Polyester polyols with improved performance properties

Abstract

A polyester polyol comprising structural units derived from: (a) a polyacid; and (b) a polyol mixture comprising: (i) a diol having a linear or branched hydrocarbon chain between two hydroxyl groups wherein the hydrocarbon chain has an odd number of carbon atoms from 3 to 19; (ii) a polyol having a cyclic structure; and (iii) 2, 2, 4, 4-tetraalkyl-1, 3-cyclobutanediol (TACD), and a process for producing the same.

Description

Technical Field

[0001] Embodiments of the present disclosure relate generally to polyester polyols and, more particularly, to polyester polyols having improved performance properties. Background Art

[0002] Polyester polyols are widely used to prepare polyurethanes for coatings, adhesives, sealants and elastomer applications due to their outstanding mechanical strength and chemical resistance. However, many conventional polyester polyols are solid or highly viscous liquids at room temperature, which makes them unsuitable for room temperature applications such as electronic potting and conformal coating applications. In addition, high viscosity limits the amount of fillers or additives that can be added to the formulation.

[0003] To overcome this challenge, polyester polyols have been used together with other polyols (such as polyether polyols and polybutadiene polyols) having lower viscosity at room temperature. However, polyester polyols, such as those with a molecular weight greater than 800 Daltons, have very limited compatibility with polyether polyols or polybutadiene polyols. When polyether or polybutadiene polyols have a molecular weight greater than 1,000 Daltons, compatibility is even further limited. Poor compatibility may affect the stability of the formulation as well as its appearance (such as transparency). This may be particularly important in coatings and adhesives.

[0004] In addition, in some applications, such as coating, adhesive, elastomer, sealant or foam application, coating, adhesive, elastomer, sealant or foam can be exposed to moisture at high temperature. For example, when packaging is subjected to distillation, the coating or adhesive used in food packaging may experience high temperature and moisture. In the case of using polyurethane based on conventional polyester polyol, when polyester polyol is exposed to moisture at high temperature, due to the rupture of ester bond in the main chain, polyester polyol will usually be hydrolyzed. These shortcomings can significantly limit the use of polyester polyol in polyurethane applications that are essential requirements for thermal stability and hydrolytic stability.

[0005] To improve the hydrolytic stability of polyurethanes based on conventional polyester polyols, hydrolytic stabilizers (such as those based on polymeric carbodiimides) can be added to the formulation. Another method to improve hydrolytic stability is to add dimer fatty acids to the synthesis of polyester polyols. Although these solutions improve the overall hydrolytic stability of polyester polyols, the solutions neither address the viscosity characteristics of polyester polyols at room temperature nor improve their compatibility with polyether or polybutadiene polyols.

[0006] Therefore, there remains a need for a polyester polyol that is a low viscosity liquid at room temperature, has improved compatibility with polyether and polybutadiene polyols, and exhibits improved hydrolytic stability and heat resistance. Summary of the invention

[0007] In the embodiments of the present invention, polyester polyols are disclosed. The polyester polyols include structural units derived from: (a) a polyacid; and (b) a polyol mixture, the polyol mixture including: (i) a diol having a straight or branched hydrocarbon chain between two hydroxyl groups, wherein the hydrocarbon chain has an odd number of carbon atoms from 3 to 19; (ii) a polyol having a cyclic structure; and (iii) 2,2,4,4-tetraalkyl-1,3-cyclobutanediol (TACD).

[0008] Further disclosed in the embodiments herein is a method for making a polyester polyol. The method comprises reacting: (a) a polyacid; and (b) a polyol mixture, the polyol mixture comprising: (i) a diol having a straight or branched hydrocarbon chain between two hydroxyl groups, wherein the hydrocarbon chain has an odd number of carbon atoms from 3 to 19; (ii) a polyol having a cyclic structure; and (iii) 2,2,4,4-tetraalkyl-1,3-cyclobutanediol (TACD) to form a polyester polyol.

[0009] Further disclosed in the embodiments of this invention is a method for producing polyurethane. The method includes reacting a polyisocyanate with a polyester polyol, wherein the polyester polyol comprises a structural unit derived from: (a) a polyacid; and (b) a polyol mixture, wherein the polyol mixture comprises: (i) a diol having a straight or branched hydrocarbon chain between two hydroxyl groups, wherein the hydrocarbon chain has an odd number of carbon atoms from 3 to 19; (ii) a polyol having a cyclic structure; and (iii) 2,2,4,4-tetraalkyl-1,3-cyclobutanediol (TACD).

[0010] Polyurethane is further disclosed in the embodiments herein. The polyurethane comprises the reaction product of a polyisocyanate and a polyester polyol, wherein the polyester polyol comprises a structural unit derived from: (a) a polyacid; and (b) a polyol mixture, wherein the polyol mixture comprises: (i) a diol having a straight or branched hydrocarbon chain between two hydroxyl groups, wherein the hydrocarbon chain has an odd number of carbon atoms from 3 to 19; (ii) a polyol having a cyclic structure; and (iii) 2,2,4,4-tetraalkyl-1,3-cyclobutanediol (TACD).

[0011] In one or more embodiments herein, the polyol mixture comprises 20 to 80 mole % of component (i), 15 to 35 mole % of component (ii), and 5 to 20 mole % of component (iii), wherein the mole % is based on the total polyol mixture.

[0012] In one or more embodiments herein, component (i) includes 3-methyl-1,5-pentanediol, 1,5-pentanediol, 1,3-propylene glycol, or a combination thereof.

[0013] In one or more embodiments herein, component (ii) includes 1,4-cyclohexanedimethanol, 4,4'-isopropylidenedicyclohexanol, 1,3-cyclopentanediol, 1,4-cyclohexanediol, 1,4-benzenedimethanol, 4,8-bis(hydroxymethyl)tricyclo[5.2.1.02,6]decane, or a combination thereof.

[0014] In one or more embodiments herein, the polyol mixture further comprises (iv) an acyclic diol or polyol different from component (i), component (ii), and component (iii).

[0015] In one or more embodiments herein, the polyol mixture is substantially free of fused heterocyclic bicyclic polyols.

[0016] In one or more embodiments herein, the polyacid is selected from adipic acid, sebacic acid, dodecanedioic acid, azelaic acid, succinic acid, glutaric acid, pimelic acid, suberic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, naphthalene dicarboxylic acid, phthalic anhydride, hexahydrophthalic anhydride, and combinations thereof.

[0017] In one or more embodiments herein, the molar ratio of the polyol mixture to the polyacid is from 1.4:1 to 1.01:1.

[0018] Additional features and advantages of the embodiments will be set forth in the detailed description that follows, and some of the additional features and advantages will be readily apparent to those skilled in the art from the detailed description or recognized by practicing the embodiments described herein. It should be understood that the above and following detailed descriptions describe various embodiments and are intended to provide an overview or framework for understanding the nature and character of the claimed subject matter. DETAILED DESCRIPTION

[0019] Now will be referred to in detail polyester polyol, its manufacture method, the method for producing polyurethane and embodiment of polyurethane.Polyester polyol can be used for making polyurethane.Polyurethane can be used for coating, adhesive, elastomer, sealant or foam application.However, it should be noted that this is only the illustrative specific implementation of embodiment disclosed herein.These embodiments are applicable to other technologies that are susceptible to problems similar to those discussed above.

[0020] In embodiments herein, polyester polyols include structural units derived from polyacids and polyol mixtures. As used herein, the term "polyol" refers to an alcohol having at least two hydroxyl (OH) groups. In some embodiments herein, the molar ratio of the polyol mixture to the polyacid is 1.4:1 to 1.01:1. All individual values ​​and subranges are included and disclosed herein. For example, in some embodiments, the molar ratio of the polyol mixture to the polyacid is 1.3:1 to 1.01:1, 1.25:1 to 1.05:1, 1.25:1 to 1.10:1, or 1.25:1 to 1.15:1.

[0021] In embodiments herein, polyacid can be dicarboxylic acid, dicarboxylic acid derivative or its combination.Polyacid as herein described may be substituted or may not be substituted.In some embodiments, polyacid can be aliphatic or aromatic dicarboxylic acid, aliphatic or aromatic dicarboxylic acid derivative or its combination.In some embodiments, polyacid is selected from adipic acid, sebacic acid, dodecanedioic acid, azelaic acid, succinic acid, glutaric acid, pimelic acid, suberic acid, isophthalic acid, terephthalic acid, cyclohexane dicarboxylic acid, naphthalene dicarboxylic acid, phthalic anhydride, hexahydrophthalic anhydride and its combination.

[0022] In embodiments herein, the polyol mixture comprises: (i) a diol having a straight or branched hydrocarbon chain between two hydroxyl groups, wherein the hydrocarbon chain has an odd number of carbon atoms from 3 to 19; (ii) a polyol having a cyclic structure; and (iii) 2,2,4,4-tetraalkyl-1,3-cyclobutanediol (TACD). In some embodiments herein, the polyol mixture comprises 20 mol % to 80 mol % of component (i), 15 mol % to 35 mol % of component (ii) and 5 mol % to 20 mol % of component (iii), wherein the mol % is based on the total polyol mixture. All individual values ​​and subranges are included and disclosed herein. For example, in some embodiments, the polyol mixture comprises from 20, 30, 40, or 50 mole % to 80, 75, or 70 mole % of component (i), from 15, 20, 35, 30, or 25 mole % of component (ii), and from 5, 10, 20, 15, or 10 mole % to 20, 15, or 10 mole % of component (iii), wherein the mole % are based on the total polyol mixture.

[0023] In one or more embodiments herein, examples of suitable component (i) alcohols may include, but are not limited to, C3-C19 aliphatic or aromatic diols, substituted C3-C19 aliphatic or aromatic diols, C7-C19 aliphatic or aromatic triols, of course, where the hydrocarbon chain has an odd number of carbon atoms excluding the carbon atoms in the side chains. In some embodiments, component (i) is selected from 1,3-propylene glycol, substituted 1,3-propylene glycol, 1,5-pentanediol, substituted 1,5-pentanediol (such as 3-methyl-1,5-pentanediol), heptanediol, substituted heptanediol, nonanediol, substituted nonanediol, undecanediol, substituted undecanediol, tridecanediol, substituted tridecanediol, pentadecanediol, substituted 1,15-pentadecandiol, heptadecandiol, substituted heptadecandiol, nonadecandiol, substituted nonadecandiol. In some embodiments herein, component (i) includes 3-methyl-1,5-pentanediol, 1,5-pentanediol, 1,3-propylene glycol, or a combination thereof.

[0024] In one or more embodiments herein, examples of suitable component (ii) alcohols may include, but are not limited to, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, cis-1,2-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,3-cyclohexanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 4-methyl-1,2-cyclohexanedimethanol, 4-cyclopentene-1,3-diol, 4,4'-isopropylidene dicyclohexanol, 1,4-benzenedimethanol, hydroquinone bis(2-hydroxyethyl) ether, 1,2-benzenedimethanol, 1,4-bis(2-hydroxyethyl)benzene, resorcinol bis(2-hydroxyethyl) ether, terephthalic acid bis(2-hydroxyethyl ester), 2,2'-(o-phenylenedioxy)diethanol, and the like. In some embodiments herein, component (ii) includes 1,4-cyclohexanedimethanol, 4,4'-isopropyldicyclohexanol, 1,4-cyclohexanediol, 1,4-benzenedimethanol, 1,3-cyclopentanediol, 4,8-bis(hydroxymethyl)tricyclo[5.2.1.0 2,6 ]decane or a combination thereof.

[0025] Examples of TACD include 2,2,4,4-tetramethylcyclobutane-1,3-diol (TMCD), 2,2,4,4-tetraethylcyclobutane-1,3-diol, 2,2,4,4-tetra-n-propylcyclobutane-1,3-diol, 2,2,4,4-tetra-n-butylcyclobutane-1,3-diol, 2,2,4,4-tetra-n-pentylcyclobutane-1,3-diol, 2,2,4,4-tetra-n-hexylcyclobutane-1,3-diol, 2,2,4,4-tetra-n-heptylcyclobutane-1,3-diol, 2,2,4,4-tetra-n-octylcyclobutane-1,3-diol, and 2,2,4,4-tetra-n-octylcyclobutane-1,3-diol. ,3-diol, 2,2-dimethyl-4,4-diethylcyclobutane-1,3-diol, 2-ethyl-2,4,4-trimethylcyclobutane-1,3-diol, 2,4-dimethyl-2,4-diethyl-cyclobutane-1,3-diol, 2,4-dimethyl-2,4-di-n-propylcyclobutane-1,3-diol, 2,4-n-dibutyl-2,4-diethylcyclobutane-1,3-diol, 2,4-dimethyl-2,4-diisobutylcyclobutane-1,3-diol and 2,4-diethyl-2,4-diisopentylcyclobutane-1,3-diol. In one or more embodiments herein, TACD may include or be TMCD.

[0026] In the embodiments of this invention, the polyol mixture may further comprise (iv) an acyclic diol or polyol different from component (i), component (ii) and component (iii). Examples of suitable acyclic diols or polyols may include, but are not limited to, 1,2-propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,6-hexanediol, 2,2,4,4-tetramethyl-1,6-hexanediol, ethylene glycol, diethylene glycol, dipropylene glycol, tripropylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, neopentyl glycol, dimethylbutylene glycol, trimethylolpropane, 1,8-octanediol, 1,10-decanediol, etc.

[0027] In the embodiments herein, the polyol mixture may be substantially free of heterocyclic fused bicyclic polyols. As used herein, "fused" bicyclic polyols refer to alcohols with two ring structures, wherein the two rings share two carbons and a bond. Examples of fused heterocyclic bicyclic polyols may include, but are not limited to, isosorbide, bis(2-hydroxyethyl)isosorbide, benzofurandiol (e.g., 1-benzofuran-5,6-diol), substituted benzofurandiols, quinolinediols, substituted quinolonediols, etc.

[0028] In the embodiments described herein, a method for manufacturing polyester polyols is also disclosed. The method includes reacting: (a) a polyacid; and (b) a polyol mixture, the polyol mixture comprising: (i) a diol having a straight or branched hydrocarbon chain between two hydroxyls, wherein the hydrocarbon chain has an odd number of carbon atoms of 3 to 19; (ii) a polyol having a cyclic structure; and (iii) 2,2,4,4-tetraalkyl-1,3-cyclobutanediol (TACD). Polyacids and polyol mixtures are previously described herein and are incorporated by reference.

[0029] In the embodiments described herein, a method for producing polyurethane is also disclosed. The method includes reacting polyester polyol described herein with polyisocyanate. Polyurethane is obtained by this method. As used herein, "polyisocyanate" is any compound containing two or more isocyanate groups. In some embodiments, polyisocyanate can be an aliphatic isocyanate or an alicyclic isocyanate. The example of suitable aliphatic polyisocyanate can include an aliphatic polyisocyanate having 3 to 16 carbon atoms, or alternatively 4 to 12 carbon atoms in a straight or branched alkylene residue. The example of suitable alicyclic polyisocyanate can include an alicyclic polyisocyanate having 4 to 18 carbon atoms, or alternatively 6 to 15 carbon atoms in a cycloalkylene residue. Other examples of suitable aliphatic and cycloaliphatic polyisocyanates include, but are not limited to, cyclohexane diisocyanate, methyl cyclohexane diisocyanate, ethyl cyclohexane diisocyanate, propyl cyclohexane diisocyanate, methyl diethyl cyclohexane diisocyanate, propane diisocyanate, butane diisocyanate, pentane diisocyanate, hexane diisocyanate, heptane diisocyanate, octane diisocyanate, nonane diisocyanate, nonane triisocyanate such as 4-isocyanatomethyl-1,8-octane diisocyanate (TIN), decane diisocyanate and triisocyanate, undecane diisocyanate and triisocyanate, and dodecane diisocyanate and triisocyanate, isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), diisocyanatodicyclohexylmethane (DICH ... 12In some embodiments, the polyisocyanate is selected from the group consisting of polymeric methylene diphenyl diisocyanate, hexamethylene diisocyanate biuret, hexamethylene diisocyanate isocyanurate, hexamethylene diisocyanate uretdione, hexamethylene diisocyanate iminooxadiazinedione, hexamethylene diisocyanate allophanate and mixtures thereof. The polyurethane can be used in coating formulations, elastomer formulations, adhesive formulations, sealant formulations or foamable compositions.

[0030] Test Method Viscosity The viscosity of the material was measured by a Brookfield viscometer using a #27 spindle at 30° C. The viscosity is reported in centipoise (cp).

[0031] Tensile Strength Tensile strength was measured according to ASTM D412 using a 100 Newton load cell on an MTS Criterion Model 46. Tensile strength is reported in megapascals (MPa).

[0032] Hydroxyl (OH) value The hydroxyl value is measured according to ASTM E 1899. The hydroxyl value is reported in mg KOH / g.

[0033] Acid value Acid value is measured according to ASTM D 664. Acid value is reported in mg KOH / g.

[0034] Compatibility with polyether and polybutadiene polyols The compatibility of example polyester polyols with polyether and polybutadiene polyols is further described below.

[0035] Example The following specific examples are given to illustrate the methods and properties associated with polyester polyols. Inventive and Comparative Examples The details of the formulations are provided below and the results are provided in Tables 1-3.

[0036] Table 1 – Raw materials

[0037] Embodiment 1 of the present invention In a four-neck 5-liter glass reactor equipped with a mechanical stirrer, a thermocouple, a heated partial condenser (100°C), a Dean-Stark trap, a cooled condenser (15°C) and a nitrogen inlet, 2072.70 grams of dodecanedioic acid, 893.37 grams of 3-methyl-1,5-pentanediol, 311.47 grams of 1,4-cyclohexanedimethanol, 155.74 grams of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 3.43 grams of IRGAFOS™ 168 and 3.43 grams of WESTON™ 618F were loaded. The reactor was placed in a heating jacket connected to a temperature controller. With nitrogen turned on, the mixture in the reactor was slowly heated to 110°C. Once the mixture melted, stirring was applied at 200 rpm. With stirring under a nitrogen purge, the mixture was heated to 230°C at a ramp rate of 0.2°C / minute. The mixture was further reacted at 230°C under a nitrogen blanket. Samples were taken after 6 hours at 230°C for acid value analysis. If the acid value was greater than 1.0 mg KOH / g, the reaction was allowed to continue until the acid value of the reaction mixture reached less than or equal to 1.0 mg KOH / g. The resulting material was a clear liquid at room temperature with a viscosity of 6300 cp at 30°C. The hydroxyl value and acid value of the material were found to be 54 mg KOH / g and 0.9 mgKOH / g, respectively.

[0038] Embodiment 2 of the present invention Example 1 was repeated except that 2072.70 g of dodecanedioic acid, 730.78 g of 1,5-pentanediol, 155.74 g of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 389.34 g of 1,4-cyclohexanedimethanol, 3.35 g of IRGAFOS™ 168 and 3.35 g of WESTON™ 618F were charged to the reactor. After the reaction was complete, the finished product was a clear liquid at room temperature with a viscosity of 5800 cp at 30°C. The hydroxyl value and acid value of the material were found to be 57 mg KOH / g and 0.6 mg KOH / g, respectively.

[0039] Comparative Example A Example 1 was repeated except that 1842.40 grams of dodecanedioic acid, 1171.16 grams of 1.10-decanediol, 138.43 grams of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 276.86 grams of 1,4-cyclohexanedimethanol, 3.43 grams of IRGAFOS™ 168 and 3.43 grams of WESTON™ 618F were charged to the reactor. After the reaction was complete, the finished product was solid at room temperature. The hydroxyl value and acid value of the material were found to be 44 mg KOH / g and 1.0 mg KOH / g, respectively. Since the material was solid at room temperature, it was not suitable for room temperature processing (a key processing feature of the present invention). No further evaluation of the composition was performed.

[0040] Embodiment 3 of the present invention Example 1 was repeated except that 2022.50 g of sebacic acid, 874.44 g of 1,5-pentanediol, 173.04 g of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 346.08 g of 1,4-cyclohexanedimethanol, 3.42 g of IRGAFOS™ 168 and 3.42 g of WESTON™ 618F were charged to the reactor. After the reaction was complete, the finished product was a clear liquid at room temperature with a viscosity of 4825 cp at 30°C. The hydroxyl value and acid value of the material were found to be 60 mg KOH / g and 0.5 mg KOH / g, respectively.

[0041] Comparative Example B Example 1 was repeated except that 2022.50 grams of sebacic acid, 850.90 grams of 1,6-hexanediol, 86.52 grams of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 605.64 grams of 1,4-cyclohexanedimethanol, 3.57 grams of IRGAFOS™ 168 and 3.57 grams of WESTON™ 618F were charged to the reactor. After the reaction was complete, the finished product was solid at room temperature. The hydroxyl value and acid value of the material were found to be 65 mg KOH / g and 1.0 mg KOH / g, respectively. Since the material was solid at room temperature, it was not suitable for room temperature processing (a key processing feature of the present invention). No further evaluation of the composition was performed.

[0042] Comparative Example C Example 1 was repeated except that 910.13 g of sebacic acid, 638.12 g of 3-methyl-1,5-pentanediol, 1.55 g of IRGAFOS™ 168, and 1.55 g of WESTON™ 618F were charged to the reactor. After the reaction was complete, the finished product was a liquid at room temperature with a viscosity of 2530 cp at 30°C. The hydroxyl value and acid value of the material were found to be 64 mg KOH / g and 1.0 mg KOH / g, respectively. The material was suitable for room temperature processing, and the thermal and hydrolytic stability were further evaluated.

[0043] Embodiment 4 of the present invention Example 1 was repeated except that 1753.20 g of adipic acid, 1040.58 g of 1,5-pentanediol, 205.9 g of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 411.84 g of 1,4-cyclohexanedimethanol, 3.41 g of IRGAFOS™ 168 and 3.41 g of WESTON™ 618F were charged to the reactor. After the reaction was complete, the finished product was a clear liquid at room temperature with a viscosity of 5180 cp at 30°C. The OH and acid values ​​of the material were found to be 61 mg KOH / g and 0.8 mg KOH / g, respectively.

[0044] Comparative Example D Example 1 was repeated except that 1753.20 grams of adipic acid, 995.55 grams of 1,6-hexanediol, 101.23 grams of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 708.60 grams of 1,4-cyclohexanedimethanol, 3.56 grams of IRGAFOS™ 168 and 3.56 grams of WESTON™ 618F were charged to the reactor. After the reaction was complete, the finished product was solid at room temperature. The hydroxyl value and acid value of the material were found to be 65 mg KOH / g and 1.0 mg KOH / g, respectively. Since the material was solid at room temperature, it was not suitable for room temperature processing (a key processing feature of the present invention). No further evaluation of the composition was performed.

[0045] Comparative Example E Example 1 was repeated except that 774.33 g of adipic acid, 739.04 g of 3-methyl-1,5-pentanediol, 1.51 g of IRGAFOS™ 168, and 1.51 g of WESTON™ 618F were charged to the reactor. After the reaction was complete, the finished product was a liquid at room temperature with a viscosity of 4150 cp at 30°C. The hydroxyl value and acid value of the material were found to be 54 mg KOH / g and 0.8 mg KOH / g, respectively. The material was suitable for room temperature processing, and the thermal and hydrolytic stability were further evaluated.

[0046] Embodiment 5 of the present invention Example 1 was repeated except that 774.33 g of adipic acid, 147.81 g of 3-methyl-1,5-pentanediol, 45.09 g of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 315.64 g of 1,4-cyclohexanedimethanol, 369.55 g of 1,6-hexanediol, 1.58 g of IRGAFOS™ 168, and 1.58 g of WESTON™ 618F were charged to the reactor. After the reaction was complete, the finished product was a clear liquid at room temperature with a viscosity of 7100 cp at 30°C. The hydroxyl value and acid value of the material were found to be 62 mg KOH / g and 1.0 mg KOH / g, respectively. In contrast to Comparative Example D, the addition of 3-methyl-1,5-pentanediol to the composition resulted in a low viscosity liquid at room temperature.

[0047] Embodiment 6 of the present invention Example 1 was repeated except that 730.50 g of adipic acid, 277.70 g of 3-methyl-1,5-pentanediol, 42.36 g of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 254.15 g of 1,4-cyclohexanedimethanol, 255.97 g of 1,10-decanediol, 1.58 g of IRGAFOS™ 168, and 1.58 g of WESTON™ 618F were charged to the reactor. After the reaction was complete, the finished product was a clear liquid at room temperature with a viscosity of 7600 cp at 30°C. The hydroxyl value and acid value of the material were found to be 65 mg KOH / g and 1.1 mg KOH / g, respectively. In contrast to Comparative Example D, the addition of 3-methyl-1,5-pentanediol to the composition resulted in a low viscosity liquid at room temperature.

[0048] Compatibility with polybutadiene and polyether polyols In order to examine the compatibility of the inventive examples and comparative examples with polybutadiene polyols and polyether polyols, the inventive examples and comparative examples were mixed with KRASOL™ LBH 2000 (2,000 Mw polybutadiene polyol) and VORANOL™ 220-056N (2,000 Mw polyether polyol) in a weight ratio of 50:50, respectively. The mixture was thoroughly mixed manually by a spatula. After conditioning at room temperature for 8 hours, the appearance of the mixture was visually inspected. A mixture that was transparent to the naked eye was considered compatible, while a mixture that was turbid to the naked eye was considered incompatible. Tables 2 and 3 summarize the results of the compatibility study.

[0049] Table 2 - Examples of the present invention Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Dodecanedioic acid 2072.7 (100 mol%) 2187.85 (100 mol%) Sebacic acid 2022.5 (100 mol%) Adipic acid 1753.2 (100 mol%) 774.33 (100 mol%) 730.5 (100 mol%) 3-Methyl-1,5-pentanediol 893.37 (60 mol%) 147.81 (20 mol%) 277.7 (40 mol%) 1,5-Pentanediol 830.72 (70 mol%) 874.44 (70 mol%) 1040.58 (70 mol%) 1,4-Cyclohexanedimethanol 311.47 (30 mol%) 410.97 (25 mol%) 346.08 (20 mol%) 411.84 (20 mol%) 270.55 (30 mol%) 254.15 (30 mol%) 2,2,4,4-Tetramethyl-1,3-cyclobutanediol 155.74 (10 mol%) 82.19 (5 mol%) 173.04 (10 mol%) 205.9 (10 mol%) 45.09 (5 mol%) 42.36 (5 mol%) 1,6-Hexanediol 332.59 (45 mol%) 1,10-Decanediol 255.97 (25 mol%) IRGAFOS™ 168 3.43 3.35 3.42 3.41 1.58 1.58 WESTON™ 618F 3.43 3.35 3.42 3.41 1.58 1.58 OH / COOH ratio 1.2 1.2 1.2 1.19 1.17 1.18 Hydroxyl value 54.0 57.0 60.0 61.0 62.0 65.0 Acid value 0.9 0.6 0.5 0.8 1.0 1.0 Appearance at 30°C liquid liquid liquid liquid liquid liquid Viscosity at 30°C, cp 6300 5800 4825 5180 7100 7600 Compatibility with polybutadiene polyols yes yes no no no no Compatibility with polyether polyols yes yes yes yes yes yes

[0050] Table 3 - Comparative Examples Comparative Example A Comparative Example B Comparative Example C Comparative Example D Comparative Example E Dodecanedioic acid 1842.4 (100 mol%) Sebacic acid 2022.5 (100 mol%) 910.13 (100 mol%) Adipic acid 1753.2 (100 mol%) 774.33 (100 mol%) 3-Methyl-1,5-pentanediol 638.12 (100 mol%) 739.04 (100 mol%) 1,5-Pentanediol 1,4-Cyclohexanedimethanol 276.86 (20 mol%) 605.64 (35 mol%) 708.6 (35 mol%) 2,2,4,4-Tetramethyl-1,3-cyclobutanediol 138.43 (10 mol%) 86.52 (5 mol%) 101.23 (5 mol%) 1,6-Hexanediol 850.9 (60 mol%) 995.55 (60 mol%) 1,10-Decanediol 1171.16 (70 mol%) IRGAFOS™ 168 3.43 3.57 1.55 3.56 1.51 WESTON™ 618F 3.43 3.57 1.55 3.56 1.51 OH / COOH ratio 1.2 1.2 1.2 1.17 1.18 Hydroxyl value 44.0 65.0 64.0 65.0 54.0 Acid value 1.0 1.0 1.0 1.0 0.8 Appearance at 30°C solid solid liquid solid liquid Viscosity at 30°C, cp NA NA 2530 NA 4150 Compatibility with polybutadiene polyols no no no no no Compatibility with polyether polyols no no no no no

[0051] As shown in the table above, the formulations of the present invention exhibit low viscosity at 30°C and improved compatibility with polybutadiene polyol or polyether polyol compared to the comparative examples.

[0052] The dimensions and values ​​disclosed herein should not be understood as being strictly limited to the exact numerical values ​​recited. Instead, unless otherwise indicated, each such dimension is intended to mean the recited value and a functionally equivalent range around that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm".

[0053] Unless expressly excluded or otherwise limited, each document cited herein, if any, including any cross-referenced or related patents or applications and any patent applications or patents to which this application claims priority or the benefit of, is hereby incorporated by reference in its entirety. The citation of any document is not an admission that it is prior art with respect to any invention disclosed or claimed herein, nor is it an admission that it alone or in any combination with any other reference or references teaches, suggests or discloses any such invention. In addition, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall prevail.

[0054] Although specific embodiments of the present invention have been illustrated and described, it will be apparent to those skilled in the art that various other changes and modifications may be made without departing from the spirit and scope of the present invention. Therefore, it is intended to cover all such changes and modifications within the scope of the present invention in the appended claims.

Claims

1. A polyester polyol comprising structural units derived from: (a) polyacids; and (b) a polyol mixture, the polyol mixture comprising: (i) a diol having a linear or branched hydrocarbon chain between two hydroxyl groups, wherein the hydrocarbon chain has an odd number of carbon atoms from 3 to 19; (ii) a polyol having a cyclic structure; and (iii) 2,2,4,4-Tetraalkyl-1,3-cyclobutanediol (TACD).

2. The polyester polyol of claim 1, wherein the polyol mixture comprises 20 to 80 mol % of component (i), 15 to 35 mol % of component (ii), and 5 to 20 mol % of component (iii), wherein the mol % are based on the total polyol mixture.

3. The polyester polyol according to claim 1 or 2, wherein component (i) comprises 3-methyl-1,5-pentanediol, 1,5-pentanediol, 1,3-propylene glycol or a combination thereof.

4. The polyester polyol according to claim 1-3, wherein component (ii) comprises 1,4-cyclohexanedimethanol, 4,4'-isopropyldicyclohexanol, 1,3-cyclopentanediol, 1,4-cyclohexanediol, 1,4-benzenedimethanol, 4,8-bis(hydroxymethyl)tricyclo[5.2.1.0 2,6 ]decane or a combination thereof.

5. The polyester polyol according to claims 1 to 4, wherein the polyol mixture further comprises (iv) an acyclic diol or polyol different from component (i), component (ii) and component (iii).

6. The polyester polyol of claims 1-5, wherein the polyol mixture is substantially free of fused heterocyclic, bicyclic polyols.

7. The polyester polyol according to claims 1-6, wherein the polyacid is selected from the group consisting of adipic acid, sebacic acid, dodecanedioic acid, azelaic acid, succinic acid, glutaric acid, pimelic acid, suberic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, naphthalene dicarboxylic acid, phthalic anhydride, hexahydrophthalic anhydride, and combinations thereof.

8. The polyester polyol according to claims 1-7, wherein the molar ratio of the polyol mixture to the polyacid is 1.4:1 to 1.01:

1.

9. A method for the manufacture of polyester polyols, comprising: (a) polyacids; and (b) a polyol mixture, the polyol mixture comprising: (i) a diol having a linear or branched hydrocarbon chain between two hydroxyl groups, wherein the hydrocarbon chain has an odd number of carbon atoms from 3 to 19; (ii) polyols having a cyclic structure; and (iii) 2,2,4,4-tetraalkyl-1,3-cyclobutanediol (TACD) to form a polyester polyol.

10. The method of claim 9, wherein the polyol mixture comprises 20 to 80 mol% of component (i), 15 to 35 mol% of component (ii), and 5 to 20 mol% of component (iii), wherein the mol% are based on the total polyol mixture.

11. The method of claims 9-10, wherein component (i) comprises 3-methyl-1,5-pentanediol, 1,5-pentanediol, 1,3-propylene glycol, or a combination thereof.

12. The method according to claims 9-11, wherein component (ii) comprises 1,4-cyclohexanedimethanol, 4,4'-isopropyldicyclohexanol, 1,3-cyclopentanediol, 1,4-cyclohexanediol, 1,4-benzenedimethanol, 4,8-bis(hydroxymethyl)tricyclo[5.2.1.0 2,6 ]decane or a combination thereof.

13. The method of claims 9-12, wherein the polyol mixture further comprises (iv) an acyclic diol or polyol different from component (i), component (ii) and component (iii).

14. The method of claims 9-13, wherein the polyol mixture is substantially free of fused heterocyclic bicyclic polyols.

15. The method of claims 9-14, wherein the polyacid is selected from the group consisting of adipic acid, sebacic acid, dodecanedioic acid, azelaic acid, succinic acid, glutaric acid, pimelic acid, suberic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, naphthalene dicarboxylic acid, phthalic anhydride, hexahydrophthalic anhydride, and combinations thereof.

16. The method of claims 9-15, wherein the molar ratio of the polyol mixture to the polyacid is from 1.4:1 to 1.01:

1.

17. A process for producing polyurethane, the process comprising reacting the polyester polyol according to claims 1 to 8 with a polyisocyanate.

18. The method of claim 17, wherein the polyisocyanate is selected from the group consisting of polymeric methylene diphenyl diisocyanate, hexamethylene diisocyanate biuret, hexamethylene diisocyanate isocyanurate, hexamethylene diisocyanate uretdione, hexamethylene diisocyanate iminooxadiazinedione, hexamethylene diisocyanate allophanate, and mixtures thereof.

19. A polyurethane obtained by the method according to claim 17 or 18.

20. Use of the polyurethane according to claim 19 in a coating formulation, an elastomer formulation, an adhesive formulation, a sealant formulation or a foamable composition.

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