BIO-BASED POLYOLS AND POLYMERS MADE THEREFROM

FIELD

[0001 ] This disclosure relates to compositions resulting from the dehydration and esterification of a sugar alcohol (i.e., an alditol). In some particular embodiments, the composition comprises mono-acylated sorbitan and/or mono-acylated isosorbide.

SUMMARY

[0002] In a first aspect, a composition is provided, the composition comprising:

at least one of a substituted mo

and a substituted dianhydrohexitol (II)

wherein at least one of R ¹ , R ² , R ³ , and R ⁴ is an acyl group, at least one of R ⁵ and R ⁶ is an acyl group, and the compositio has a hydroxyl number of less than about 500 mg KOH/g. In some embodiments, at least one of R ¹ , R ² , R ³ , and R ⁴ is -CHO, -COCH ₃ , or -COCH ₂ CH ₃ and at least one of R ⁵ and R ⁶ is -CHO, -COCH ₃ , or -COCH ₂ CH3. In some embodiments, the composition has a viscosity of less than about 25 Pa ^» s at 25 °C, In some embodiments, the composition has a number average molecular weight of greater than about 140 Da and less than about 250 Da, In some embodiments, the composition has a number average hydroxyl functionality of greater than 0 and less than about 3.5. In some embodiments, the composition comprises at least one of a mono-acylated sorbitan and a mono-acylated isosorbide. n some embodiments, the composition comprises at least one of a mono- acetylated sorbitan and a mono-acetylated isosorbide. In some embodiments, a rigid foam made from a reaction of the composition with a polyisocyanate is provided. In some embodiments, the rigid foam is manufactured using an isocyanate index of from about 50 to about 300. In some embodiments, the rigid foam has an initial k -Factor of less than about 0.025 W/m» . In some embodiments, the rigid foam has a flame spread index of less than about 75. In some embodiments, the rigid foam has a smoke index of less than about 450.

[0003] In a second aspect, provided is a composition comprising: at least one of a substituted monoanhydrohexitol (I)

and a substituted dianhydrohexitol (II)

wherein at least one of R ^! , R ² , R ³ , and R ⁴ is an acyl group, at least one of R ⁵ and R ⁶ is an acyi group, and the ratio of monoanhydrohexitol equivalents to dianhydrohexitol equivalents is about 90: 10 to about 1 0:90. In some embodiments, the ratio of monoanhydrohexitol equivalents to dianhydrohexitol equivalents is about 70:30 to about 30:70. In some embodiments, the ratio of monoanhydrohexitol equivalents to dianhydrohexitol equivalents is about 60:40 to about 40:60. In some embodiments, at least one of R ¹ , R ² , R ³ , and R ⁴ is - CHO, -COCH3, and -COCH ₂ CH ₃ and at least one of R ⁵ and R ⁶ is -CHO, -COCH3, and - COCH2CH3. In some embodiments, the composition has a viscosity of less than about 25 Pa ^« s at 25 °C. In some embodiments, the composition has a number average molecular weight of greater than about 140 Da and less than about 250 Da. In some embodiments, the composition has a number average hydroxy! functionality of greater than 0 and less than about 3.5. In some embodiments, the composition comprises a mono-acylated sorbitan and a mono-acylated isosorbide. In some embodiments, the composition comprises a mono- acetylated sorbitan and a mono-acetylated isosorbide. In some embodiments, provided is a rigid foam made from a reaction of the composition with a polyisocyanate. In some embodiments, the rigid foam is manufactured using an isocyanate index of from about 50 to about 300. In some embodiments, the rigid foam has an initial k -Factor of less than about 0.025 W/m» . In some embodiments, the rigid foam has a flame spread index of less than about 75. In some embodiments, the rigid foam has a smoke index of less than about 450.

[0004] In a third aspect, provided is a method of preparing a composition, the method comprising; combining a hexitol, an acid catalyst, and at least one of an organic acid, an acid chloride, or an acid anhydride to form a mixture; and heating the mixture to provide the composition, wherein the composition comprises at least one of:

a substituted monoanhydrohexitol (I)

and a substituted dianhydrohexitol (11)

wherein at least one of R ¹ , R ² , R ² , and R ⁴ is -an acyl group, at least one of R ⁵ and R ⁶ is an acyl group, and the composition has a hydroxyl number of less than about 500 mg KOH/g. In some embodiments, the acid catalyst comprises sulfuric acid. In some embodiments, the organic acid is selected from the group consisting of formic acid, acetic acid, and propionic acid. In some embodiments, the mixture is heated to a temperature of about 1 15 °C to about 130 °C. In some embodiments, the mixture is heated at a pressure of greater than 0 mm Hg and less than 760 mm Hg. In some embodiments, provided is a rigid foam made from a reaction a polyisocyanate with the composition prepared by the disclosed methods. In some embodiments, the rigid foam is manufactured using an isocyanate index of from about 50 to about 300. In some embodiments, the rigid foam has a k -Factor of less than about 0.025 W/m*K. In some embodiments, the rigid foam has a flame spread index of less than about 75. In some embodiments, the rigid foam has a smoke index of less than about 450. BRIEF DESCRIPTION OF THE DRAWINGS

[0005] FIG. 1 is a gel permeation chromatogram ("GPC") of the reaction products prepared as described in Example 8.

[0006] FIG, 2 is a GPC of the reaction products prepared as described in Example 8 overlayed with the product of its methanolysis as described in Example 9.

[0007] FIG. 3 is a GPC of the reaction products prepared as described in Example 10.

[0008] FIG. 4 is a graph comparing the k-Factors for thermal insulation properties of two foams.

[0009] FIG. 5 is a photograph showing deformation of foams after a burn test.

DETAILED DESCRIPTION

Terms and Definitions

[0010] As used herein "polyol" refers to a molecule having an average of greater than 1 .0 hydroxy! groups per molecule (i.e., a number average hydroxyl functionality ("Fn") of greater than 1 .0). A polyol may also include functionality other than hydroxyl groups.

[001 1 ] "Hydroxyl number" ("OH#") is a measure of the hydroxy! ("-OH") groups present in a material. The hydroxyl number is reported in units of mg OH/gram and is measured according to the procedure of AOCS Cd 13-60 (2009).

[0012] "Number average molecular weight" (" _n ") is the average molecular weight of a mixture expressed in the units of Daltons ("Da") as calculated by summing the weight fraction times the molecular weight in Daltons of each species in the mixture.

[001 3] "F _n " is the number average hydroxyl functionality expressed in number of hydroxyl groups per polyol molecule. F„ is calculated using the equation:

F _n = (OH#)(Mn)/56, I 00

[0014] "Oligomer" for purposes of this disclosure refers to a molecule containing one or more intermolecular ether linkages that are formed during the dehydration process, Intermolecular ether linkages, for example, can be formed between two sorbitol molecules, between a sorbitol and a sorbitan molecule, between two sorbitan molecules, between two isosorbide molecules, between a sorbitol molecule and an isosorbide molecule, between an isosorbide molecule and a sorbitan molecule, etc. Isosorbide and sorbitan, which only include intramolecular ether linkages, are not considered oligomers for purposes of this disclosure,

[0015] "Acid Value" ("AV") is determined using a modified version of the American Oil Chemists Society method AOCS Cd 3d-63 (2009) in which water is substituted for the tsopropano!/toluene solvent. AV is reported in units of mg KOH/gram of material.

[0016] "Viscosity" is measured using an AR 2000 Rheometer (TA Instruments Inc., New Castle, DE). Measurement conditions include: cone and plate measuring system, gap distance of 150μιη, plate diameter of 25 mm, cone angle of 5 degrees, and temperature of 25 °C.

[0017] "Jsocyanate index" as used herein, refers to a measure of the stoichiometric balance between the equivalents of isocyanate groups used, to the equivalents of active hydrogens present from polyols, water, and other isocyanate-reactive components. An isocyanate index of 100 means enough isocyanate groups are provided to be able to theoretically react with all the active hydrogen groups present in the formulation. An isocyanate index of 200 means there are two times the isocyanate groups needed to react with all the active hydrogen groups present in the formulation.

[0018] "Isosorbide equivalents" as used herein, refers to unsubstituted isosorbide, mono- substituted isosorbide, and di-substituted isosorbide, where substitution refers to the replacement of a hydroxyl moiety with an acyloxy moiety.

[0019] "Sorbitan equivalents" as used herein, refers to unsubstituted sorbitan, mono- substituted sorbitan, di-substituted sorbitan, tn-substituted sorbitan, and tetra-substituted sorbitan, where substitution refers to the replacement of a hydroxyl moiety with an acyloxy moiety.

[0020] "Polyisocyanurate ("PIR") foam" for purposes of this disclosure refers to a polyurethane foam that results from the reaction of methylenediphenyldiisocyanate ("MDI") and a polyol with an isocyanate index above 150. The catalysts utilized typically vary from commonly-used polyurethane foam catalysts. The cataiysts utilized for PIR foams promote the trimerization reaction to form isocyanurates. Examples of these catalysts typically are metal salts (preferably Group I metal salts, such as, for example, potassium acetate and potassium octoate). Examples of other PIR catalysts are amine-based isocyanate trimerization catalysts, for example DABCO TMR ^® (Air Products and Chemicals, Inc., Allentown, PA). The PIR foams typically are stiffer than poiyurethane foams made with a lower isocyanate index. The PIR foams typically are more chemically and thermally stable than non PIR poiyurethane foams. The isocyanate index utilized for PIR foams may be less than 500. In some embodiments, the isocyanate index utilized to make PIR foams may be from about about 150 to 300. The density of PIR foams can be adjusted depending on the overall physical properties desired in the foams. In some embodiments, the PIR foam may have a k-Factor less than about 0.025 W/K*m. In some embodiments, the PIR foam may have a flame spread index of less than about 75. In some embodiments, the PIR foam may have a smoke index of less than about 450.

[0021 ] Gel permeation chromatographic ("GPC") analysis is done using a liquid chromatographic system (Waters Corporation, Milford, MA) consisting of a 1515 isocratic pump, a 717 autosampler, a WAT038040 column oven, a 2414 Differential Refractometer detector, and BREEZE™ software (Waters Corporation, Milford, MA). For Example 8 and Example 9 a series of GPC columns (Phenomenex, Torrance , CA) are used consisting of a Phenogel 5 -Li near/Mixed 50 x 7.8 mm guard column, and Phenogel 5-50A 300 mm x 7.8 mm, Phenogel 5-100A 300 mm x 7.8 mm, Phenogel 5- l ⁰³ A 300 mm x 7.8 mm, and Phenogel 5- l ⁰ A 300 mm x 7.8 mm columns. Tetrahydrofuran ("THE") is used as the mobile phase at a flow rate of 1 mL/minute. The samples are injected as approximately 1% (w/v) solutions in THF with a 50 injection volume. The columns and detector are maintained at 30°C. GPC analysis of Example 10 used the same setup, except that the Phenogel 5-1 ⁰⁴ Λ column is not used, since it is demonstrated that this column does not improve separations, but simply adds to retention time.

[0022] For the four-column system, the GPC chromatogram shows three major peaks with e!ution times with maximum intensities at approximately 36.5 minutes, 38 minutes, and 40 m inutes. The peaks at 38 minutes and 40 minutes are assigned to acetylated sorbitan molecules and acetylated isosorbide molecules, respectively, based on the analysis of pure compounds. The peak eluting from 35.5 minutes to approximately 37 minutes is assigned to higher molecular weight oligomers. For the three-column GPC system, the elution times are approximately ten minutes lower with corresponding times of 26.5 minutes, 27.7 minutes, and 29.4 minutes. The peaks at 27.7 minutes and 29.4 minutes are assigned to the sorbitan and isosorbide acetyls, respectively. The peak eluting from 25 minutes to approximately 27 minutes is assigned to higher molecular weight oligomers. One skilled in the art will understand that while the position (elution time) of the peaks may shift from run to run, the relative position of the peaks for the molecules of interest will remain the same.

[0023] Unless otherwise indicated, "molecular weight" refers to number average molecular weight.

[0024] Water content is measured according to the method of ASTM El 064-08 using a Coulometric Karl Fischer titration.

[0025] "k-Factor" is measured in accordance with the procedures of ASTM-C51 8-04, "Initial k-Factor" is measured within one week of foam preparation. k-Factor is reported in units of watts per kelvin-meter (W/K»m).

[0026] "Compression strength" is measured according to the procedures of ASTM-D1623 - 00.

[0027] "Density" of the foams is measured according to the procedures of ASTM-D1622- 98.

Dehydration, Cycltzation, and Esterification of Sugar Alcohols

[0028] Sugar alcohols are the hydrogenated form of carbohydrates wherein the aldehyde or ketone group of the corresponding carbohydrate is reduced to a hydroxy! group. Examples of sugar alcohols include, without limitation, arabitol, dulcitol, erythritol, glycerol, glycols, iditol, isomalt, lactitol. mannitol, polyglycitol, ribitol, sorbitol, threitol, xylitol, and maltitol. Sugar alcohols can undergo esterification and dehydration reactions to form various products.

[0029] For example, hexitols, hexahydric acyclic alcohols having the general formula HOCH2(CHOH)4CH ₂ OH, (also known as 1 ,2,3,4,5,6-hexahydroxyhexane) can lose a first water molecule to form a monoanhydrohexitol and can lose a second water molecule to form a dianhydrohexitol. Structures for hexitol, monoanhydrohexitol, and dianhydrohexitol are shown in Scheme 1 .

Hexitol Monoanhydrohexitol Dianhydrohexitol Scheme I . Structures for hexitol, monoanhydrohexitol, and dianhydrohexitol.

[0030] Hexitols, monoanhydrohexitols, and dianhydrohexitols can undergo reactions, such as, for example, esterification reactions, to form, mono-, di-, and tri-substituted products, such as, for example, mono-, di-, and tri-substituted esters. (Hexitols can have as many as six ester groups, the monoanhydrohexitols four ester groups, and the dianhydrohexitols two ester groups).

[0031 ] Sorbitol is a widely-available sugar alcohol {i.e., an alditol) and can be readily dehydrated to form a bicyclic ring structure. Sorbitol (CgHsCOHJe) is a six carbon sugar alcohol that is typically made by the hydrogenation of a glucose-containing composition. The giucose-containing composition may contain at least about 40 % by weight glucose, at least about 50 % by weight glucose, at least about 90 % by weight glucose, or at least about 95 % by weight glucose. Sorbitol can also be obtained in a mixture by the hydrogenation of a composition obtained from the hydrolysis of sucrose. For example, unrefined sugar from sugar cane and/or sugar beets can be hydrolyzed and then hydrogenated to obtain a composition typically containing from about 40 % to 80 % by weight sorbitol (the remainder typically comprising from 20 % to 60 % by weight mannito! and other materials). Similarly high fructose corn syrup, obtained by the enzymatic conversion of glucose, can be hydrogenated to a composition comprising sorbitol and mannitol.

[0032] As shown in Scheme 2, the single dehydration reaction of sorbitol typically produces sorbitan. Isosorbide can be obtained from a double dehydration reaction of a sorbitol molecule. Isosorbide is a bicyclic fused ring molecule having the chemical formula: Ο,Η^Ο^ The reaction to form isosorbide is an intramolecular cyclization reaction.

Scheme 2. Dehydration of sorbitol to form sorbitan and isosorbide

[0033] The dehydration reaction may be catalyzed or imcatalyzed. Both acid and base catalysts may be utilized. The reaction preferably is catalyzed with an acid, which can be an inorganic or organic acid of either the Bronsted or Lewis types. The acid catalyst may also be a homogeneous or heterogeneous catalyst. The latter includes a homogeneous catalyst (eg. sulfuric acid) immobilized on a solid support {e.g., silica, alumina, zeolites). Examples of inorganic acid catalysts that may be utilized include sulfurous, sulfuric, hydrochloric, hydrofluoroboric, phosphoric, and hypophorous acids. Examples of organic acid catalysts that can be utilized include p-toiuenesuifonic acid and trifluoromethanesulfonic acid. Examples of base catalysts that may be utilized include sodium hydroxide, potassium hydroxide and sodium carbonate. When an acid catalyst is utilized, the catalyst typically comprises from 0.001 to 5 weight percent of the reactive mixture, preferably from about 0.01 to 2.0 percent by weight of the reactive mixture, and more preferably from 0.03 to 1 .0 percent by weight of the reactive mixture and sometimes from 0.05 to 0.5 percent by weight of the reactive mixture.

[0034] Esterification of polyols present in the reactive mixture to provide acylated monoanhydrohexitols and acylated dianhydrohexitols can be accomplished by the addition of an acylating agent to the reactive mixture. An acyiating agent can include, for example, an organic acid, an acid chloride, or an acid anhydride to the reactive mixture. Organic acids can include, for example, formic acid, acetic acid, propionic acid, and mixtures thereof. Acid halides can include, for example, formyl chloride, acetyl chloride, propionyl chloride, and mixtures thereof. Acid anhydrides can include, for example, formic anhydride, acetic anhydride, propionic anhydride, and mixtures thereof.

[0035] In some embodiments, the acyiating agent can be added to the reaction mixture including the hexitol and the catalyst at the beginning of the reaction (i.e., before dehydration of the hexitol), followed by heating of the reaction mixture to produce dehydration and acylation products such as, for example, acylated monoanhydrohexitol, acylated dianhydrohexitol, and mixtures thereof. In soine embodiments, the acylated monoanhydrohexitols may include a mono-acylated monoanhydrohexitol and the acylated dianhydrohexitol may include a mono-acylated dianhydrohexitol. In some embodiments, the acylated monoanhydrohexitols may include a mono-acetylated monoanhydrohexitol and the acylated dianhydrohexitol may include a mono-acetylated dianhydrohexitol.

[0036] In some embodiments, the hexitol and the catalyst may be combined and heated to cause dehydration of the hexitol before addition of the acyiating agent. In some embodiments, at least about 1 0%, at least about 20 %, at least about 30 %>, at least about 40%, at least about 50%>, at least about 60%>, at least about 70%>, at least about 80%), at least about 90%, at least about 95%o, at least about 99%o, or about 100%o of the hexitol by weight may undergo dehydration before addition of the acylating agent. In some embodiments, less than about 100%, less than about 90%, less than about 80%, less than about 70,%, less than about 60%, less than about 50%, less than about 40%, less than about 30%, less than about 20%, or less than about 10% of the hexitol by weight may undergo dehydration before addition of the acylating agent. In some embodiments, about 30% to about 80%, about 40% to about 70%, or about 50% to about 60% of the hexitol by weight may undergo dehydration before addition of the acylating agent.

[0037] The reaction typically is carried out at temperatures from about 100°C to about 200°C, from about 1 10 ^° C to about 180 °C, or from about 120 ^° C to about 160 ^° C , and from about 120 °C to about 140 ^° C . The pressure of the reaction may be from a slight vacuum, i.e., just below 760 mm Hg, to a pressure of less than about 500mm Hg, less than about 400 mm Hg, or less than about 300 mm Hg. mm Hg . Water is removed during the reaction in order to promote/enhance the formation of the reaction product. As described above, a slight vacuum typically is applied to the reactor in order to enhance the removal of water. The reaction typically is carried out until the desired isosorbide equivalents (this includes the esters) content is obtained. Then the reaction typically is stopped. Methods known to one of skill in the art can be utilized to stop the reaction. For example, the temperature can be reduced below the reaction temperature. Alternatively, an additive can be introduced that stops the reaction. For example, if a catalyst is used, an agent can be introduced to stop or greatly reduce the reaction. For example, if an acid catalyst is utilized, a base compound can be introduced to neutralize the acid catalyst. Likewise, if a base catalyst is utilized, an acid compound can be introduced to neutralize the base catalyst. Also, the additive can be utilized in connection with lowering the temperature, in order to obtain the desired concentration of isosorbide. In an alternative aspect, no additive is utilized, but the addition of heat is removed from the reaction before the reaction is complete and the reaction continues as the residual heat is removed until the desired final isosorbide equivalents content is reached in the reaction product.

[0038] The desired level of isosorbide equivalents may be from about 30 % to about 90 % by weight, from about 35 % to about 80 % by weight, from about 40 % to about 70 % by weight, and from about 45 % to about 60 % by weight of the reaction product. The desired level of sorbitan equivalents may be from about 10 % to about 70 % by weight, from about 15 % to about 60 % by weight, from about 25 % to about 60 % by weight, and from about 30 % to about 50 % by weight of the reaction product. The equivalents of isosorbide and sorbitan are measured using gel permeation chromatography ("GPC") analysis.

[0039] The total amount of sorbitan equivalents and isosorbide equivalents present during the reaction does not need to be measured directly. Instead, the amount of water and organic acid removed may be used to estimate how far the reaction has progressed. By carrying out several test manufacturing runs, correlations can be developed that relate the amount of sorbitan equivalents and isosorbide equivalents present in the reaction product to the amount of water and organic acid removed from the reactor. Also, the amount of weight loss from the reactor can be monitored in order to determine the amount of sorbitan equivalent and isosorbide equivalent formation and this information can be used to determine when to stop adding heat to the reaction (and/or when to begin cooling the reaction). Also, once appropriate experience has been gained in the manufacture of the reaction product; knowledge of the reactants, the temperatures and pressures utilized and the time for cooling the reaction may be utilized to determine when to stop adding heat to the reaction (and/or when to begin cooling the reaction) to obtain the desired isosorbide equivalents content in the reaction product.

The Reaction Product

[0040] In some embodiments, the reaction product may include at least one of a substituted monoanhydrohexitol (I)

wherein at least one of R ¹ , R ² , R ³ , and R ⁴ is an acyi group, at least one of R ⁵ and R ⁶ is an acyl group.

I I [0041 ] In some embodiments, the ratio of monoanhydrohexitol equivalents to dianhydrohexitoi equivalents is about 90: 10 to about 10:90, about 70:30 to about 30:70, or about 60:40 to about 40:60.

[0042] In some embodiments, the reaction product may have a viscosity of about 30 Pa*s or less at 25°C, 25 Pa*s, 20 Pa»s or less at 25°C, or 15 Pa*s or less, for example, 10 Pa»s or less at 25°C.

[0043] As described above, the "Number average molecular weight" ("Mn") is the average molecular weight of a mixture expressed in units of Daltons ("Da"), and can be calculated by summing the weight fraction times the molecular weight in Daltons of each species in the mixture. The molecular weight for the different species can be determined utilizing GPC, by comparing the experimental product with a standard curve obtained using a series of compounds with known molecular weights and software program in the GPC instrument automatically calculates the Mn based on these standards.

[0044] A theoretical average molecular weight can also be estimated in the following manner. The product comprises acylated monoanhydro- and dianhydrohexitoi equivalents. Methanolysis of this product yields a non-acetylated material, containing mostly monoanhydrohexitols and dianhydrohexitois, with very small amounts of oligomeric polyols. The relative amount of the monoanhydrohexitols and dianhydrohexitois can be determined by GPC, and if necessary utilizing HPLC and standard concentration versus response curves for each species. This information can then be used to determine the OH# of the product after methanolysis, but can also be determined experimentally. Since the OH# of the product before methanolysis can also be determined experimentally, the number of hydroxyl groups that are esterified can be calculated, assuming a statistical distribution between all the available hydroxy! groups. This information can then be used to calculate the average molecular weight. Utilizing the calculated average molecular weight of the acylated product, and the measured OH#, the average functionality can be calculated based on the equation provided above.

[0045] In some embodiments, the reaction product may have a number average molecular weight of greater than about 140 Da and less than about 250 Da.

[0046] In some embodiments, the reaction product may have a number average hydroxyl functionality of greater than 0 and less than about4, less than about 3.5, less than about 3, less than about 2.5, or less than about 2. [0047] The reaction product typically has at least about 2 percent by weight oligomers, at least about 3 percent by weight oligomers, and may have at least about 5, about 7, about 9 percent by weight, at least about 10 percent by weight, for example at least about 1 5 percent by weight oligomers based on the weight of the reaction product. The reaction product may have a hydroxyl number of about 600 mg KOH/gram or less, about 500 mg KOH/gram or less, about 400 mg KOH/gram or less, or about 300 mg KOH/g or less. In some aspects, the reaction product may have a hydroxyl number from about 150 to about 500 mg KOH/gram or from about 200 to about 400 mg KOH/gram.

[0048] The reaction product typically comprises residual water, typically less than 5 percent by weight residual water. For some applications (such as polyisocyanurate foams) it may be preferable to limit the amount of water in the reaction product to about 2 percent by weight or less, about 1.5 percent by weight or less, about 1.0 percent by weight or less, about 0.7 percent by weight or less, or about 0.5 percent by weight or less.

Uses for the Composition Containing the Reaction Product:

[0049] The reaction products can be utilized in a variety of end-use applications. For example, the reaction product can be used in the manufacture of polyesters and poiyurethanes. For polyurethanes, the reaction products can be utilized in foam applications and in coatings, adhesives, sealants, and elastomers ("CASE") type applications. The reaction products can be used in the preparation of such polyurethanes ustilizing an isocyantate index of about 50 to about 1 50. In one particular preferred embodiment, the reaction product is utilized in the manufacture of rigid polyurethane foams. In another particular preferred embodiment, the reaction product is utilized in the production of polyisocyanurate foams.

EXAMPLES

[0050] Aspects of certain embodiments in accordance with aspects of the disclosure are illustrated in the following Examples. The materials and methods described in these Examples are illustrative and not intended to be limiting.

[0051 ] Materials: SORBIDEX™ P 1661 3, sorbitol powder (Cargill Inc., Minneapolis,

MN); C* SORBIDEX™ C-1 6106, 70% sorbitol solution in water (Cargill Inc., Minneapolis,

MN); acetic acid, glacial (EMD Chemicals, Inc., Philadelphia, PA); formic acid, 98%) (EMD

Chemicals, Inc., Philadelphia, PA); propionic acid, 99.5% (Sigma-Aldrich, St. Louis, MO); sulfuric acid, 95-98% (EMD Chemicals, Inc., Philadelphia, PA); diethylene glycol ("DEG"), industrial grade (Univar USA, Redmond, WA); diethanolamine ("DEOA"), 99% (Alfa Aesar, Ward Hill, MA); potassium hydroxide, 88% peliets (Mallinckrodt Chemical Inc., St. Louis, MO); sodium hydroxide, 97% flakes (Sigma- Aldrich, St. Louis, MO); TERATE ^® 4020 (Invista, Wichita, KS); TEGOSTAB® B8535 (Evonik Industries AG, Essen, Germany); SURFONIC® N-95 (Huntsman Corporation, The Woodlands, TX); SAYTEX ^® RB-7001 (Albemarle Corporation, Baton Rouge, LA); DABCO* K- 15 (Air Products and Chemicals, Inc., Allentown, PA); POLYCAT® (Air Products and Chemicals, Inc., Ailentown, PA); DABCO TMR-3® (Air Products and Chemicals, Inc., Allentown, PA); TR- 52 (Ele Corporation, Lyons, IL); «-Pentane (ConocoPhiliips Company, Houston, Texas); MONDUR ^®' E-489 (Bayer MateriaiScience LLC, Pittsburg, PA).

Example 1 : Esterification and dehydration of 70% sorbitol water solution and acetic acid

[0052] Into a 1000 mL three-neck round-bottomed flask equipped with mechanical stirrer, heating mantle, temperature controller, nitrogen sparge and water collector, are charged C* SORBIDEX™ C-16106 (428.57g), glacial acetic acid (300 g) and concentrated sulfuric acid (3 g). A Vigreux distillation column is inserted between the water collector and the flask. Heat is applied to the flask while stirring the contents of the flask, and nitrogen is sparged through the contents. The temperature is maintained at 120- 130 °C for two hours. A high vacuum (about 5-35 mm Hg) is then applied, and the temperature is raised to 120- 130 °C, and maintained at that temperature for another one to 1 .5 hours until most of the un-reacted acetic acid and water is stripped out. Once the distillate decreases to a trickle, the vacuum is released, and the flask is cooled to below 100 °C. The reaction product is transferred to a glass container and stored at room temperature. The entire reaction typically takes between three and four hours. The reaction product has the physical and chemical properties indicated in Table 1.

Table 1. Example 1 Reactants and Properties of Reaction Product

Example 2: Esterification and dehydration of sorbitol powder and acetic acid

[0053] Into a 1000 mL three-neck round-bottomed flask equipped with a mechanical stirrer, heating mantle, temperature controller, nitrogen sparge, and water collector, are charged SORB1DEX™ P 16613 (Sample 2-1 , 300 g; Sample 2-2, 300 g; Sample 2-3, 450 g; and Sample 2-4, 200 g), glacial acetic acid (Sample 2-1 , 300 g; Sample 2-2, 200 g; Sample 2- 3, 150 g; and Sample 2-4, 300), and 1 : 1 sulfuric acid solution in water (Sample 2- 1 , 6 g; Sample 2-2, 5 g; Sample 2-3; 6 g; and Sample 2-4, 5 g). A Vigreux distillation column is inserted between the water collector and the flask. Heat is applied to the flask while stirring the contents of the flask, and nitrogen is sparged through the contents. The temperature is maintained at 120-130 °C for two hours. A high vacuum (about 5-35 mm Hg ) is then applied, and the temperature is raised to 120- 130 °C, and maintained at that temperature for another one to 1 .5 hours until most of the un-reacted acetic acid and water is stripped out. The vacuum is released and the flask is cooled to below 100 °C. The reaction product is transferred to a glass container and stored at room temperature. The entire reaction typically takes between three and four hours. The reaction products have the physical and chemical properties indicated in Table 2.

Table 2. Example 2 Reactants and Properties of Reaction Product

Example 3 : Esterification and dehydration of dried sorbitol obtained from 70% sorbitol solution with semi-continuous addition of glacial acetic acid

[0054] A 1000 mL three-neck round-bottomed flask equipped with a mechanical stirrer, heating mantle, temperature controller, nitrogen sparge, and water collector is charged with C* SORBIDEX™C-161 6 (571 .43 g). Water begins to distill from the flask once the material in the flask reaches a temperature of from about 1 10 to 120 °C. The temperature is mainiained at aboul 130- 140 °C for about 30 minutes, until the water distilling over slows down to a trickle. [0055] A medium vacuum (about 150-225 mm Hg) is applied, and the temperature is maintained at from about 130- 140 °C for another 20 minutes until about 99% of the water in the sorbitol solution is stripped out. The flask containing the dried sorbitol is allowed to cool down to a temperature of about 120- 130 °C. A 1 : 1 sulfuric acid solution in water (1.8 g) is charged into the flask and the temperature is maintained at about 120- 130 °C. A Vigreux distillation column is inserted between the water collector and the reaction flask at this time.

[0056] For Sample 3-1 , the reaction flask is charged with 200 g total of glacial acetic acid in four aliquots of 50 g, with 30 minutes between the additions of each aliquot. For Sample 3-2, the reaction flask is charged with 200 grams total of glacial acetic acid in eight aliquots of 25 g, with 15 minutes between the additions of each aliquot. The reaction temperature is maintained at about 120- 130 °C, and a medium vacuum (about 300 mm Hg) is applied during the time acetic acid is being added. After the last aliquot of acetic acid is added, the reaction flask is kept at about 120-130 °C for about 10-20 minutes. A high vacuum (about 5-35 mm Hg) is applied, and the temperature is maintained at from about 120- 130°C for another 1 -1.5 hours until most of the un-reacted acetic acid and water was stripped out.

[0057] Once the distillate is reduced to a trickle, the vacuum is released and the flask is cooled to below 100 °C. The reaction product is transferred to a glass container and stored at room temperature. The entire reaction typically takes from between four and five hours. The resulting reaction products have the physical and chemical properties indicated in Table 3.

Table 3. Example 3 Reactants and Properties of Reaction Product

Example 4: Esterification and dehydration of dried sorbitol obtained from 70% sorbitol aqueous solution with continuous addition of glacial acetic acid

[0058] A 1000 mL three-neck round -bottomed flask equipped with a mechanical stirrer, heating mantle, temperature controller, nitrogen sparge, and water collector is charged with C* SORB1DEX™ C- 16106 (Sample 4-1 , 642.8 g; Sample 4-2, 571 .43 g; Samples 4-3 and 4- 4, 428.57 g). Water begins to distill from the flask once the material in the flask reaches a temperature of about 1 10 to 120 °C. The temperature is maintained at about 130-140 °C for about 30 minutes until the water distilling over slows down to a trickle. A medium vacuum (about 150-225 mm Hg) is applied, and the temperature is maintained at from about 130- 140 °C for another 20 minutes until about 99% of the water in the sorbitol solution is stripped out. The flask with dried sorbitol is allowed to cool down to a temperature of about 120-130°C, then a 1 : 1 sulfuric acid solution in water ( 1 .8 g) is charged into the flask. The temperature is maintained at about 120- 130 °C. A Vigreux distillation column is inserted between the water collector and the reaction flask at this time. Glacial acetic acid (Sample 4-1 , 1 0 g; Sample 4-2, 200 g, Samples 4-3 and 4-4, 300 g) is continuously charged into the reaction flask with a peristaltic pump over a period of about two hours. The reaction temperature is maintained at about 120-3 30 °C, and a medium vacuum (about 300 mm Hg) is applied during the addition of acetic acid.

[0059] After the acetic acid addition is finished, the reaction flask is kept at about 120- 130 °C for about 5-10 minutes. A high vacuum (about 5-35 mm Hg) is then applied, and the temperature is maintained at about 120- 130 °C for another 1 -1.5 hours until most of the un- reacted acetic acid and water is stripped out. Once the amount of distillate is reduced to a trickle, the vacuum is released, and the flask is cooled to below 100 °C. The reaction product is transferred to a glass container and stored at room temperature. The entire reaction typically takes between four and five hours. The resulting reaction products have the physical and chemical properties indicated in Table 4.

Table 4. Example 4 Reactants and Properties of Reaction Product

Example 5 : Esterification and dehydration of sorbitol powder with continuous addition of aqueous acetic acid solution

[0060] into a 1000 mL three-neck round-bottomed flask equipped with a mechanical stirrer, heating mantle, temperature controller, nitrogen sparge, and water collector, is charged SORBIDEX ^rs ' P 16613 (300 g). A Vigreux distillation column is inserted between the water collector and the flask. Heat is applied to the flask while stirring the contents of the flask and sparging nitrogen through the contents. When the temperature reaches about 120 °C, a 1 : 3 sulfuric acid solution in water (1.8 g) is added to the contents and the flask temperature is maintained at about 120-130 °C. Acetic acid solution in water (Sample 5-1 , 315,79 g of 95% acetic acid; Sample 5-2, 333.33 g of 90% acetic acid; Sample 5-3, 375 g of 80% acetic acid; and Sample 5-4, 428.57 g of 70% acetic acid) is added continuously using a peristaltic pump immediately after the 1 : 1 sulfuric acid solution in water is added. The reaction temperature is maintained at about 120- 130 °C, and a medium vacuum (about 300 mm Hg) is applied during the addition of acetic acid. The addition of acetic acid solution is completed within two hours, and the same temperature and vacuum are maintained for about 5- 10 minutes after the addition of acetic acid is finished. A high vacuum (about 5-35 mm Hg) is then applied, and the temperature is maintained at from about 120-130 °C for another 1 - 1 .5 hours until most of the un-reacted acetic acid and water is stripped out. Once the distillate is reduced to a trickle), the vacuum is released and the flask is cooled to below 100 °C. The reaction product is transferred to a glass container and stored at room temperature. The entire reaction typically takes between four and five hours. The resulting reaction products have the physical and chemical properties indicated in Table 5.

Table 5. Example 5 Reactants and Properties of Reaction Product

Example 6: Esterification and dehydration with glacial acetic acid of partially dehydrated sorbitol

[0061 ] Slep-1 Partial dehydration of Sorbitol: A 1000 mL three-neck round-bottomed flask equipped with a mechanical stirrer, heating mantle, temperature controller, nitrogen sparge, and water collector is charged with C* SORBIDEX™ C-16106 (714.29 g, 70% sorbitol solution in water; Cargill Inc., Minneapolis, Minnesota). Heat is applied to the flask while stirring the contents of the flask and sparging nitrogen through the contents. Water distills from the flask once the material in the flask reaches a temperature of from about 1 10 to 120 °C. The temperature is increased to 130-140 °C, and maintained there for about 30 minutes until the water distilling over slows down to a trickle. A medium vacuum (about 150-225 mm Hg) is applied, and the temperature is maintained at about 130-140 °C for another 20 minutes until about 99% of the water in the sorbitol solution is stripped out.

[0062] A solution of 1 : 1 sulfuric acid in water (1.43 g - 1.53 g) is charged to the flask. The flask temperature is raised to about 160 °C under a vacuum (about 95- 1 15 mm Hg) with agitation and a nitrogen sparge. The reaction is continued for about 30 minutes to about two hours until a target level of isosorbide is achieved.

[0063] Step-2 Esterif ation and Further Dehydration of partially-dehydrated Sorbitol with Glacial Acetic Acid; A 1000 mL three-neck round-bottomed flask equipped with a mechanical stirrer, heating mantle, temperature controller, nitrogen sparge, and water collector is charged with partially dehydrated sorbitol (prepared as described in Example 6 Step 1 above), glacial acetic acid and a solution of 3 : 1 sulfuric acid in water. The amounts of reactants used to prepare Samples 6- 1 to 6-3 1 are listed in Table 6. A Vigreux distillation column is inserted between the water collector and the flask. Heat is applied to the flask while stirring the contents of the flask and sparging nitrogen through the contents. The temperature is maintained at about 120- 130 °C for about two hours. A high vacuum (about 5- 35 mm Hg) is then applied, and the temperature is maintained from about 120- 130 °C for another 1 - 1 .5 hours until most of the un-reacted acetic acid and water is stripped out. Once the distillate is reduced to a trickle), the vacuum is released and the flask is cooled to below 100 °C. The reaction product is transferred to a glass container and stored at room temperature. The entire reaction typically takes between four and six hours. The resulting reaction products have the physical and chemical properties indicated in Table 6.

Table 6. Example 6 Reactants and Properties of Reaction Product

Initial initial

Initial Initial Dried acetic sulfuric Product Product Product

Sample Isosorbide Sorbitol acid acid OH# Viscosity State

[mg

(%) [parts] [parts] [parts] OH/g] [Pa»s] (25 °C)

Partial

6- 1 35 450 150 6 472 5.8 liquid*

Partial

6-2 48 450 1 50 6 468 8.8 liquid*

6-3 57 450 150 6 448 12.2 Partial liquid*

Partial

6-4 66 450 150 6 456 10.0 liquid*

Partial

6-5 42 450 150 6 467 7.6 liquid*

6-6 50 400 100 1 .5 567 6.6 Solid

6-7 40 450 50 1 .5 529 10.4 Solid

6-8 70 450 50 1 .5 568 16.1 Solid

6-9 43 400 200 1.8 417 3.9 Liquid

6-10 28 400 200 1.8 424 3.1 Liquid

6-1 1 49 400 200 1 .8 436 4.8 Liquid

Partial liquid" refers to a liquid with some suspended solids.

Example 7: Esterification and dehydration of fully dehydrated sorbitol with glacial acetic acid

[0064] Step-1 Full dehydration of Sorbitol: A 1000 mL three-neck round-bottomed flask equipped with a mechanical stirrer, heating mantle, temperature controller, nitrogen sparge, and water collector is charged with SORBIDEX™ C-l 63 06 (714.29 g). Heat is applied to the flask while stirring the contents of the flask, and sparging nitrogen through the contents. Water begins to distill from the flask once the material in the flask reaches a temperature of about 1 10 to 120 °C. The temperature is maintained at about 130-140 °C for about 30 minutes until the water distilling over slows down to a trick!e. A medium vacuum (about 150-225 mm Hg) is then applied, and the temperature is maintained at about 130-140 °C for another 20 minutes until about 99% of the water in the sorbitol solution is stripped out. 1 .43- 1 .53 grams of 1 : 1 sulfuric acid in water was charged to the flask. The temperature is raised to 360°C, and this temperature is maintained under vacuum of about 95- 1 15 mm Hg with agitation and a nitrogen sparge until the reaction has continued to a point where the product has at least 80% isosorbide. These products are referred to as fully dehydrated sorbitol, and are used in the following Step-2.

[0065] Step-2 Esterification of Fully Dehydrated Sorbitol with Glacial Acetic Acid: A 1000 mL three-neck round-bottomed flask equipped with mechanical stirrer, heating mantle, temperature controller, nitrogen sparge, and water collector is charged with the fully dehydrated sorbitol (prepared as described in Example 7 Step 1 above), glacial acetic acid, and a solution of 1 : 1 sulfuric acid and water. The amounts of reactants used to prepare Samples 7- 1 to 7-5 are listed in Table 7. A Vigreux distillation column is inserted between the water collector and the reaction flask. Heat is applied to the flask while stirring the contents of the flask and sparging nitrogen through the contents. The temperature is maintained at about 120-130 °C for about two hours. A high vacuum (about 5-35 mm Hg) is applied, and the temperature is raised to about 120-130 °C, and maintained at this temperature for another 1 - 1 .5 hours until most of the un-reacted acetic acid and water in the sorbitol solution is stripped out. Once the distillate is reduced to a trickle, the vacuum is released and the flask is cooled to below 100 °C. The reaction product is transferred to a glass container and stored at room temperature. The entire reaction typically takes between six and eight hours. The resulting reaction products have the physical and chemical properties indicated in Table 7.

Table 7. Example 7 Reactants and Properties of Reaction Product

* Partial liquid" refers to a liquid with some suspended solids.

Example 8: Esterification and dehydration of dried sorbitol obtained from 70% aqueous sorbitol with continuous addition of glacial acetic acid in a 190-liter reactor.

[0066] The reactor consists of a 190-liter 304 stainless steel pressure vessel with a cooling water jacket and an internal coil for heating with hot oil. Agitation is provided by an air powered motor. The reactor is equipped with an overhead condenser shell and tube heat exchanger with cooling water on the shell side. Condensate drains to a 23-liter receiver. When needed, vacuum is pulled on the reactor through the overhead condenser using a mechanical vacuum pump. A dry ice trap is installed between the outlet of the overhead condenser and the inlet of the vacuum pump to condense any vapors not condensed at the cooling water temperature.

[0067] In the first step water is removed from the aqueous 70% sorbitol solution by heating under vacuum. In a typical reaction, the reactor is charged with 186 kg of 70% aqueous sorbitol and the agitator is started and set to approximately 2,500 rpm. The oil heater is set to maintain the reactor temperature at 120°C. When the reactor temperature reaches 120°C the vacuum pump is started and the vent valve to the vacuum pump is slowly closed, gradually establishing a vacuum of about 150 mm Hg to remove water from the sorbitol solution. The reactor sight glass is observed for foaming and air is bled into the vacuum pump if necessary to minimize foaming. The pressure is gradually reduced to obtain a vacuum of about 1 10- 1 15 mm Hg while maintaining the temperature at approximately 120°C. A total of approximately 52 kg water is removed over a period of about 4 hours. The reactor is brought to atmospheric pressure by introducing nitrogen to the reactor. By calculation, the water content of the dried sorbitol is approximately 2.8%.

[0068] The second step consists of co-dehydration and esterification of sorbitol with glacial acetic acid. To the agitated dried sorbitol at approximately 120°C to 125°C is added 0.206 kilograms of 95 weight % sulfuric acid. The pressure is reduced to approximately 500 mm Hg. Subsurface addition of glacial acetic acid is started at a rate of approximately 1 .10 kg/min and continues for approximately two hours, during which time the temperature is maintained at approximately 1 10°C to 120°C and the pressure at 500 mm Hg. After removal of 31 kg of an acetic acid - water mixture the reactor is vented to atmospheric pressure with nitrogen and held at 105°C while continuing agitation. After 19 hours the pressure is reduced to 334 mm Hg and removal of acetic acid and water is continued. The temperature is increased to 120°C and the pressure reduced to 9 mm Hg over four hours and an additional 84 kg of acetic acid - water distillate is collected (a total of 1 1 5 kg). The reactor is brought to atmospheric pressure with nitrogen and cooled to approximately 60°C. The product is unloaded to a 55-gallon drum. The total weight of product is 147 kg. The properties of the product are shown in Table 8. A GPC of the reaction product is shown in FIG. 1 .

Table 8. Product Properties

Property Method Result

Hydroxyl Number AOCS CD 13-60 340 mg KOH/gram

Acid Value AOCS Cd 3d-63 4.6 mg KOH/gram

Viscosity, 25°C ASTM 2196-8B 1 1 Pa«s

Water, % ASTM D2164 0.09

Composition:

Acetylated isosorbide Gel Phase Permeation 53.1 %

Acetylated sorbitan Gel Phase Permeation 44.4%

Oligomeric species Gel Phase Permeation 2.5% Example 9. Methanolvsis of esterifted and dehydrated sorbitol with acetic acid for the purpose of analyzing acetic acid content in the products

[0069] Into a 250 mL three-neck round-bottomed flask equipped with magnetic stirrer, heating mantle, temperature controller, and reflux condenser are charged the composition prepared as described in Examples 1 -8 above (30 g), methanol (60 g), and sodium methoxide powder (0.45g). Heat is applied to the flask while stirring the contents of the flask. The contents of the flask are kept boiling at about 60-70 °C for about 2-3 hours. The reacted contents are quantitatively transferred into a single- neck flask, and the un-reacted methanol and generated methyl acetate are stripped out by heating at 80 °C under high vacuum (below 5 mm Hg) for one hour. The mass of dried product is accurately weighed; the difference in mass between the starting material (i.e., the 30 g of composition), and the dried product is attributed to the mass of acetate groups in the starting material. The composition of Example 8 products and Example 9 products are shown in Table 9.

Table 9. Composition of Example 8 and 9, before and after Methanolysis.

[0070] FIG. 2 shows an overlay of GPCs of reaction products from Examples 8 and 9. The chromatogram with peaks at approximately 39 m inutes and 40.5 minutes is Example 8 product; the chromatogram with peaks at approximately 38 and 40 minutes is Example 9, the product after methanolysis.

Example 10. Esterification and dehydration of dried sorbitol obtained from 70% aqueous sorbitol with continuous addition of glacial acetic acid in a 190-liter reactor.

[0071 ] The reactor consists of a 190-liter 304 stainless steel pressure vessel with a cooling water jacket and an internal coil for heating with hot oil. Agitation is provided by an air powered motor. The reactor is equipped with an overhead condenser shell and tube heat exchanger with cooling water on the shell side. Condensate is drained to a 23-liter receiver. When needed, vacuum is pulled on the reactor through the overhead condenser using a mechanical vacuum pump. A dry ice trap is installed between the outlet of the overhead condenser and the inlet of the vacuum pump to condense any vapors not condensed at the cooling water temperature. At the end of the reaction the product is unloaded through a 50- micron polyester filter element in a stainless steel filter housing.

[0072] In the first step water is removed from the aqueous 70% sorbitol solution by heating under vacuum. In a typical reaction, the reactor is charged with 186 kg of 70% aqueous sorbitol and the agitator is started and set to approximately 2,500 rpm. The oil heater is set to maintain the reactor temperature at 120°C. When the reactor temperature reaches 120°C the vacuum pump is started and the vent valve to the vacuum pump is slowly closed, gradually establishing a vacuum of about 1 50 mm Hg to remove water from the sorbitol solution. The overhead sight glass is observed for foaming and air is bled into the vacuum pump if necessary to minimize foaming. The pressure is gradually reduced to obtain a vacuum of about 1 10-1 1 5 mm Hg while maintaining the temperature at 120°C. A total of 53 kg water is removed over a period of about 4 hours. The reactor is brought to atmospheric pressure by introducing nitrogen to the reactor. By calculation, the water content of the dried sorbitol is approximately 2.5%.

[0073] The second step consists of co-dehydration and esterification of sorbitol with glacial acetic acid. To the agitated dried sorbitol is added 0.194 kilograms of 98 wt% sulfuric acid. The reactor temperature is gradually increased to approximately I 30°C. The vacuum pump is re-started and a vacuum of approximately 350 mm Hg is established. Subsurface addition of glacial acetic acid is started at a rate of approximately 1 .45 kg/min and continued for approximately two hours, during which time the temperature is maintained at approximately 130°C and 350 mm Hg. A total of 1 31 kg of glacial acetic acid is added over a period of two hours. After the acetic acid addition is complete, the excess acetic acid and remaining water is removed by gradually reducing the reactor pressure to approximately 10-20 mm Hg over approximately three to five hours while maintaining a temperature of 130°C. Approximately 1 12 kg of condensate (water plus acetic acid) is recovered. The product has an acid value of approximately 7 mg KOH/gram. The total weight of the product is approximately 1 6 kg. Products prepared by this procedure have the properties shown in Table 10. A typical GPC of product made according to the methods of this Example is shown in FIG. 3.

Table 10. Properties of Reaction Products of Example 10 Property Method Result

Hydroxyl Number AOCS CD 13-60 350-375 mg OH/gram

Acid Value AOCS Cd 3d-63 <1.0 mg KOH/gram

Viscosity, 25°C ASTM 2196-8B 7.5-8.0 PaS

Composition:

Isosorbide Equivalents Gel Phase Permeation 49-54%

Sorbitan Equivalents Gel Phase Permeation 42-47%

Oligomeric species Gel Phase Permeation 2.0-4.0%

Example 1 1 : Neutralization of products from Examples 8 and 10 to reduce their acid value.

A. Neutralization of Example 8 product

[0074] To a measured quantity of the Example 8 product at 50°C-60°C with an acid value of approximately 1 1 mg KOH/gram in a 55-gallon drum is added a solution of 10 weight % potassium hydroxide in diethylene glycol calculated to result in 500 ppm potassium acetate. The drum is rolled several hours. To the drum of Example 8 product at 50°C-60°C previously neutralized with potassium hydroxide is added a solution of 13.5 weight % sodium hydroxide in diethylene glycol calculated to provide a 1 .2/1.0 equivalent ratio of sodium hydroxide to residual acid. The drum is rolled for several hours. The resulting AV is 3-4 mg KOH/gram, To the drum of Example 8 product at 50°C~60°C previously neutralized with 1 3.5% sodium hydroxide above is added an additional quantity of 13.5 weight % sodium hydroxide in diethylene glycol calculated to provide a 1 .2/1.0 equivalent ratio of sodium hydroxide to residual acid. The drum is rolled at for several hours. The resulting AV is still greater than 1 mg KOH/gram. To the thrice-neutralized Example 8 product at 50°C-60°C is added a quantity of diethanoiamine calculated to provide a 1 .2/1 .0 equivalent ratio of diethanoiamine to residual acid. The drum is rolled at for several hours. The final product has an acid value of "0".

B. Neutralization of Example JO product

[0075] To a measured quantity of the Example 1 0 product at 50°C-60°C with an acid value of approximately 8 mg KOH/gram in a 55-gailon drum is added a solution of 10 weight % potassium hydroxide in diethylene glycol calculated to result in 500 ppm potassium acetate. To the Example 10 product at 50°C-60°C is added a quantity of diethanoiamine calculated to provide a 1 .3/1 .0 equivalent ratio of diethanoiamine to residual acid. The drum is rolled at for several hours. The final product has an acid value of 2-3 mg OH/gram. To the preceding Example 10 product at 50°C-60°C is added a quantity of diethanolamine calculated to provide a 1.5/1 .0 equivalent ratio of diethanolamine to residual acid. The drum is rolled at for several hours. The final product has an acid value of approximately 0.4 mg KOH/gram.

Example 12: Estenfication and dehydration of sorbitol powder with propionic acid

[0076] Into a 1000 mL three-neck round-bottomed flask equipped with a mechanical stirrer, heating mantle, temperature controller, nitrogen sparge, and water collector, are charged SORB1DEX™ P 16613 (Sample 12- 1 , 300 g; Sample 12-2, 400 g), propionic acid (Sample 12-1 , 300 g; Sample 12-2, 200 g), and 1 : 1 sulfuric acid solution in water (Sample 8- 1 , 1 .8 g). A Vigreux distillation column is inserted between the water collector and the flask. Heat is applied to the flask while stirring the contents of the flask, and nitrogen is sparged through the contents. The temperature is maintained at about 120- 130 °C for two hours. A high vacuum (about 5-35 mm Hg ) is applied, and the temperature is maintained at about 120- 130 °C for another one to 1.5 hours until most of the un-reacted propionic acid and water is stripped out. Once the distillate is reduced to a trickle), the vacuum is released and the flask is cooled to below 100 °C. The reaction product is transferred to a glass container and stored at room temperature. The entire reaction typically takes between three and four hours. The reaction products have the physical and chemical properties indicated in Table 3 1 .

Table 1 1 . Example 12 Reactants and Properties of Reaction Product

Example 1 3 : Esterification and dehydration of sorbitol powder with formic acid

[ 0077] Into a 1000 mL three-neck round-bottomed flask equipped with a mechanical stirrer, heating mantle, temperature controller, nitrogen sparge, and water collector, are charged SORBIDEX™ P 16613 (Sample 33-1 , 300 g; Sample 13-2, 400 g), formic acid (Sample 13- 1 , 300 g; Sample 1 3-2, 200 g), and 3 : 3 sulfuric acid solution in water (Sample 13- 1 , 1 .8 g; Sample 13-2, 1 .8 g). A Vigreux distillation column is inserted between the water col lector and the flask. Heat is applied to the flask while stirring the contents of the flask, and nitrogen is sparged through the contents. The temperature is maintained at about 1 20- 130 °C for two hours. A high vacuum (about 5-35 mm Hg ) is applied, and the temperature is maintained from 120-130 °C for another one to 1 .5 hours until most of the un- reacted formic acid and water is stripped out. Once the distillate is reduced to a trickle, the vacuum is released and the flask is cooled to below 1 00 °C. The reaction product is transferred to a glass container and stored at room temperature. The entire reaction typically takes between three and four hours. The reaction products have the physical and chemical properties indicated in Table 12.

Table 12, Example 13 Reactants and Properties of Reaction Product

Example 14: Commercial Bunstock Foam Trial

[0078] A commercial bunstock rigid isocyanurate foam line is used to evaluate the performance of the compositions prepared in Example 1 1 . A foam formulation (Table 13) is developed to run on the line. Four runs are made: two control runs, Runs 1 and 2, that do not include the compositions prepared in Example 1 1 and two trial runs, Runs 3 and 4, where approximately 30% of the TERATE*" 4020 is replaced with the compositions prepared in Example 1 1 B and 1 1 A respectively.

[0079] The formulations containing compositions prepared in Example 1 1 react more slowly than the control and therefore require higher levels of catalysts, as set forth in Table 1 3. The isocyanate index is fixed at 250 for Runs 1 and 3 and at 225 for Runs 2 and 4. A target of 32 kg/m ³ for density of the foams is attempted for all runs. Prior to each run. a blend of polyol, fire retardant, surfactants, and water is weighed into an agitated run tank according to the form ulations in Table 1 3. The blend is circu lated through the tow-pressure mix head and back to the run tank. During each run, catalyst flows are individually metered d irectly into the mix head. The n-pentane is metered into the run tank line, through a static mixer, located just prior to the mix head. MONDUR® E-489 is metered directly into the mix head. A total flow rate of about 1 10 kg/minute is run with a line speed of about 3 meters/minute.

Table 13. Foam Formulations, Run Conditions, and Properties

TR-52 1.1 1.1 0.9 0.83 n-PENTANE 13.4 13.19 11.7 14.51

WATER 0.37 0.37 0.23 0.22

ISOCYANATE 250 225 250 225 INDEX

A:B RATIO (by 63:37 60:40 65:35 61:39 weight)

LINESPEED (m/min) 3.1 3.1 3.1 3.1

TOTAL FLOW 110 110 110 110 (kg/min)

Table 14. Properties of the Polyisocyanurate Foams

Run 1 Foam Run 3 Foam

Density (kg/m ³ ) 33.9 31.4

Compressive 1.16 1.40 Strength (kPa)

93.3

% Closed Cells 92.8 k-FactorfW/mx ) 0.0241 0.0228 Day 1 k-Factor(W/mxK) 0.0251 0.0240 k-Factor (W/mxK) 0.0255 0.0243 Day 60

k-Factor (W/mxK) 0.0259 0.0248 Day 90

[0080] As the data in Table 14 show, the foam prepared using composition prepared in Example 1 1 B provided higher compressive strength and a lower k-Factor than the control foam formulations. The lower k-Factor enhances the insulation capacity of the rigid polyisocyanurate foams. Other physical properties of the polyisocyanurate foam prepared using composition prepared in Example 1 1 B (i.e., Run 3) are comparable to the properties of the polyisocyanurate control foam (i.e., Run 1 ).

[0081 ] The foams from Runs 1 and 3 were tested initially after being made and over a period of time to determine their respective k-Factors. During the time between testing, the foams were maintained in a 25°C environment with a relative humidity of 50%. As shown in FIG. 4, the polyisocyanurate foams prepared using composition prepared in Example 1 1 B (i.e., Run 3) showed a much lower k-Factor initially and over time than the control foams. This lower k-Factor can result in better insulation properties for the foams prepared using composition prepared in Example 1 1 B versus the control foam.

Table 1 . ASTM E84 Burn Test Results

[0082] As the data in Table 1 5 shows, the foam prepared using composition prepared in Example 1 1 A performed similarly to the control foam in the industry standard burn test (ASTM E84). These results are based on the foams produced in Run 2 and Run 4 which were run at a 225 index. As shown in FIG. 5, the foam produced in Run 4 (BOTTOM) is not as deformed as the control foam (TOP) after the standard burn test. The foam produced in Run 4 has more surface char, which in turn protects the fresh foam underneath from being exposed to the flame.