 
                 75 
                 50 
                 0 
               
               
                 Polyfarnesene diol 
                 0 
                 25 
                 50 
                 100 
               
               
                 2-ethyl-1,3-hexanediol 
                 11.87 
                 11.58 
                 11.28 
                 10.81 
               
               
                 2,4′ Diphenylmethane 
                 31.49 
                 31.63 
                 31.79 
                 32.28 
               
               
                 Diisocyanate 
               
               
                 20% T-12 solution in DBP, 
                 4 
                 5 
                 5 
                 4 
               
               
                 drops 
               
               
                 Hard segment content, wt % 
                 30.24 
                 30.17 
                 30.10 
                 30.11 
               
               
                 Hardness of PU, Shore A 
                 72 
                 66 
                 60 
                 55 
               
               
                 Tensile strength, psi 
                 1920 
                 1029 
                 742 
                 572 
               
               
                 Elongation at break, % 
                 584 
                 468 
                 479 
                 412 
               
               
                 Modulus, psi 
                 494 
                 332 
                 228 
                 164 
               
               
                 Tear strength, Ibf/in 
                 269 
                 214 
                 172 
                 109 
               
               
                 Tg of polyurethane product, ° C. 
                 −28.0 
                 −31.0 
                 −36.6 
                 −47.5 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
               
             
               
                   
                 TABLE 10 
               
               
                   
                   
               
               
                   
                 Comp. 
                   
                   
                   
               
               
                   
                 Ex. C1 
                 C2 
                 C3 
                 C4 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
            
               
                 Krasol LBH 2000 LO 
                 100 
                 75 
                 50 
                 0 
               
               
                 Polyfarnesene diol 
                 0 
                 25 
                 50 
                 100 
               
               
                 2-ethyl-1,3-hexanediol 
                 20.19 
                 19.89 
                 19.59 
                 19.01 
               
               
                 2,4′ Diphenylmethane 
                 46.19 
                 46.33 
                 46.48 
                 46.77 
               
               
                 Diisocyanate 
               
               
                 20% T-12 solution in DBP, 
                 4 
                 5 
                 5 
                 4 
               
               
                 drops 
               
               
                 Hard segment content, wt % 
                 39.90 
                 39.84 
                 39.78 
                 39.68 
               
               
                 Hardness of PU, Shore A 
                 83 
                 75 
                 73 
                 71 
               
               
                 Tensile strength, psi 
                 2188 
                 1350 
                 1125 
                 982 
               
               
                 Elongation at break, % 
                 491 
                 291 
                 328 
                 347 
               
               
                 Modulus, psi 
                 860 
                 681 
                 527 
                 378 
               
               
                 Tear strength, Ibf/in 
                 392 
                 332 
                 280 
                 174 
               
               
                 Tg of polyurethane product, ° C. 
                 −26.6 
                 −29.9 
                 −33.0 
                 −45.9 
               
               
                   
               
            
           
         
       
     
     While increased concentrations of polyfarnesene diol in the polyol blend resulted in lower hardness and tensile strength in the cured samples, the higher concentration of chain extender substantially improved the physical properties of all samples. Therefore, the appropriate selection of the type and amount of chain extender should provide a polyurethane prepolymer derived from a substantial amount of polyfarnesene diol with both improved viscosity prior to curing and adequate physical properties upon curing. 
     Tables 11 to 16 below provide data associated with the physical properties of polyurethane samples prepared using the two-shot method. Polyols and isocyantes were reacted together to a form a prepolymer at approximately 80° C. for about three hours followed by the addition of chain extenders, such that the final polyurethane had an NCO/OH ratio of approximately 1.0. The final curing was performed in an oven and held at 85° C. for 5 hours and overnight at 60° C. 
     For the samples of Examples D3-8, E3-8, and F3-8, polyfarnesene diol (Mw=5000) was evaluated having a higher molecular weight than the polyfarnesene diol (Mw=2000) of Examples G3-8, H3-8, and I3-8. Each sample sheet was post cured for one week at room temperature before testing of its physical properties. Relative parameters were tested by referring to ASTM D412, ASTM D624 Die C, and using DSC, Shore type Durometers, a Brookfield viscometer, and an EJA Vantage-10 tensile tester and the results provided in Tables 11 to 16. 
     
       
         
           
               
               
               
               
               
             
               
                   
                 TABLE 11 
               
             
            
               
                   
                   
               
               
                   
                 Comp. Ex. 
                 Example 
                 Example 
                 Example 
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                   
                 D1 
                 D2 
                 D3 
                 D4 
                 D5 
                 D6 
                 D7 
                 D8 
               
               
                   
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                 Krasol ® LBH 2000 LO 
                 100 
                 100 
                 75 
                 75 
                 50 
                 50 
                 0 
                 0 
               
               
                 Polyfarnesene diol 
                 0 
                 0 
                 25 
                 25 
                 50 
                 50 
                 100 
                 100 
               
               
                 2-ethyl-1,3-hexanediol 
                 11.80 
                   
                 12.30 
                   
                 12.80 
                   
                 13.80 
               
               
                 2,2,4-trimethyl-1,3- 
                   
                 11.80 
                   
                 12.30 
                   
                 12.80 
                   
                 13.80 
               
               
                 pentanediol 
               
               
                 2,4′ Diphenylmethane 
                 31.09 
                 31.09 
                 30.57 
                 30.57 
                 30.06 
                 30.06 
                 29.03 
                 29.03 
               
               
                 Diisocyanate 
               
               
                 20% T-12 in DBP, drop 
                 3 
                 3 
                 3 
                 3 
                 3 
                 3 
                 3 
                 3 
               
               
                 Shore A/D hardness 
                 73/28 
                 76/31 
                 72/30 
                 74/30 
                 71/27 
                 71/27 
                 55/16 
                 49/12 
               
               
                 Tg, ° C. 
                 −29.0 
                 −28.5 
                 −37.0 
                 −38.6 
                 −48.9 
                 −47.3 
                 −60.6 
                 −62.4 
               
               
                 Modulus, psi 
                 339 
                 372 
                 474 
                 387 
                 442 
                 452 
                 171 
                 121 
               
               
                 Tensile strength, psi 
                 1136 
                 675 
                 1508 
                 641 
                 1507 
                 816 
                 657 
                 447 
               
               
                 Elongation at break, % 
                 862 
                 779 
                 730 
                 634 
                 665 
                 526 
                 473 
                 744 
               
               
                 Tear resistance, lbf/in 
                 238 
                 205 
                 275 
                 213 
                 248 
                 212 
                 121 
                 104 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
               
             
               
                   
                 TABLE 12 
               
             
            
               
                   
                   
               
               
                   
                 Comp. Ex. 
                 Example 
                 Example 
                 Example 
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                   
                 E1 
                 E2 
                 E3 
                 E4 
                 E5 
                 E6 
                 E7 
                 E8 
               
               
                   
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                 Krasol ® LBH 2000 LO 
                 100 
                 100 
                 75 
                 75 
                 50 
                 50 
                 0 
                 0 
               
               
                 Polyfarnesene diol 
                 0 
                 0 
                 25 
                 25 
                 50 
                 50 
                 100 
                 100 
               
               
                 2-ethyl-1,3-hexanediol 
                 20.40 
                   
                 21.00 
                   
                 21.63 
                   
                 22.50 
               
               
                 2,2,4-trimethyl-1,3- 
                   
                 20.40 
                   
                 21.00 
                   
                 21.63 
                   
                 22.50 
               
               
                 pentanediol 
               
               
                 2,4′ Diphenylmethane 
                 46.17 
                 46.17 
                 45.82 
                 45.82 
                 45.54 
                 45.54 
                 44.28 
                 44.28 
               
               
                 Diisocyanate 
               
               
                 20% T-12 in DBP, drops 
                 3 
                 3 
                 3 
                 3 
                 3 
                 3 
                 3 
                 3 
               
               
                 Shore A/D hardness 
                 91/48 
                 91/44 
                 87/42 
                 86/40 
                 82/38 
                 83/35 
                 66/21 
                 63/18 
               
               
                 Tg, ° C. 
                 −26.8 
                 −30.0 
                 −36.6 
                 −40.8 
                 −45.5 
                 −46.1 
                 −62.1 
                 −61.5 
               
               
                 Modulus, psi 
                 1163 
                 1146 
                 1118 
                 1068 
                 1043 
                 977 
                 387 
                 323 
               
               
                 Tensile strength, psi 
                 2106 
                 1347 
                 1976 
                 1345 
                 1671 
                 1191 
                 602 
                 520 
               
               
                 Elongation at break, % 
                 452 
                 383 
                 453 
                 399 
                 343 
                 272 
                 200 
                 314 
               
               
                 Tear resistance, lbf/in 
                 464 
                 378 
                 404 
                 369 
                 351 
                 283 
                 116 
                 110 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
               
             
               
                   
                 TABLE 13 
               
             
            
               
                   
                   
               
               
                   
                 Comp. Ex. 
                 Example 
                 Example 
                 Example 
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                   
                 F1 
                 F2 
                 F3 
                 F4 
                 F5 
                 F6 
                 F7 
                 F8 
               
               
                   
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                 Krasol ® LBH 2000 LO 
                 100 
                 100 
                 75 
                 75 
                 50 
                 50 
                 0 
                 0 
               
               
                 Polyfarnesene diol 
                 0 
                 0 
                 25 
                 25 
                 50 
                 50 
                 100 
                 100 
               
               
                 2-ethyl-1,3-hexanediol 
                 32.60 
                   
                 33.10 
                   
                 33.60 
                   
                 34.60 
               
               
                 2,2,4-trimethyl-1,3- 
                   
                 32.60 
                   
                 33.10 
                   
                 33.60 
                   
                 34.60 
               
               
                 pentanediol 
               
               
                 2,4′ Diphenylmethane 
                 67.55 
                 67.55 
                 67.03 
                 67.03 
                 66.52 
                 66.52 
                 65.49 
                 65.49 
               
               
                 Diisocyanate 
               
               
                 20% T-12 solution in DBP, 
                 3 
                 3 
                 3 
                 3 
                 3 
                 3 
                 3 
                 3 
               
               
                 drops 
               
               
                 Shore A/D hardness 
                 95/58 
                 96/57 
                 92/52 
                 94/48 
                 82/39 
                 89/42 
                 72/19 
                 68/18 
               
               
                 Tg, ° C. 
                 −31.3 
                 −29.2 
                 −41.5 
                 −38.6 
                 −50.3 
                 −49.2 
                 −62.9 
                 −62.2 
               
               
                 Modulus, psi 
                 2160 
                 2099 
                 1841 
                 1784 
                 1581 
                 1400 
                 258 
                 No data 
               
               
                 Tensile strength, psi 
                 3093 
                 2207 
                 2305 
                 1851 
                 1834 
                 1449 
                 262 
                 242 
               
               
                 Elongation at break, % 
                 429 
                 290 
                 338 
                 232 
                 231 
                 186 
                 133 
                 88 
               
               
                 Tear resistance, lbf/in 
                 627 
                 561 
                 498 
                 463 
                 362 
                 283 
                 80 
                 64 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
               
             
               
                   
                 TABLE 14 
               
             
            
               
                   
                   
               
               
                   
                 Comp. Ex. 
                 Example 
                 Example 
                 Example 
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                   
                 G1 
                 G2 
                 G3 
                 G4 
                 G5 
                 G6 
                 G7 
                 G8 
               
               
                   
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                 Krasol ® LBH 2000 LO 
                 100 
                 100 
                 75 
                 75 
                 50 
                 50 
                 0 
                 0 
               
               
                 Polyfarnesene diol 
                 0 
                 0 
                 25 
                 25 
                 50 
                 50 
                 100 
                 100 
               
               
                 2-ethyl-1,3-hexanediol 
                 11.80 
                   
                 11.60 
                   
                 11.40 
                   
                 11.00 
               
               
                 2,2,4-trimethyl-1,3- 
                   
                 11.80 
                   
                 11.60 
                   
                 11.40 
                   
                 11.00 
               
               
                 pentanediol 
               
               
                 2,4′ Diphenylmethane 
                 31.09 
                 31.09 
                 31.29 
                 31.29 
                 31.51 
                 31.51 
                 31.91 
                 31.91 
               
               
                 Diisocyanate 
               
               
                 20% T-12 in DBP, drops 
                 3 
                 3 
                 3 
                 3 
                 3 
                 3 
                 3 
                 3 
               
               
                 Shore A/D hardness 
                 73/28 
                 76/31 
                 69/26 
                 68/23 
                 66/19 
                 62/20 
                 58/15 
                 57/15 
               
               
                 Tg, ° C. 
                 −29.0 
                 −28.5 
                 −32.6 
                 −33.5 
                 −38.8 
                 −37.3 
                 −55.5 
                 −49.7 
               
               
                 Modulus, psi 
                 339 
                 372 
                 320 
                 274 
                 219 
                 212 
                 98 
                 68 
               
               
                 Tensile strength, psi 
                 1136 
                 675 
                 1267 
                 635 
                 1048 
                 560 
                 577 
                 314 
               
               
                 Elongation at break, % 
                 862 
                 779 
                 833 
                 728 
                 939 
                 760 
                 903 
                 866 
               
               
                 Tear resistance, lbf/in 
                 238 
                 205 
                 211 
                 202 
                 157 
                 142 
                 77 
                 64 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
               
             
               
                   
                 TABLE 15 
               
             
            
               
                   
                   
               
               
                   
                 Comp. Ex. 
                 Example 
                 Example 
                 Example 
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                   
                 H1 
                 H2 
                 H3 
                 H4 
                 H5 
                 H6 
                 H7 
                 H8 
               
               
                   
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                 Krasol ® LBH 2000 LO 
                 100 
                 100 
                 75 
                 75 
                 50 
                 50 
                 0 
                 0 
               
               
                 Polyfarnesene diol 
                 0 
                 0 
                 25 
                 25 
                 50 
                 50 
                 100 
                 100 
               
               
                 2-ethyl-1,3-hexanediol 
                 20.40 
                   
                 20.20 
                   
                 20.00 
                   
                 19.60 
               
               
                 2,2,4-trimethyl-1,3- 
                   
                 20.40 
                   
                 20.20 
                   
                 20.00 
                   
                 19.60 
               
               
                 pentanediol 
               
               
                 2,4′ Diphenylmethane 
                 46.17 
                 46.17 
                 46.37 
                 46.37 
                 46.58 
                 46.58 
                 46.98 
                 46.98 
               
               
                 Diisocyanate 
               
               
                 20% T-12 in DBP, drops 
                 3 
                 3 
                 3 
                 3 
                 3 
                 3 
                 3 
                 3 
               
               
                 Shore A/D hardness 
                 91/48 
                 91/44 
                 88/41 
                 88/40 
                 82/36 
                 88/39 
                 84/35 
                 84/37 
               
               
                 Tg, ° C. 
                 −26.8 
                 −30.0 
                 −33.9 
                 −34.3 
                 −39.0 
                 −40.2 
                 −48.11 
                 −50.46 
               
               
                 Modulus, psi 
                 1163 
                 1146 
                 1059 
                 1026 
                 801 
                 830 
                 687 
                 714 
               
               
                 Tensile strength, psi 
                 2106 
                 1347 
                 1869 
                 1586 
                 1659 
                 1291 
                 1477 
                 1027 
               
               
                 Elongation at break, % 
                 452 
                 383 
                 460 
                 490 
                 548 
                 483 
                 514 
                 396 
               
               
                 Tear resistance, lbf/in 
                 464 
                 378 
                 395 
                 385 
                 346 
                 326 
                 260 
                 240 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
               
             
               
                   
                 TABLE 16 
               
             
            
               
                   
                   
               
               
                   
                 Comp. Ex. 
                 Example 
                 Example 
                 Example 
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                   
                 I1 
                 I2 
                 I3 
                 I4 
                 I5 
                 I6 
                 I7 
                 I8 
               
               
                   
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                 Krasol ® LBH 2000 LO 
                 100 
                 100 
                 75 
                 75 
                 50 
                 50 
                 0 
                 0 
               
               
                 Polyfarnesene diol 
                 0 
                 0 
                 25 
                 25 
                 50 
                 50 
                 100 
                 100 
               
               
                 2-ethyl-1,3-hexanediol 
                 32.50 
                   
                 32.30 
                   
                 32.10 
                   
                 31.70 
               
               
                 2,2,4-trimethyl-1,3- 
                   
                 32.50 
                   
                 32.30 
                   
                 32.10 
                   
                 31.70 
               
               
                 pentanediol 
               
               
                 2,4′ Diphenylmethane 
                 67.38 
                 67.38 
                 67.58 
                 67.58 
                 67.79 
                 67.79 
                 68.19 
                 68.19 
               
               
                 Diisocyanate 
               
               
                 20% T-12 in DBP, drop 
                 3 
                 3 
                 3 
                 3 
                 3 
                 3 
                 3 
                 3 
               
               
                 Shore A/D hardness 
                 95/58 
                 96/57 
                 92/49 
                 95/53 
                 95/48 
                 85/48 
                 96/55 
                 95/52 
               
               
                 Tg, ° C. 
                 −31.3 
                 −29.2 
                 −35.9 
                 −34.5 
                 −36.7 
                 −41.3 
                 −62.1 
                 −63.6 
               
               
                 Modulus, psi 
                 2160 
                 2099 
                 1955 
                 1915 
                 1824 
                 1710 
                 1623 
                 1557 
               
               
                 Tensile strength, psi 
                 3093 
                 2207 
                 2415 
                 2133 
                 3230 
                 1761 
                 2355 
                 1669 
               
               
                 Elongation at break, % 
                 429 
                 290 
                 314 
                 280 
                 425 
                 235 
                 329 
                 203 
               
               
                 Tear resistance, lbf/in 
                 627 
                 561 
                 564 
                 542 
                 527 
                 471 
                 427 
                 420 
               
               
                   
               
            
           
         
       
     
     Similar to the samples obtained by the one-shot procedure, increased concentrations of polyfarnesene diol in the polyol blend resulted in lower hardness and tensile strength in the cured samples. The use of 2-ethyl-1,3-hexanediol instead of 2,2,4-trimethyl-1,3-pentanediol provided improved physical properties of all samples suggesting that the appropriate selection of the type and amount of chain extender may counter the effects of increasing the concentration of farnesene-based soft segments in the polyurethane. 
     B1, B2, B3, and B4 were prepared by the one shot procedure and had a hard segment content (chain extender plus diisocyanate) based on the total weight of the composition of about 30 wt %. G1, G3, G5, and G7 also had a hard segment content of about 30 wt %, but were produced by the two-shot method. G1, G3, G5, and G7 exhibited a slightly improved tensile strength. Increasing the hard segment content generally improved overall physical performance. For example, compare C1, C2, C3, and C4 with H1, H3, H5, and H7, which all have a hard segment content of about 40 wt. %. 
     While preferred embodiments of the invention have been shown and described herein, it will be understood that such embodiments are provided by way of example only. Numerous variations, changes, and substitutions will occur to those skilled in the art without departing from the spirit of the invention. Accordingly, it is intended that the appended claims cover all such variations as fall within the spirit and scope of the invention.