Polycaprolactone polyols, polyurethanes, and methods of making and using same

Abstract

A caprolactone polyol and a polyurethane material or adhesive comprising the caprolactone polyol are described herein. The caprolactone polyol is prepared by mixing an initiator and a caprolactone monomer to form an initiator-caprolactone mixture or a reaction mixture; adding a catalyst to the initiator-caprolactone mixture to form a reaction mixture; and polymerizing the caprolactone monomer in the reaction mixture, thereby forming the caprolactone polyol, where the initiator includes a hydroquinone bis (2-hydroxyethyl) ether, a dodecane glycol, a penta-spirodiol, or a combination thereof. The polyurethane materials or adhesives described herein have reduced open time while having reduced viscosity, improved adhesion, and improved tensile strength as compared to caprolactone polyols prepared without the use of initiators of the present disclosure. Also described herein are methods of making and using the caprolactone polyol and the polyurethane material or adhesive.

Description

[0001] Cross-reference to related applications

[0002] This application claims priority to and the benefit of U.S. Provisional Application No. 63 / 484,265, filed on February 10, 2023, and U.S. Provisional Application No. 63 / 490,692, filed on March 16, 2023, each of which is incorporated herein by reference in its entirety for all purposes. Technical Field

[0003] The present disclosure relates to caprolactone polyols, compositions including the disclosed caprolactone polyols, such as polyurethane compositions and adhesives (e.g., hot melt adhesives and reactive hot melt adhesives), and methods for making and using caprolactone polyols and compositions containing the same. Background Art

[0004] Reactive hot melt adhesives (RHMA) are a key subsegment of the adhesives market, with a projected market size of USD 1.8 billion by 2025. Typical end-use applications for RHMAs include flat lamination (bonding wood to decorative substrates), flooring construction (e.g., cork, nonwoven fabrics, various plastics, etc.), edge tape, and binding.

[0005] RHMA is a component of polyurethane adhesive formulations, typically formulated to have an excess of 1-5% monomeric isocyanate (NCO), but more commonly an excess NCO content of 2-3%. Depending on the final application, the adhesive is applied at about 120°C to about 160°C (e.g., about 120°C to about 130°C) through a hot melt dispensing gun or nozzle connected to a melting tank. As the adhesive cools from the elevated temperature to ambient temperature, the crystallization rate controls the initial adhesive strength (commonly referred to as green strength), and the cure rate dictates the "open time" of the adhesive. The open time is the period from application of the adhesive to a substrate to the point at which bonding to a second substrate is impossible.

[0006] After physical cooling and the resulting curing of the adhesive, a secondary moisture cure mechanism occurs when the excess NCO content of the adhesive formulation reacts with moisture to convert the polymer into a thermoset. NCO reacts with moisture to form carbamic acid, which, in turn, emits CO2 to convert to amines. The amines further react with NCO to form urea bonds.

[0007] Adhesives made with alternatives to polyester polyols, such as current caprolactone-based polyol chemistries, have significantly longer open times compared to polyester polyols. Therefore, the adhesive market needs alternatives to currently available polyester polyols and caprolactone polyols.

[0008] Polyurethane materials or adhesives are formed by reacting a hydroxyl-containing moiety (polyol) with an isocyanate-functional material. The structure of a polyurethane is segmented and can be described in terms of hard domains / segments and soft domains / segments. In the case of reactive hot melt adhesives (RHMAs), the hard domains containing isocyanate molecules are typically dimethylmethane-4,4'-diisocyanate (MDI), and the soft domains are controlled by the chemistry of the polyol, which is typically a polyether, polyester, or caprolactone-based polyol.

[0009] RHMA is typically produced by adding polyols to a reactor and drying them to remove residual moisture from the product. Subsequently, MDI is added to the polyols and reacted under vacuum to achieve the final polyurethane prepolymer with the desired excess NCO content.

[0010] The adhesive is applied to a first substrate at an elevated temperature (about 120°C to about 130°C), and then a second substrate is contacted with the adhesive to bond the article. The bonding mechanism is driven in two parts, where the initial bond strength (first part) is controlled by the physical cooling of the adhesive, and the overall properties of the adhesive (second part) are determined by the reaction between the excess isocyanate and the moisture present in the environment.

[0011] Therefore, there remains a need in the art for alternatives to polyester polyols and current caprolactone polyols that provide good / acceptable open time, viscosity, adhesion, and tensile strength. The present disclosure describes novel caprolactone polyols that surprisingly and unexpectedly provide polyurethane materials or adhesives (such as RHMA) having reduced open time, reduced viscosity, improved adhesion, and improved tensile strength compared to caprolactone polyols prepared without the initiators of the present disclosure. The present disclosure further provides polyurethane compositions or adhesives comprising the caprolactone polyols of the present disclosure, as well as methods for preparing the caprolactone polyols of the present disclosure and the polyurethane compositions or adhesives of the present disclosure. Summary of the Invention

[0012] The present invention describes a multifunctional polyol resin, a curable composition comprising the multifunctional polyol resin, a polyurethane resin and a melamine-based resin derived from the multifunctional polyol resin, a method for preparing the same and uses thereof.

[0013] Thus, in one aspect, the present disclosure provides a caprolactone polyol prepared by a method comprising: mixing an initiator and a caprolactone monomer to form an initiator-caprolactone mixture or reaction mixture; adding a catalyst (e.g., a stannous octoate catalyst such as T-9) to the initiator-caprolactone mixture to form a reaction mixture; and polymerizing (e.g., ring-opening polymerization) the caprolactone monomer in the reaction mixture to form the caprolactone polyol, wherein the initiator comprises hydroquinone bis(2-hydroxyethyl) ether, dodecanediol (e.g., 1,12-dodecanediol), pentaspiroglycol, or a combination thereof.

[0014] Another aspect of the present disclosure provides a method for preparing the caprolactone polyol of the present disclosure. The method comprises: mixing an initiator and a caprolactone monomer to form an initiator-caprolactone mixture or reaction mixture; adding a catalyst (e.g., a stannous octoate catalyst such as T-9) to the initiator-caprolactone mixture to form a reaction mixture; and polymerizing (e.g., ring-opening polymerization) the caprolactone monomer in the reaction mixture to form the caprolactone polyol, wherein the initiator comprises hydroquinone bis(2-hydroxyethyl) ether, dodecanediol (e.g., 1,12-dodecanediol), pentaspirodiol, or a combination thereof.

[0015] In any aspect or embodiment described herein, the method further comprises: (i) withdrawing the initiator-caprolactone mixture prior to adding the catalyst (e.g., bubbling the initiator-caprolactone mixture with nitrogen); (ii) incubating the initiator-caprolactone mixture prior to adding the catalyst (e.g., incubating for about 0.5 hours to about 1.5 hours, about 0.75 hours to about 1.25 hours, or about 1 hour, such as when exciting the initiator-caprolactone mixture); (iii) heating the initiator-caprolactone mixture to about 70°C to about 100°C (e.g., about 75°C to about 95°C); or (iii) a combination thereof.

[0016] In any aspect or embodiment described herein, the polymerization is carried out: (i) at reflux; (ii) at about 150°C to about 190°C (e.g., about 150°C to about 180°C); (iii) for about 4 hours to about 6 hours; or (iv) a combination thereof.

[0017] In any aspect or embodiment described herein, the method further comprises adding an additional catalyst (e.g., a stannous octoate catalyst such as T-9) to the reaction mixture (e.g., adding the additional catalyst while heating the reaction mixture, such as heating to about 150°C to about 190°C, such as about 150°C to about 160°C), thereby forming the caprolactone polyol.

[0018] In any aspect or embodiment described herein, the initiator-caprolactone mixture further comprises an antioxidant and / or stabilizer (e.g., a phenolic antioxidant and / or stabilizer, a sterically hindered phenolic antioxidant and / or stabilizer, pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) ( 1010), phosphite antioxidants and / or stabilizers, bis(2,4-di-tert-butylphenol) pentaerythritol diphosphate (such as 126) Anti-hydrolysis agent ( 1), acid scavenger ( I), carbodiimide (such as monomeric carbodiimide) or a combination thereof).

[0019] In any aspect or embodiment described herein, at least one of the following is true: the caprolactone monomer is present in an amount of about 85 wt % to about 98 wt % (e.g., about 90 wt % to about 97 wt %, about 93 wt % to about 97 wt %, or about 95 wt %) of the initiator-caprolactone mixture; the initiator is present in an amount of about 2 wt % to about 15 wt % (e.g., about 3 wt % to about 10 wt %, about 3 wt % to about 7 wt %, or about 5 wt %) of the initiator-caprolactone mixture; the caprolactone monomer is present in an amount of about 85 wt % to about 98 wt % (e.g., about 90 wt % to about 97 wt %, about 93 wt % to about 97 wt %, or about 95 wt %) of the reaction mixture. 7 wt %, about 93 wt % to about 97 wt % or about 95 wt %) of the reaction mixture; the initiator is present in an amount of about 2 wt % to about 13 wt % (e.g., about 3 wt % to about 10 wt %, about 3 wt % to about 7 wt % or about 5 wt %) of the reaction mixture; the catalyst is present in an amount of about 0.001 wt % to about 5 wt % (e.g., about 0.001 wt % to about 5 wt %, about 0.001 wt % to about 4 wt %, about 0.001 wt % to about 3 wt %, about 0.001 wt % to about 2 wt %, about 0.001 wt % to about 1 wt %, about 0.001 wt % to about About 0.5 wt%, about 0.001 wt% to about 0.25 wt%, about 0.1 wt% to about 5 wt%, about 0.1 wt% to about 4 wt%, about 0.1 wt% to about 3 wt%, about 0.1 wt% to about 2 wt%, about 0.1 wt% to about 1 wt%, about 0.1 wt% to about 0.5 wt%, about 0.1 wt% to about 0.25 wt%, about 0.2 wt% to about 5 wt%, about 0.2 wt% to about 4 wt%, about 0.2 wt% to about 3 wt%, about 0.2 wt% to about 2 wt%, about 0.2 wt% to about 1 wt%, about 0.2 wt% to about 0.5 wt%, about 0.5 wt% to about 5wt%, about 0.5wt% to about 4wt%, about 0.5wt% to about 3wt%, about 0.5wt% to about 2wt%, about 0.5wt% to about 1wt%, about 0.75wt% to about 5wt%, about 0.75wt% to about 4wt%, about 0.75wt% to about 3wt%, about 0.75wt% to about 2wt%, about 0.75wt% to about 1wt%, about 1wt% to about 5wt%, about 1wt% to about 4wt%, about 1wt% to about 3wt%, about 1wt% to about 2wt%, about 1.5wt% to about 5wt%, about 1.5wt% to about 4wt%, about 1.5 wt % to about 3 wt %, about 2 wt % to about 5 wt %, about 2 wt % to about 4 wt %, about 2 wt % to about 3 wt %, about 3 wt % to about 5 wt %, about 3 wt % to about 4 wt %, or about 4 wt % to about 5 wt %); the antioxidant or stabilizer is present in an amount of up to about 2 wt % (e.g., up to about 1.5 wt %, up to about 1 wt %, up to about 0.5 wt %, up to about 0.25 wt %, about 0.1 wt % to about 2 wt %, about 0.1 wt % to about 1.5 wt %, about 0.1 wt % to about 1 wt %, about 0.1 wt % to about 0.75 wt %, about 0.1 wt % to about 0.5 wt %, or about 0.1 wt % to about 0.25 wt %) of the reaction mixture; or a combination thereof.

[0020] In any aspect or embodiment described herein, the caprolactone polyol has a molecular weight of about 2,000 g / mol (MW) to about 4500 MW (eg, about 2,000 MW to about 4,000 MW or about 3,500 MW to about 4,000 MW).

[0021] In any aspect or embodiment described herein, the caprolactone polyol comprises less than about 5% (e.g., less than about 4%, less than about 3%, less than about 2%, less than about 1%, less than about 0.5%, less than about 0.5%, less than about 0.25%, less than about 0.1%) caprolactone monomer.

[0022] In any aspect or embodiment described herein, at least one of the following is true: the catalyst is a catalyst for ring-opening polymerization (e.g., zinc lactate, zinc oxide, zinc powder, diethyl zinc, tin lactate, tin oxide, tin dioxide, stannous oxide, stannous lactate, stannous octoate, stannous chloride, tin powder, propionic acid, or tetrabutyl titanate, or a combination thereof).

[0023] Another aspect of the present disclosure provides a polyurethane material or adhesive (e.g., a polyurethane material or adhesive based on caprolactone polyol), which is prepared by a method comprising reacting the caprolactone polyol of the present disclosure with an isocyanate (e.g., a diisocyanate or a polyisocyanate) containing two or more isocyanate groups, thereby forming the polyurethane material.

[0024] Another aspect of the present disclosure provides a method for preparing the polyurethane material or adhesive of the present disclosure. The method comprises reacting the caprolactone polyol of the present disclosure with an isocyanate (e.g., a diisocyanate or a polyisocyanate) containing two or more isocyanate groups to form the polyurethane material.

[0025] In any aspect or embodiment described herein, the method further comprises: (i) heating the caprolactone polyol and / or the isocyanate (e.g., to about 70°C to about 100°C, about 80°C to about 90°C, about 82°C to about 88°C, or about 85°C) prior to reacting with the isocyanate; (ii) drying the polyurethane material or adhesive; (iii) bubbling the caprolactone polyol prior to reacting (e.g., bubbling with nitrogen and / or bubbling for about 0.5 hours to about 1.5 hours, about 0.75 hours to about 1.25 hours, or about 1 hour); or (iv) a combination thereof.

[0026] In any aspect or embodiment described herein, reacting the caprolactone polyol and the isocyanate is carried out: (i) under bubbling (e.g., bubbling with nitrogen); (ii) under heating (e.g., reacting the caprolactone polyol and the isocyanate at 100°C to about 150°C (e.g., about 110°C to about 140°C, 115°C to about 135°C, or 120°C to 130°C); (iii) for about 1.0 hour to about 3.0 hours (e.g., about 1.25 hours to about 2.75 hours, about 1.5 hours to about 2.5 hours, about 1.75 hours to about 1.25 hours, or about 2.0 hours); or (iv) a combination thereof.

[0027] In any aspect or embodiment described herein, at least one of the following is true: (i) the isocyanate is a monomer, oligomer, polymer, or a mixture thereof; (ii) the catalyst is a urethane catalyst (e.g., a tertiary amine compound, an amine having an isocyanate-reactive group, an organometallic compound, or a mixture thereof); or (iii) a combination thereof.

[0028] In any aspect or embodiment described herein, the isocyanate comprises 2,2'-methylenediphenyl diisocyanate; 2,4'-methylenediphenyl diisocyanate; 4,4'-methylenediphenyl diisocyanate (MDI); 3,3'-dimethyl-4,4'-diphenylidene diisocyanate (TODI); toluene diisocyanate (TDI); polymeric MDI; modified liquid 4,4'-methylenediphenyl diisocyanate; hexamethylene diisocyanate ("HDI"); 4,4'-dicyclohexylmethane diisocyanate ("HDI"); 12MDI”); isophorone diisocyanate (“IPDI”); p-phenylene diisocyanate (“PPDI”); m-phenylene diisocyanate (“MPDI”); tetramethylene diisocyanate; dodecane diisocyanate; octamethylene diisocyanate; decamethylene diisocyanate; cyclobutane-1,3-diisocyanate; 1,2-cyclohexane diisocyanate; 1,3-cyclohexane diisocyanate; 1,4-cyclohexane diisocyanate; 2,4-methylcyclohexane diisocyanate; 2,6-methylcyclohexane diisocyanate; 4,4′-dicyclohexyl diisocyanate; 2,4′-dicyclohexyl diisocyanate; 1,3,5-cyclohexane triisocyanate; isocyanato-methylcyclohexane isocyanate; isocyanatoethylcyclohexane isocyanate; bis(isocyanatomethyl)-cyclohexane diisocyanate; 4,4'-bis(isocyanatomethyl)dicyclohexane; 2,4'-bis(isocyanatomethyl)dicyclohexane; isophorone diisocyanate; 2,4-hexahydrotoluene diisocyanate; 2,6-hexahydrotoluene diisocyanate; 1,2-phenylene diisocyanate; 1,3-phenylene diisocyanate; 1,4-phenylene diisocyanate; triphenylmethane-4,4',4"-triisocyanate; naphthylene-1,5-diisocyanate; 2,4'-biphenyl diisocyanate; 4,4'-biphenyl diisocyanate; 2,2-biphenyl diisocyanate; polyphenyl polymethylene polyisocyanate ("PMDI"); m-tetramethylxylene diisocyanate ("m-TMXDI"); p-tetramethylxylene diisocyanate ("p-TMXDI"); or mixtures thereof.

[0029] In any aspect or embodiment described herein, the isocyanate comprises dimethylmethane-4,4'-diisocyanate (MDI).

[0030] In any aspect or embodiment described herein, the catalyst is: (i) a tertiary amine catalyst (e.g., a tertiary amine catalyst present in an amount of about 0.02 wt% to about 5 wt% of the reaction mixture) comprising triethylenediamine, N-methylmorpholine, N,N-dimethylcyclohexylamine, pentamethyldiethylenetriamine, tetramethylethylenediamine, bis(dimethylaminoethyl)ether, 1-methyl-4-dimethylaminoethyl-piperazine, 3-methoxy-N-dimethylpropylamine, N-ethylmorpholine; dimethylethanolamine, N-cocomorpholine, N,N-dimethyl-N',N'-dimethylisopropylpropylenediamine, N,N-diethyl (ii) an organometallic catalyst (e.g., an organometallic catalyst present in an amount of about 0.001 wt % to 1 wt % of the reaction mixture), the organometallic catalyst comprising an organobismuth, an organomercury, an organolead, an organoferric, an organotin catalyst, or a combination thereof (preferably, an organotin catalyst); (iii) a tin catalyst comprising stannous chloride, a tin carboxylate (e.g., dibutyltin dilaurate), stannous octoate, or a combination thereof; (iv) a catalyst comprising an alkali metal alkoxide, the catalyst being used to trimerize a polyisocyanate; or (v) a combination thereof.

[0031] In any aspect or embodiment described herein, the reactive polyurethane material or adhesive has an excess NCO (cyanate ester) content of at least about 1% (e.g., about 1% to about 5%, about 1% to about 4%, about 1% to about 3%, about 1% to about 2%, about 2% to about 5%, about 2% to about 4%, about 2% to about 3%, about 3% to about 5%, or about 4% to about 5%).

[0032] In any aspect or embodiment described herein, the polyurethane material is an adhesive (eg, a hot melt adhesive) or a polyurethane reactive adhesive (eg, a reactive hot melt adhesive).

[0033] Another aspect of the present disclosure provides a method of bonding a first substrate and a second substrate, the method comprising: applying the polyurethane material of the present invention to the first substrate, the second substrate, or the first substrate and the second substrate; and contacting the first substrate and the second substrate with the polyurethane material located therebetween.

[0034] In any aspect or embodiment described herein, the method further comprises: (i) applying pressure to the contacted first and second substrates; (ii) incubating the contacted first and second substrates; or (iii) a combination thereof.

[0035] The aforementioned general practical areas are given for illustrative purposes only and are not intended to limit the scope of the present disclosure and the appended claims. Based on the claims, description, and examples of the present invention, those skilled in the art will understand the additional objects and advantages associated with the compositions, methods, and processes of the present disclosure. For example, the various aspects and embodiments of the present disclosure can be utilized in numerous combinations, all of which are explicitly contemplated by the present disclosure. These additional advantageous objects and embodiments are explicitly included within the scope of the present disclosure. Publications and other materials herein that are used to illustrate the background of the present invention and to provide additional details about practice in certain circumstances are incorporated by reference. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] The accompanying drawings, which are incorporated into and constitute a part of this specification, illustrate several embodiments of the present disclosure and, together with the description, serve to explain the principles of the present disclosure. The accompanying drawings are only for the purpose of illustrating the embodiments of the present disclosure and are not to be construed as limiting the present disclosure. Further objects, features, and advantages of the present disclosure will become apparent from the following detailed description made in conjunction with the accompanying drawings, which show illustrative embodiments of the present disclosure.

[0037] Figure 1 : Open time measurement of an exemplary reactive hot melt adhesive formulated to 3% excess NCO. Times are shown in minutes and seconds.

[0038] Figure 2 : Fmax (N / mm) for each adhesive tested on aluminum, polycarbonate and beech wood 2 ) Lap shear adhesion.

[0039] Figure 3 : Viscosity of different adhesives measured by Brookfield using spindle 27 (mPa·s).

[0040] Figure 4 : For each adhesive examined, the tensile strength Fmax (N / mm 2 ). DETAILED DESCRIPTION

[0041] The present disclosure will now be described more fully below, but not all embodiments of the present disclosure are shown. Although the present disclosure has been described in conjunction with exemplary embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the present disclosure. In addition, many modifications may be made to adapt specific structures or materials to the teachings of the present disclosure without departing from the substantive scope of the present disclosure.

[0042] Where a range of values ​​is provided, it is understood that each intermediate value between the upper and lower limits of the range, as well as any other stated or intermediate values ​​in the stated range, is encompassed within the present invention. The upper and lower limits of these smaller ranges may independently be included in smaller ranges and also encompassed within the present invention, subject to any specifically excluded limits within the stated range. Where the stated range includes one or both of the limits, ranges excluding either or both of the included limits are also encompassed within the present disclosure.

[0043] The following terms are used to describe the present invention. Where a term is not specifically defined herein, that term is given the art-recognized meaning by those of ordinary skill in the art when applying that term in the context of describing the present invention.

[0044] As used herein and in the appended claims, the articles "a" and "an" are used herein to refer to one or more than one (i.e., at least one) of the grammatical object of the article, unless the context clearly dictates otherwise. For example, "an element" means one element or more than one element.

[0045] As used herein in the specification and in the claims, the phrase "and / or" should be understood to mean "either or both" of the elements so combined, i.e., elements that exist together in some cases and separately in other cases. Multiple elements listed with "and / or" should be interpreted in the same manner, i.e., "one or more" of the elements so combined. In addition to the elements specifically identified by the "and / or" clause, other elements may optionally be present, whether related or unrelated to those specifically identified. Thus, as a non-limiting example, in one embodiment, when used in conjunction with open language such as "comprising," a reference to "A and / or B" may refer to only A (optionally including elements other than B); in another embodiment, to only B (optionally including elements other than A); in yet another embodiment, to both A and B (optionally including other elements); etc.

[0046] As used herein in this specification and claims, "or" should be understood to have the same meaning as "and / or" as defined above. For example, when separating the items in a list, "or" or "and / or" should be interpreted as inclusive, i.e., including at least one, but also including more than one of many elements or lists of elements, and optionally, items that are not listed in addition. Only terms that clearly indicate the contrary, such as "only one of..." or "exactly one of..." or when used in a claim, "consisting of..." will refer to including exactly one element of multiple elements or lists of elements. In general, when preceded by an exclusive term, such as "any one of," "one of...", "only one of..." or "exactly one of...", the term "or" as used herein should only be interpreted as indicating an exclusive alternative (i.e., "one or the other, but not both").

[0047] As used herein in this specification and claims, "at least one" with respect to a list of one or more elements should be understood to mean at least one element selected from any one or more elements in the list of elements, but not necessarily including at least one element of every element specifically listed in the list of elements, and not excluding any combination of elements in the list of elements. This definition also allows for the optional presence of elements other than the elements specifically identified in the list of elements to which the phrase "at least one" refers, whether related or unrelated to those elements specifically identified. Thus, as a non-limiting example, in one embodiment, "at least one of A and B" (or equivalently, "at least one of A or B," or equivalently, "at least one of A and / or B") may refer to at least one that optionally includes more than one A, does not have B (and optionally includes elements other than B); in another embodiment, may refer to at least one that optionally includes more than one B, does not have A (and optionally includes elements other than A); in yet another embodiment, may refer to at least one that optionally includes more than one A and at least one that optionally includes more than one B (and optionally includes other elements); etc.

[0048] In the claims and the foregoing description, all transitional phrases such as "comprising," "including," "carrying," "having," "containing," "involving," "having," "consisting of," and the like are to be understood as open-ended, i.e., meaning including but not limited to. Only the transitional phrases "consisting of" and "consisting essentially of" shall be closed or semi-closed transitional phrases, respectively, as set forth in Section 2111.03 of the United States Patent Office Manual of Patent Examining Procedures.

[0049] As used herein in this specification and claims, the phrase "at least one" with respect to a list of one or more elements should be understood to mean at least one element selected from any one or more elements in the list of elements, but not necessarily including at least one element of every element specifically listed in the list of elements, and not excluding any combination of elements in the list of elements. This definition also allows for the optional presence of elements other than the elements specifically identified in the list of elements to which the phrase "at least one" refers, whether related or unrelated to those specifically identified elements. Thus, as a non-limiting example, in one embodiment, "at least one of A and B" (or equivalently, "at least one of A or B," or equivalently, "at least one of A and / or B") may refer to at least one that optionally includes more than one A, does not have B (and optionally includes elements other than B); in another embodiment, may refer to at least one that optionally includes more than one B, does not have A (and optionally includes elements other than A); in yet another embodiment, may refer to at least one that optionally includes more than one A and at least one that optionally includes more than one B (and optionally includes other elements); etc. It should also be understood that, unless explicitly stated to the contrary, in any method claimed herein that includes more than one step or action, the order of the method steps or actions is not necessarily limited to the order in which the method steps or actions are recited.

[0050] Surprisingly and unexpectedly, the inventors have found that the caprolactone polyols of the present disclosure provide polyurethane materials or adhesives with reduced open time, reduced viscosity, improved adhesion and improved tensile strength compared to caprolactone polyols prepared without the initiator of the present disclosure. In any aspect or embodiment described herein, the caprolactone polyols are prepared by a method comprising: mixing an initiator and a caprolactone monomer to form an initiator-caprolactone mixture or a reaction mixture; adding a catalyst (e.g., a stannous octoate catalyst, such as T-9) to the initiator-caprolactone mixture to form a reaction mixture; and polymerizing the caprolactone monomers in the reaction mixture (e.g., ring-opening polymerization) to form the caprolactone polyols, wherein the initiator comprises hydroquinone bis(2-hydroxyethyl) ether, dodecanediol (e.g., 1,12-dodecanediol), pentaspirodiol, or a combination thereof.

[0051] Caprolactone polyol disclosed herein and preparation method thereof

[0052] One aspect of the present disclosure provides a caprolactone polyol, which is prepared by a method comprising: mixing an initiator and a caprolactone monomer to form an initiator-caprolactone mixture or reaction mixture; adding a catalyst (e.g., a stannous octoate catalyst such as T-9) to the initiator-caprolactone mixture to form a reaction mixture; and polymerizing (e.g., ring-opening polymerization) the caprolactone monomer in the reaction mixture to form the caprolactone polyol, wherein the initiator comprises hydroquinone bis(2-hydroxyethyl) ether, dodecanediol (e.g., 1,12-dodecanediol), pentaspirodiol, or a combination thereof.

[0053] Another aspect of the present disclosure provides a method for preparing the caprolactone polyol of the present disclosure. The method comprises: mixing an initiator and a caprolactone monomer to form an initiator-caprolactone mixture or reaction mixture; adding a catalyst (e.g., a stannous octoate catalyst such as T-9) to the initiator-caprolactone mixture to form a reaction mixture; and polymerizing (e.g., ring-opening polymerization) the caprolactone monomer in the reaction mixture to form the caprolactone polyol, wherein the initiator comprises hydroquinone bis(2-hydroxyethyl) ether, dodecanediol (e.g., 1,12-dodecanediol), pentaspirodiol, or a combination thereof.

[0054] In any aspect or embodiment described herein, the method further comprises: (i) withdrawing the initiator-caprolactone mixture prior to adding the catalyst (e.g., bubbling the initiator-caprolactone mixture with nitrogen); (ii) incubating the initiator-caprolactone mixture prior to adding the catalyst (e.g., incubating for about 0.5 hours to about 1.5 hours, about 0.75 hours to about 1.25 hours, or about 1 hour, such as when exciting the initiator-caprolactone mixture); (iii) heating the initiator-caprolactone mixture to about 70°C to about 100°C (e.g., about 75°C to about 95°C); or (iii) a combination thereof.

[0055] In any aspect or embodiment described herein, the polymerization is carried out: (i) at reflux; (ii) at about 150°C to about 190°C (e.g., about 150°C to about 180°C); (iii) for about 4 hours to about 6 hours; or (iv) a combination thereof.

[0056] In any aspect or embodiment described herein, the method further comprises adding an additional catalyst (e.g., a stannous octoate catalyst such as T-9) to the reaction mixture (e.g., adding the additional catalyst while heating the reaction mixture, such as heating to about 150°C to about 190°C, such as about 150°C to about 160°C), thereby forming the caprolactone polyol.

[0057] In any aspect or embodiment described herein, the initiator-caprolactone mixture further comprises an antioxidant and / or stabilizer (e.g., a phenolic antioxidant and / or stabilizer, a sterically hindered phenolic antioxidant and / or stabilizer, pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) ( 1010), phosphite antioxidants and / or stabilizers, bis(2,4-di-tert-butylphenol) pentaerythritol diphosphate (such as 126) Anti-hydrolysis agent ( 1), acid scavenger ( I), carbodiimide (such as monomeric carbodiimide) or a combination thereof).

[0058] In any aspect or embodiment described herein, at least one of the following is true: the caprolactone monomer is present in an amount of about 85 wt % to about 98 wt % (e.g., about 90 wt % to about 97 wt %, about 93 wt % to about 97 wt %, or about 95 wt %) of the initiator-caprolactone mixture; the initiator is present in an amount of about 2 wt % to about 15 wt % (e.g., about 3 wt % to about 10 wt %, about 3 wt % to about 7 wt %, or about 5 wt %) of the initiator-caprolactone mixture; the caprolactone monomer is present in an amount of about 85 wt % to about 98 wt % (e.g., about 90 wt % to about 97 wt %, about 93 wt % to about 97 wt %, or about 95 wt %) of the reaction mixture. 7 wt %, about 93 wt % to about 97 wt % or about 95 wt %) of the reaction mixture; the initiator is present in an amount of about 2 wt % to about 13 wt % (e.g., about 3 wt % to about 10 wt %, about 3 wt % to about 7 wt % or about 5 wt %) of the reaction mixture; the catalyst is present in an amount of about 0.001 wt % to about 5 wt % (e.g., about 0.001 wt % to about 5 wt %, about 0.001 wt % to about 4 wt %, about 0.001 wt % to about 3 wt %, about 0.001 wt % to about 2 wt %, about 0.001 wt % to about 1 wt %, about 0.001 wt % to about About 0.5 wt%, about 0.001 wt% to about 0.25 wt%, about 0.1 wt% to about 5 wt%, about 0.1 wt% to about 4 wt%, about 0.1 wt% to about 3 wt%, about 0.1 wt% to about 2 wt%, about 0.1 wt% to about 1 wt%, about 0.1 wt% to about 0.5 wt%, about 0.1 wt% to about 0.25 wt%, about 0.2 wt% to about 5 wt%, about 0.2 wt% to about 4 wt%, about 0.2 wt% to about 3 wt%, about 0.2 wt% to about 2 wt%, about 0.2 wt% to about 1 wt%, about 0.2 wt% to about 0.5 wt%, about 0.5 wt% to about 5wt%, about 0.5wt% to about 4wt%, about 0.5wt% to about 3wt%, about 0.5wt% to about 2wt%, about 0.5wt% to about 1wt%, about 0.75wt% to about 5wt%, about 0.75wt% to about 4wt%, about 0.75wt% to about 3wt%, about 0.75wt% to about 2wt%, about 0.75wt% to about 1wt%, about 1wt% to about 5wt%, about 1wt% to about 4wt%, about 1wt% to about 3wt%, about 1wt% to about 2wt%, about 1.5wt% to about 5wt%, about 1.5wt% to about 4wt%, about 1.5 wt % to about 3 wt %, about 2 wt % to about 5 wt %, about 2 wt % to about 4 wt %, about 2 wt % to about 3 wt %, about 3 wt % to about 5 wt %, about 3 wt % to about 4 wt %, or about 4 wt % to about 5 wt %); the antioxidant or stabilizer is present in an amount of up to about 2 wt % (e.g., up to about 1.5 wt %, up to about 1 wt %, up to about 0.5 wt %, up to about 0.25 wt %, about 0.1 wt % to about 2 wt %, about 0.1 wt % to about 1.5 wt %, about 0.1 wt % to about 1 wt %, about 0.1 wt % to about 0.75 wt %, about 0.1 wt % to about 0.5 wt %, or about 0.1 wt % to about 0.25 wt %) of the reaction mixture; or a combination thereof.

[0059] In any aspect or embodiment described herein, the caprolactone polyol has a molecular weight of about 2,000 g / mol (MW) to about 4500 MW (eg, about 2,000 MW to about 4,000 MW or about 3,500 MW to about 4,000 MW).

[0060] In any aspect or embodiment described herein, the caprolactone polyol comprises less than about 5% (e.g., less than about 4%, less than about 3%, less than about 2%, less than about 1%, less than about 0.5%, less than about 0.5%, less than about 0.25%, less than about 0.1%) caprolactone monomer.

[0061] In any aspect or embodiment described herein, at least one of the following is true: the catalyst is a catalyst for ring-opening polymerization (e.g., zinc lactate, zinc oxide, zinc powder, diethyl zinc, tin lactate, tin oxide, tin dioxide, stannous oxide, stannous lactate, stannous octoate, stannous chloride, tin powder, propionic acid, or tetrabutyl titanate, or a combination thereof).

[0062] As used herein, the term "caprolactone" is intended to encompass both unsubstituted caprolactone and substituted caprolactones. The term "ε-caprolactone" is intended to encompass both unsubstituted ε-caprolactone and substituted ε-caprolactones. Unsubstituted ε-caprolactone is particularly preferred.

[0063] In any aspect or embodiment described herein, the copolymerization can include copolymerizing caprolactone, particularly ε-caprolactone, with a mixture of different caprolactones, such as a mixture of substituted and unsubstituted caprolactones or caprolactones with different substituents.

[0064] In any aspect or embodiment described herein, substituted ε-caprolactone monomers that can be used to produce caprolactone polyols include C 1-12 Alkyl substituted ε-caprolactone, C 1-12 Alkenyl substituted ε-caprolactone, C1-12 Alkynyl substituted ε-caprolactone, C 1-18 Cycloalkyl substituted ε-caprolactone, C 1-12 Alkoxy substituted ε-caprolactone, C 1-18 Aryl substituted ε-caprolactone, C 1-18 Alkaryl substituted ε-caprolactone, C 1-18 Aralkyl substituted ε-caprolactone, C 1-18 Aryloxy-substituted ε-caprolactones and mixtures thereof.

[0065] In any aspect or embodiment described herein, the substituted ε-caprolactone monomers that can be used to produce the auxiliary caprolactone polyol include monosubstituted, disubstituted, or trisubstituted monomers. In any aspect or embodiment described herein, exemplary substituted ε-caprolactone monomers include monomethyl ε-caprolactone, monoethyl ε-caprolactone, monopropyl ε-caprolactone, monomethoxy ε-caprolactone, monoethoxy ε-caprolactone, monopropoxy ε-caprolactone, monobenzyl ε-caprolactone, monophenyl ε-caprolactone, dimethyl ε-caprolactone, diethyl ε-caprolactone, dipropyl ε-caprolactone, dimethoxy ε-caprolactone, diethoxy ε-caprolactone, dipropoxy ε-caprolactone, dibenzyl ε-caprolactone, diphenyl ε-caprolactone, and mixtures thereof.

[0066] Polyurethane material or adhesive disclosed herein and preparation method thereof

[0067] Another aspect of the present disclosure provides a polyurethane material or adhesive (e.g., a polyurethane material or adhesive based on caprolactone polyol), which is prepared by a method comprising reacting the caprolactone polyol of the present disclosure with an isocyanate (e.g., a diisocyanate or a polyisocyanate) containing two or more isocyanate groups, thereby forming the polyurethane material.

[0068] Another aspect of the present disclosure provides a method for preparing the polyurethane material or adhesive of the present disclosure. The method comprises reacting the caprolactone polyol of the present disclosure with an isocyanate (e.g., a diisocyanate or a polyisocyanate) containing two or more isocyanate groups to form the polyurethane material.

[0069] In any aspect or embodiment described herein, the method further comprises: (i) heating the caprolactone polyol and / or the isocyanate (e.g., to about 70°C to about 100°C, about 80°C to about 90°C, about 82°C to about 88°C, or about 85°C) prior to reacting with the isocyanate; (ii) drying the polyurethane material or adhesive; (iii) bubbling the caprolactone polyol prior to reacting (e.g., bubbling with nitrogen and / or bubbling for about 0.5 hours to about 1.5 hours, about 0.75 hours to about 1.25 hours, or about 1 hour); or (iv) a combination thereof.

[0070] In any aspect or embodiment described herein, reacting the caprolactone polyol and the isocyanate is carried out: (i) under bubbling (e.g., bubbling with nitrogen); (ii) under heating (e.g., reacting the caprolactone polyol and the isocyanate at 100°C to about 150°C (e.g., about 110°C to about 140°C, 115°C to about 135°C, or 120°C to 130°C); (iii) for about 1.0 hour to about 3.0 hours (e.g., about 1.25 hours to about 2.75 hours, about 1.5 hours to about 2.5 hours, about 1.75 hours to about 1.25 hours, or about 2.0 hours); or (iv) a combination thereof.

[0071] In any aspect or embodiment described herein, at least one of the following is true: (i) the isocyanate is a monomer, oligomer, polymer, or a mixture thereof; (ii) the catalyst is a urethane catalyst (e.g., a tertiary amine compound, an amine having an isocyanate-reactive group, an organometallic compound, or a mixture thereof); or (iii) a combination thereof.

[0072] In any aspect or embodiment described herein, the isocyanate comprises 2,2'-methylenediphenyl diisocyanate; 2,4'-methylenediphenyl diisocyanate; 4,4'-methylenediphenyl diisocyanate (MDI); 3,3'-dimethyl-4,4'-diphenylidene diisocyanate (TODI); toluene diisocyanate (TDI); polymeric MDI; modified liquid 4,4'-methylenediphenyl diisocyanate; hexamethylene diisocyanate ("HDI"); 4,4'-dicyclohexylmethane diisocyanate ("HDI"); 12MDI”); isophorone diisocyanate (“IPDI”); p-phenylene diisocyanate (“PPDI”); m-phenylene diisocyanate (“MPDI”); tetramethylene diisocyanate; dodecane diisocyanate; octamethylene diisocyanate; decamethylene diisocyanate; cyclobutane-1,3-diisocyanate; 1,2-cyclohexane diisocyanate; 1,3-cyclohexane diisocyanate; 1,4-cyclohexane diisocyanate; 2,4-methylcyclohexane diisocyanate; 2,6-methylcyclohexane diisocyanate; 4,4′-dicyclohexyl diisocyanate; 2,4′-dicyclohexyl diisocyanate; 1,3,5-cyclohexane triisocyanate; isocyanato-methylcyclohexane isocyanate; isocyanatoethylcyclohexane isocyanate; bis(isocyanatomethyl)-cyclohexane diisocyanate; 4,4'-bis(isocyanatomethyl)dicyclohexane; 2,4'-bis(isocyanatomethyl)dicyclohexane; isophorone diisocyanate; 2,4-hexahydrotoluene diisocyanate; 2,6-hexahydrotoluene diisocyanate; 1,2-phenylene diisocyanate; 1,3-phenylene diisocyanate; 1,4-phenylene diisocyanate; triphenylmethane-4,4',4"-triisocyanate; naphthylene-1,5-diisocyanate; 2,4'-biphenyl diisocyanate; 4,4'-biphenyl diisocyanate; 2,2-biphenyl diisocyanate; polyphenyl polymethylene polyisocyanate ("PMDI"); m-tetramethylxylene diisocyanate ("m-TMXDI"); p-tetramethylxylene diisocyanate ("p-TMXDI"); or mixtures thereof.

[0073] In any aspect or embodiment described herein, the isocyanate comprises dimethylmethane-4,4'-diisocyanate (MDI).

[0074] In any aspect or embodiment described herein, the catalyst is: (i) a tertiary amine catalyst (e.g., a tertiary amine catalyst present in an amount of about 0.02 wt% to about 5 wt% of the reaction mixture) comprising triethylenediamine, N-methylmorpholine, N,N-dimethylcyclohexylamine, pentamethyldiethylenetriamine, tetramethylethylenediamine, bis(dimethylaminoethyl)ether, 1-methyl-4-dimethylaminoethyl-piperazine, 3-methoxy-N-dimethylpropylamine, N-ethylmorpholine; dimethylethanolamine, N-cocomorpholine, N,N-dimethyl-N',N'-dimethylisopropylpropylenediamine, N,N-diethyl (ii) an organometallic catalyst (e.g., an organometallic catalyst present in an amount of about 0.001 wt % to 1 wt % of the reaction mixture), the organometallic catalyst comprising an organobismuth, an organomercury, an organolead, an organoferric, an organotin catalyst, or a combination thereof (preferably, an organotin catalyst); (iii) a tin catalyst comprising stannous chloride, a tin carboxylate (e.g., dibutyltin dilaurate), stannous octoate, or a combination thereof; (iv) a catalyst comprising an alkali metal alkoxide, the catalyst being used to trimerize a polyisocyanate; or (v) a combination thereof.

[0075] In any aspect or embodiment described herein, the reactive polyurethane material or adhesive has an excess NCO (cyanate ester) content of at least about 1% (e.g., about 1% to about 5%, about 1% to about 4%, about 1% to about 3%, about 1% to about 2%, about 2% to about 5%, about 2% to about 4%, about 2% to about 3%, about 3% to about 5%, or about 4% to about 5%).

[0076] In any aspect or embodiment described herein, the polyurethane material is an adhesive (eg, a hot melt adhesive) or a polyurethane reactive adhesive (eg, a reactive hot melt adhesive).

[0077] As used herein, "hot melt adhesive" refers to a reactive hot melt adhesive composition that is heated to obtain a liquid having a flowable viscosity and, after application to a substrate, is cooled to obtain a solid. After the hot melt adhesive solidifies upon cooling to a temperature below its melt temperature or below its solidification transition temperature, an adhesive bond is formed between the substrate and the adhesive material.

[0078] Hot melt adhesives are commonly used to bond two substrates together to maintain a fixed relationship between the two substrates. Hot melt adhesives are also used in articles comprising nonwoven layers to bond the nonwoven layer and polymer film layers together. Hot melt adhesives are further used to bond packaging structures (e.g., bags, boxes, cartons, cases, and pallets) together to construct packaging, close packaging, or both. They are also used as pressure-sensitive adhesives for tapes and labels.

[0079] Hot melt adhesives are typically sought for commercial applications in terms of adhesion properties, open time, set time, and open time. The adhesive properties of hot melt adhesives must be good during use, as loss of adhesion could, for example, lead to the opening of a package, which is unacceptable during and after production. Therefore, the adhesion of hot melt adhesives should be good over time and under a wide range of conditions.

[0080] Another property of hot melt adhesives is setting time, which is the time required for the adhesive to form a bond with a substrate. Setting time can be important in commercial operations because it controls the time required to press the two substrates together with the adhesive. In any aspect or embodiment described herein, the setting time can be about a few seconds. For example, in any aspect or embodiment described herein, the set time is less than about 60 seconds, less than about 50 seconds, less than about 40 seconds, less than about 30 seconds, less than about 20 seconds, less than about 10 seconds, less than about 5 seconds, about 5 seconds to about 60 seconds, about 5 seconds to about 50 seconds, about 5 seconds to about 40 seconds, about 5 seconds to about 30 seconds, about 5 seconds to about 20 seconds, about 5 seconds to about 10 seconds, about 10 seconds to about 60 seconds, about 10 seconds to about 50 seconds, about 10 seconds to about 40 seconds, about 10 seconds to about 30 seconds, about 10 seconds to about 20 seconds, about 20 seconds to about 60 seconds, about 20 seconds to about 50 seconds, about 20 seconds to about 40 seconds, about 20 seconds to about 30 seconds, about 30 seconds to about 60 seconds, about 30 seconds to about 50 seconds, about 30 seconds to about 40 seconds, about 40 seconds to about 60 seconds, about 40 seconds to about 50 seconds, or about 50 seconds to about 60 seconds.

[0081] In some embodiments, the hot melt adhesive has a plurality of opening times, and the opening time is less than about 7 minutes, less than about 6.5 minutes, less than about 6 minutes, less than about 5.5 minutes, less than about 5 minutes, less than about 4.5 minutes, less than about 4 minutes, about 3 minutes to about 7 minutes, about 3 minutes to about 6.5 minutes, about 3 minutes to about 6 minutes, about 3 minutes to about 5 minutes, about 3 minutes to about 4 minutes, about 4 minutes to about 7 minutes, about 4 minutes to about 6.5 minutes, about 4 minutes to about 6 minutes, about 4 minutes to about 5 minutes, about 5 minutes to about 7 minutes, about 5 minutes to about 6.5 minutes, about 5 minutes to about 6 minutes or about 6 minutes to about 7 minutes.

[0082] Methods of using the polyurethane materials or adhesives disclosed herein

[0083] One aspect of the present disclosure provides a method of bonding a first substrate and a second substrate, the method comprising: applying the polyurethane material of the present invention to the first substrate, the second substrate, or the first substrate and the second substrate; and contacting the first substrate and the second substrate with the polyurethane material located therebetween.

[0084] In any aspect or embodiment described herein, the method further comprises: (i) applying pressure to the contacted first and second substrates; (ii) incubating the contacted first and second substrates; or (iii) a combination thereof.

[0085] In any aspect or embodiment described herein, the method is a method of performing flat lamination (bonding wood to a decorative substrate), flooring construction (such as cork, nonwoven fabrics, various plastics, etc.), edge tape, and binding. In any aspect or embodiment described herein, the method is a method of flat lamination, a method of constructing flooring, a method of edge tape, or a method of binding.

[0086] Examples

[0087] The details of the examples are considered to be additional embodiments of the described methods and compositions. Therefore, the details as set forth herein are incorporated into the detailed description as alternative embodiments. Surprisingly and unexpectedly, it was found that the caprolactone polyols of the present disclosure provide polyurethane materials or adhesives with reduced open times, reduced viscosities, improved adhesion, and improved tensile strengths compared to caprolactone polyols prepared without the initiator of the present disclosure.

[0088] A commercially available caprolactone product, Capa TM 2403D, which has three new caprolactone diols with the same molecular weight (4000 g / mol) and 7360 (3500 molecular weight polyester polyol (HDO / AA)) was used as a benchmark. Table 1 shows the properties of the compositions examined.

[0089] Table 1: List of polyols examined

[0090]

[0091] Example 1. Synthesis of Hydroquinone Bis(2-Hydroxyethyl) Ether (HQEE) Polyol, Pentaspirodiol (PSG) Polyol, and Dodecanediol Polyol

[0092] Hydroquinone bis(2-hydroxyethyl) ether (HQEE), pentaspirodiol (PSG), and dodecanediol were examined as initiator molecules for the synthesis of caprolactone polyols having a molecular weight of 4000. The structure of each exemplary initiator is shown below in Table 2. As discussed in more detail below, RHMAs were prepared and characterized using the exemplary caprolactone polyols.

[0093] Table 2: Name, structure and molecular weight of the initiator molecules used for the ring-opening polymerization of caprolactone diol

[0094]

[0095] Prepare the caprolactone polyol of about 4000MW with initiator HQEE.The reagent for reaction is shown in the following table 3.In brief, HQEE, antioxidant and caprolactone monomer are merged, loaded and bubbled under 90 ℃ / 15 mbar.It is 0.010% to measure water content.After 60 minutes incubation, the mixture is heated to 160 ℃ (240 mbar).T9 catalyst (8ppm) is added to the mixture, and the temperature is increased to 180 ℃ (240 mbar).After 4.5 hours incubation, complete reflux.Monomer content is measured to be 0.041%.Mixture is cooled and decant for inspection / characterization (data are shown below).

[0096] Table 3: Reagents used to prepare approximately 4000 MN caprolactone polyols prepared with HQEE

[0097]

[0098] *Pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate).

[0099] **Bis(2,4-di-tert-butylphenol)pentaerythritol diphosphite.

[0100] An exemplary HQEE initiated caprolactone polyol has the following properties: 0.017% water, 3988 MW (g / mol), hydroxyl value (OHV) of 28.13 mgKOH / g, acid value (AV) of 0.05 mgKOH / g, corrected OHV (COHV) of 28.183 mgKOH / g, color of 10 HU, and monomer content of 0.41%.

[0101] During the synthesis of HQEE-initiated caprolactone polyols, 1010 (sterically hindered phenolic primary antioxidant and co-stabilizer) and 126 (bis(2,4-di-tert-butylphenol)pentaerythritol diphosphate). The combination of these additives has been shown to provide thermooxidative stability and prevent discoloration during ring-opening polymerization.

[0102] About 4000NM of caprolactone polyol was prepared with initiator pentaspirodiol (PSG). The reagents used for the reaction are shown in Table 4 below. Under a positive flow of N2, caprolactone monomer and PSG were loaded into a clean 20L reactor. After two hours, the mixture was heated to 80°C and full vacuum was applied to induce bubbling. After 4 hours, the vacuum and heating were removed, and the mixture was left in the reactor overnight. After incubation overnight, the mixture was heated to 160°C. After two hours at 160°C, a 6ppm equivalent catalyst solution was added to the mixture, and the reactor was heated to 180°C for reaction. The pressure was reduced until a slight reflux was noted at 160 mbar. After 3 hours and 10 minutes, the pressure was released, and the reactor was cooled to 80°C for overnight incubation. After incubation overnight, the reactor was reheated to 180°C to continue the reaction. After 7 hours and 15 minutes, the vacuum was removed and an aliquot was taken to test the acid value. The acid value was 0.23 mgKOH / g. The reactor was set to 140°C and the I and full vacuum was applied for 30 minutes of acid treatment. The vacuum was removed and the heat was set to 80°C. After incubation overnight, the reactor was set to 140°C to continue the acid treatment. After 5 hours and 15 minutes, the PSG-initiated caprolactone polyol was discharged at 100°C.

[0103] Table 4: Reagents used to prepare approximately 4000 MN caprolactone polyols prepared with PSG

[0104]

[0105] An exemplary PSG initiated caprolactone polyol has the following properties: 0.061% water, hydroxyl value (OHV) of 27.53 mgKOH / g, acid value (AV) of 0.022 mgKOH / g, color of 28 HU, and monomer content of 0.26%.

[0106] About 4000MW of caprolactone polyol was prepared with initiator 1,12-dodecanediol. The reagents used for the reaction are shown in Table 5 below. Briefly, caprolactone monomer and 1,12-dodecanediol were loaded into a 3L reaction vessel under a stream of N2. The temperature was set to 80°C. Bubbling was started at 80°C under full vacuum. The water content was measured to be 0.019%. T9 catalyst (6ppm) was added and reflux was initiated at 173°C (148 mbar). The vacuum was removed and the temperature was set to cool overnight.

[0107] Reflux was reinitiated at 155° C. (73 mbar) and an additional 6 ppm of T9 catalyst was added (12 ppm total). Full vacuum was achieved. The vacuum was removed and the mixture was cooled overnight. The monomer content was measured to be 0.226%. The product was discharged at 80° C. for inspection / characterization (data shown below).

[0108] Table 5: Reagents used to prepare approximately 4000 MN caprolactone polyols prepared from dodecanediol

[0109] Reagents supplier Amount (g) Caprolactone monomer Ingevity 2088.7 1,12-Dodecanediol ThermoFischer 111.3 T9 Catalyst BASF 0.1643

[0110] An exemplary 1,12-dodecanediol initiated caprolactone polyol has the following properties: a waxy solid at room temperature, a light yellow viscous liquid at 80°C, 0.019% water, MW (g / mol), a hydroxyl value (OHV) of 26.88 mgKOH / g, an acid value (AV) of 0.132 mgKOH / g, a corrected OHV (COHV) of 27.01 mgKOH / g, a color of 49 HU, and a monomer content of 0.226%.

[0111] Example 2. Synthesis of reactive hot melt adhesive

[0112] Use Capa TM 2403D, 4000MW HQEE initiated caprolactone polyol, 4000MW PSG initiated caprolactone polyol and 4000MW dodecanediol initiated caprolactone polyol were used to prepare reactive hot melt adhesives with excess NCO content. Briefly, the polyols, pressure equalizing dropping funnel and methylene diphenyl diisocyanate (MDI) were preheated to 85°C in an oven.

[0113] One mL of pre-melted polyol was added to a Karl Fisher titration vessel (Karl Fisher Titration Vessel) (hereinafter referred to as "vessel"). Polyol (650 g) was back-weighed in a round-bottom flask using a funnel. Nitrogen was turned on, the inlet was below the polyol surface, the stirrer was set to 100 revolutions per minute (RPM) at 120°C or 130°C (depending on the desired temperature), and vacuum was applied for 1 hour.

[0114] Weigh 85°C MDI (117.09 g) into a preheated dropping funnel. Add the dropping funnel to the container, fully open the dropping funnel valve to quickly add the MDI, and remove the dropping funnel once the addition of MDI is complete. Allow the mixture to react for 1 hour 45 minutes to 2 hours 15 minutes at 200 RPM.

[0115] The agitator was turned off and vacuum was applied using the same method discussed above to degas the prepolymer. Once degassing was complete, the vacuum was turned off, the agitator was stopped, the container was removed from the apparatus, and the isocyanate prepolymer was aliquoted into 250 mL storage jars. The isocyanate prepolymer was blanketed with nitrogen, a lid was applied to the storage tin, and the jar was stored at room temperature in a moisture barrier bag.

[0116] The NCO content of the isocyanate prepolymers was checked by an automatic titrator program.

[0117] As mentioned above, PSG, HQEE, and dodecanediol were selected as exemplary initiators in the ring-opening polymerization of caprolactone polyols.

[0118] Its presence in the polyol backbone enhances the recrystallization rate and, in turn, reduces the open time of adhesives formulated with the caprolactone polyols of the present disclosure. As shown in Table 2, exemplary initiators contain aromatic rings or rigid cyclic structures, or, in the case of dodecanediol, longer carbon chains (12 carbons), which can promote symmetry and enhance crystallization rates.

[0119] Example 3. Open Time of Reactive Hot Melt Adhesives

[0120] Open time measurement (wooden tongue depressor method). Since many methods for checking open time are discussed and published in the adhesive art, the widely practiced and accepted method of using a wooden tongue depressor was utilized. The RHMA contained in an aluminum 310 mL cylinder was placed in an oven at 120° C. for 4 hours. Once at temperature (measured by a thermometer placed in the adhesive mass), the sealed tube was placed in a Reka TR 70 hot melt barrel extruder gun set at 120° C. and a bead of adhesive was dispensed from the gun with pneumatic assistance (6 bar).

[0121] The adhesive bead (0.2 g) was placed on a wooden tongue depressor and the open time was defined as the moment when a second wooden tongue could no longer form a bond with the adhesive bead.

[0122] result. like Figure 1 As shown, (1) the open time of 3 minutes and 45 seconds contains the market leading polyester polyol based on hexanediol and adipic acid ( 7360) and (2) a commercial caprolactone polyol Capa TM There was an observable difference in the open time of the 2403D (butylene glycol initiated) adhesive.

[0123] The open time of the adhesive decreased with the incorporation of PSG (6 minutes 15 seconds), HQEE (5 minutes 30 seconds), and dodecanediol (4 minutes 45 seconds). Figure 1 The initiator molecules were shown to reduce the open time of adhesives having altered caprolactone polyol backbones.

[0124] Example 4. Differential Scanning Calorimetry (DSC) of Polyols and Reactive Hot Melt Adhesives

[0125] Differential Scanning Calorimetry (DSC). Using DSC 25 ( The thermal behavior of both the polyol and the formulated RHMA was collected using a 10°C / min temperature ramp to capture the glass transition temperature (T g ), melting temperature (T m ) and recrystallization temperature (T c ).

[0126] result. DSC data were collected to establish a relationship between the thermal events measured by DSC and the open time measurements discussed herein. DSC data were collected on the polyols and the final cured adhesive. The glass transition temperatures (T g ) and recrystallization temperature (T c ) data.

[0127] Table 6: DSC data on polyols and fully cured adhesives collected after curing for at least 7 days at 23°C

[0128]

[0129] Example 5. Lap shear adhesion of reactive hot melt adhesives

[0130] Measurement of lap shear. The German national standard DIN EN 1465:2009-07 (Determination of the tensile lap shear strength of adhesive-bonded assemblies. January 7, 2009) is used to measure lap shear, including defining lap shear dimensions. Briefly, lap shear specimens were cleaned with a microfiber cloth and isopropyl alcohol (IPA) and then placed in a temperature-controlled humidity cabinet (50% relative humidity at 23°C). To maintain a bond line gap of 0.2 mm, a calibrated wire was attached to one of the bottom specimens (substrate) located in the mold, and adhesive was applied using a hot melt gun.

[0131] Use a stick to spread the adhesive into the shear area. The adhesive-covered shear area is mated to the top sample (substrate) and pressure is applied to the appropriate block. Excess sample is wiped away with a cotton swab. The sample is allowed to cool and solidify. Then, the sample is placed in a temperature-controlled humidity cabinet.

[0132] The lap shear products were pulled onto a ZwickRoell tensile testing machine using 10 kN load cells with asymmetric fixtures. The bonded products were pulled at a force control rate of 0.16 mPa / s. The force reported as bonding was the force maximum. Different types of failure modes were recorded for each experiment. Adhesive failure was the failure between the adhesive film and the substrate, cohesive failure was the failure within the adhesive film itself, and substrate failure was the fracture observed in the tested substrate.

[0133] result.Lap shear adhesion was measured as described above. The bonded substrates included aluminum (2 mm thick) alloy 5005A (AlMg 1), polycarbonate (6 mm thick) markoform 099, and beech wood (6 mm thick) damped and surface planarized. All substrates were purchased from Rocholl GmbH (Eschelbronn, Germany).

[0134] The results contained in Table 7 below are expressed in N / mm 2 The failure mechanisms are shown in parentheses, where AF represents adhesive failure between the adhesive and the substrate, CF represents cohesive failure within the adhesive film itself, and SF represents substrate failure where the substrate breaks before the adhesive fails.

[0135] Table 7: Lap shear adhesion of each system (aluminum, polycarbonate and beech) in N / mm 2 The maximum value of F in units

[0136]

[0137] Figure 2 Shear adhesion data (Fmax N / mm) are presented for each substrate and adhesive examined. 2 All adhesives failed due to adhesive failure when bonded to aluminum. The HQEE initiated caprolactone polyol based adhesive returned 3.8 N / mm 2 The polycarbonate substrate gave the largest scatter in the data, with 11.4 N / mm for the PSG-initiated caprolactone polyol-based adhesive. 2 , and 14.6 N / mm for HQEE initiated caprolactone polyol based adhesives 2 This can be explained by the substrate itself (polycarbonate) being less rigid than the other substrates tested. During the lap shear measurement, the polycarbonate substrate distorts due to the forces and the geometry of the bonded area changes.

[0138] During testing of the HQEE-initiated caprolactone polyol-based adhesive and the dodecanediol-initiated caprolactone polyol-based adhesive, the beechwood substrate failed and fractured. Therefore, the beechwood results are not a true reflection of the adhesion. The PSG-initiated caprolactone polyol-based adhesive did provide the lowest recorded F max value of 13.9 N / mm. 2 , and based on Capa TM The 2403D adhesive provides the highest F-max value of 16.4N / mm 2 .

[0139] Within this data set, the HQEE-initiated caprolactone polyol-based adhesive provided the highest adhesion results, with the PSG-initiated caprolactone polyol-based adhesive being considered the lowest performing adhesive examined. The substrate failure observed with beech wood and dodecanediol, as well as the HQEE-initiated caprolactone polyol-based adhesive, can be explained by better substrate wetting, resulting in a lower viscosity of the adhesive compared to the polyester polyol.

[0140] Example 6. Viscosity of Reactive Hot Melt Adhesives

[0141] Viscosity measurement (Brookfield). Rotational viscosity was measured using a Brookfield DVNext viscometer and a thermocel. The test material (10.2 g) was placed in a disposable container and added to the thermocel. The temperature was set to 120°C, the torque was between 20% and 80%, and spindle 27 was selected. Final viscosity was recorded after 30 minutes of testing.

[0142] result. The viscosity of the adhesives was measured using a Brookfield viscometer as described herein. Table 8 shows viscosity measurements taken with a 27 spindle after 30 minutes at 130°C, unless otherwise stated. The polyester polyol-based adhesives recorded the highest viscosities, at 4100 mPa.s at 120°C for the 2.5% NCO adhesive and 2775 mPa.s for the 3% NCO adhesive.

[0143] Table 8: Viscosity of formulated adhesive (mPa.s)

[0144]

[0145] When compared at 120°C, all caprolactone-based adhesives had lower viscosities than polyester polyol-based adhesives. TM The lowest viscosity reading for the 2403D adhesive was 2260 mPa.s and the PSG initiated caprolactone polyol based adhesive gave the highest caprolactone based viscosity of 3435 mPa.s. Figure 3 Viscosity data are also shown.

[0146] Lower viscosity may be considered desirable in the reactive hot melt adhesive market as it allows the adhesive to flow over the substrate and enhances the surface interaction between the adhesive and the substrate, especially where the shapes of the substrates being bonded are more complex.

[0147] The lower viscosity of caprolactone-based adhesives results from the lower polydispersity of the ring-opening polymerization compared to condensation polyesters.

[0148] Example 7. Tensile Strength of Reactive Hot Melt Adhesives

[0149] Measurement of tensile strength of adhesive films. Test sheets were produced by applying 20 grams of adhesive to a flat sheet of siliconized release liner (80 gsm Kraft paper). Using a 0.5 mm K-strip, the adhesive prepolymer was drawn down across the surface of the release liner. Once the adhesive had set (24 hours in a fume hood), the adhesive film and release liner were placed in a temperature (23° C.) and humidity controlled oven (50% relative humidity).

[0150] After one week in the humidity oven, the adhesive film and release liner were removed and tensile test pieces were punched out using the dimensions specified in ISO 37:2005, Type 2, but with a film thickness of 0.5 mm. The tensile measurements were checked using a ZwickRoell tensile machine.

[0151] result. The tensile force of 0.5 mm adhesive films was measured as described herein. Figure 4 Table 9 below shows the Fmax values ​​(N / mm) recorded for each adhesive examined. 2 ).

[0152] Table 9: Fmax values ​​(N / mm) for 0.5 mm adhesive films 2 )

[0153]

[0154] The tensile forces in film tests demonstrate the impact of varying the chemistry of the initiator molecules within the caprolactone polyol. Linear initiators dodecanediol and butanediol yielded results similar to those of polyester polyols. Cyclic initiators HQEE and PSG exhibited increased Fmax values. This can be explained by steric hindrance caused by these more bulky structures, resulting in a greater force required to overcome the hindrance.

[0155] Discussion of examples

[0156] The data indicate that there is a structure-property relationship when the initiator molecule is varied in the production of caprolactone polyols.

[0157] The main motivation for changing the initiating molecule was to reduce the open time of caprolactone based adhesives which was needed in the market as an alternative to polyester chemistries. The short open time of the 7360 adhesive (3 minutes 45 seconds) is not matched by caprolactone-based alternatives, but dates indicate that the open time of adhesives based on caprolactone polyols can be reduced to 4 minutes 45 seconds by incorporating dodecanediol into the caprolactone-backbone.

[0158] Additional adhesive characterization techniques have been examined here to understand the performance profile of adhesives based on caprolactone polyols compared to alternative polyester polyols. For example, adhesives based on caprolactone polyols have lower viscosity and improved adhesion to aluminum and induced substrate failure in beech wood.

[0159] The tensile properties of the films show a clear structure-property relationship between the nature of the initiating molecules and the final F max. The "bulgy" and sterically hindered initiating molecules provide higher tensile strength to the adhesive film.

[0160] Although several embodiments of the present invention of the present disclosure have been shown and described herein, it should be understood that such embodiments are provided as examples only. Without departing from the spirit of the present invention, many changes, modifications and substitutions will occur to those skilled in the art. On the contrary, the present disclosure will cover all modifications, equivalents and substitutes within the scope of the present disclosure defined by the following appended claims and their legal equivalents. Therefore, this specification and the appended claims are intended to cover all such changes that fall within the spirit and scope of the present invention.

[0161] The contents of all references, patents, pending patent applications, and issued patents cited throughout this application are hereby expressly incorporated herein by reference.

[0162] Those skilled in the art will recognize, or be able to determine using only routine experimentation, many equivalents to the specific embodiments of the invention described herein. Such equivalents are intended to be covered by the appended claims. It should be understood that the detailed examples and embodiments described herein are given for illustrative purposes only and are in no way to be construed as limiting the invention. Various modifications or variations thereof will be contemplated by those skilled in the art and are included within the spirit and scope of this application and are considered to be within the scope of the appended claims. For example, the relative amounts of the ingredients may be varied to optimize the desired effect, other ingredients may be added, and / or similar ingredients may be substituted for one or more of the described ingredients. Other advantageous features and functions associated with the systems, methods, and processes of the present invention will be apparent from the appended claims. In addition, those skilled in the art will recognize, or be able to determine using only routine experimentation, many equivalents to the specific embodiments of the invention described herein. Such equivalents are intended to be covered by the appended claims.

Claims

1. A caprolactone polyol prepared by a process comprising: combining an initiator and a caprolactone monomer to form an initiator-caprolactone mixture or reaction mixture; adding a catalyst (e.g., a stannous octoate catalyst such as T-9) to the initiator-caprolactone mixture to form a reaction mixture; and polymerizing (e.g., ring-opening polymerization) the caprolactone monomers in the reaction mixture to thereby form the caprolactone polyol, The initiator comprises hydroquinone bis(2-hydroxyethyl) ether, dodecanediol (eg, 1,12-dodecanediol), pentaspirodiol, or a combination thereof.

2. The caprolactone polyol of claim 1 , wherein the method further comprises: (i) withdrawing the initiator-caprolactone mixture prior to adding the catalyst (e.g., bubbling the initiator-caprolactone mixture with nitrogen); (ii) incubating the initiator-caprolactone mixture prior to adding the catalyst (e.g., incubating for about 0.5 hours to about 1.5 hours, about 0.75 hours to about 1.25 hours, or about 1 hour, such as when the initiator-caprolactone mixture is excited); (iii) heating the initiator-caprolactone mixture to a temperature of about 70° C. to about 100° C. (e.g., about 75° C. to about 95° C.); or (iii) a combination thereof.

3. The caprolactone polyol of claim 1 or 2, wherein the polymerization is carried out: (i) under reflux; (ii) at about 150° C. to about 190° C. (e.g., about 150° C. to about 180° C.); (iii) for about 4 hours to about 6 hours; or (iv) a combination thereof.

4. The caprolactone polyol of any one of claims 1 to 3, further comprising adding an additional catalyst (e.g., a stannous octoate catalyst such as T-9) to the reaction mixture (e.g., adding the additional catalyst while heating the reaction mixture, such as heating to about 150° C. to about 190° C., such as about 150° C. to about 160° C.), thereby forming the caprolactone polyol.

5. Caprolactone polyol according to any one of claims 1 to 4, wherein the initiator-caprolactone mixture further comprises an antioxidant and / or stabilizer (e.g., phenolic antioxidants and / or stabilizers, sterically hindered phenolic antioxidants and / or stabilizers, pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) 1010), phosphite antioxidants and / or stabilizers, bis(2,4-di-tert-butylphenol) pentaerythritol diphosphate (such as 126) Anti-hydrolysis agent ( 1), acid scavenger ( I), carbodiimide (such as monomeric carbodiimide) or a combination thereof).

6. The caprolactone polyol according to any one of claims 1 to 5, wherein at least one of the following is true: the caprolactone monomer is present in an amount from about 85 wt % to about 98 wt % (e.g., from about 90 wt % to about 97 wt %, from about 93 wt % to about 97 wt %, or about 95 wt %) of the initiator-caprolactone mixture; The initiator is present in an amount from about 2 wt % to about 15 wt % (e.g., from about 3 wt % to about 10 wt %, from about 3 wt % to about 7 wt %, or about 5 wt %) of the initiator-caprolactone mixture; the caprolactone monomer is present in an amount from about 85 wt % to about 98 wt % (e.g., from about 90 wt % to about 97 wt %, from about 93 wt % to about 97 wt %, or about 95 wt %) of the reaction mixture; The initiator is present in an amount from about 2 wt % to about 13 wt % (e.g., from about 3 wt % to about 10 wt %, from about 3 wt % to about 7 wt %, or about 5 wt %) of the reaction mixture; The catalyst is present in an amount of about 0.001 wt % to about 5 wt % (e.g., about 0.001 wt % to about 5 wt %, about 0.001 wt % to about 4 wt %, about 0.001 wt % to about 3 wt %, about 0.001 wt % to about 2 wt %, about 0.001 wt % to about 1 wt %, about 0.001 wt % to about 0.5 wt %, about 0.001 wt % to about 0.25 wt %, about 0.1 wt % to about 5 wt %) of the reaction mixture. %, about 0.1 wt % to about 4 wt %, about 0.1 wt % to about 3 wt %, about 0.1 wt % to about 2 wt %, about 0.1 wt % to about 1 wt %, about 0.1 wt % to about 0.5 wt %, about 0.1 wt % to about 0.25 wt %, about 0.2 wt % to about 5 wt %, about 0.2 wt % to about 4 wt %, about 0.2 wt % to about 3 wt %, about 0.2 wt % to about 2 wt %, about 0.2 wt % to about 1 wt %, about 0 .2 wt % to about 0.5 wt %, about 0.5 wt % to about 5 wt %, about 0.5 wt % to about 4 wt %, about 0.5 wt % to about 3 wt %, about 0.5 wt % to about 2 wt %, about 0.5 wt % to about 1 wt %, about 0.75 wt % to about 5 wt %, about 0.75 wt % to about 4 wt %, about 0.75 wt % to about 3 wt %, about 0.75 wt % to about 2 wt %, about 0.75 wt % to about 1 wt %, about 1 wt % % to about 5 wt%, about 1 wt% to about 4 wt%, about 1 wt% to about 3 wt%, about 1 wt% to about 2 wt%, about 1.5 wt% to about 5 wt%, about 1.5 wt% to about 4 wt%, about 1.5 wt% to about 3 wt%, about 2 wt% to about 5 wt%, about 2 wt% to about 4 wt%, about 2 wt% to about 3 wt%, about 3 wt% to about 5 wt%, about 3 wt% to about 4 wt%, or about 4 wt% to about 5 wt%); The antioxidant or stabilizer is present in an amount of up to about 2 wt % (e.g., up to about 1.5 wt %, up to about 1 wt %, up to about 0.5 wt %, up to about 0.25 wt %, from about 0.1 wt % to about 2 wt %, from about 0.1 wt % to about 1.5 wt %, from about 0.1 wt % to about 1 wt %, from about 0.1 wt % to about 0.75 wt %, from about 0.1 wt % to about 0.5 wt %, or from about 0.1 wt % to about 0.25 wt %) of the reaction mixture; or Its combination.

7. The caprolactone polyol of any one of claims 1 to 6, wherein the caprolactone polyol has a molecular weight of about 2,000 g / mol (MW) to about 4500 MW (e.g., about 2,000 MW to about 4,000 MW or about 3,500 MW to about 4,000 MW).

8. The caprolactone polyol of any one of claims 1 to 7, wherein the caprolactone polyol comprises less than about 5% (e.g., less than about 4%, less than about 3%, less than about 2%, less than about 1%, less than about 0.5%, less than about 0.5%, less than about 0.25%, less than about 0.1%) caprolactone monomer.

9. The caprolactone polyol according to any one of claims 1 to 8, wherein the catalyst is a catalyst for ring-opening polymerization (e.g., zinc lactate, zinc oxide, zinc powder, diethyl zinc, tin lactate, tin oxide, tin dioxide, stannous oxide, stannous lactate, stannous octoate, stannous chloride, tin powder, propionic acid or tetrabutyl titanate, or a combination thereof).

10. A polyurethane material or adhesive (e.g., a polyurethane material or adhesive based on a caprolactone polyol) prepared by a process comprising reacting a caprolactone polyol according to any one of claims 1 to 9 and an isocyanate comprising two or more isocyanate groups (e.g., a diisocyanate or a polyisocyanate), thereby forming the polyurethane material.

11. The polyurethane material or adhesive of claim 10, wherein the method further comprises: (i) heating the caprolactone polyol and / or the isocyanate (e.g., to about 70°C to about 100°C, about 80°C to about 90°C, about 82°C to about 88°C, or about 85°C) prior to reacting with the isocyanate; (ii) drying the polyurethane material or adhesive; (iii) sparging the caprolactone polyol (e.g., sparging with nitrogen and / or sparging for about 0.5 hours to about 1.5 hours, about 0.75 hours to about 1.25 hours, or about 1 hour) prior to reacting; or (iv) a combination thereof.

12. The polyurethane material or adhesive according to claim 10 or 11, wherein reacting the caprolactone polyol and the isocyanate is carried out: (i) under bubbling (e.g., bubbling with nitrogen); (ii) under heating (e.g., reacting the caprolactone polyol and the isocyanate at 100°C to about 150°C (e.g., about 110°C to about 140°C, 115°C to about 135°C, or 120°C to 130°C)); (iii) for about 1.0 hour to about 3.0 hours (e.g., about 1.25 hours to about 2.75 hours, about 1.5 hours to about 2.5 hours, about 1.75 hours to about 1.25 hours, or about 2.0 hours); or (iv) a combination thereof.

13. The polyurethane material or adhesive according to any one of claims 10 to 12, wherein (i) the isocyanate is a monomer, oligomer, polymer, or a mixture thereof; (ii) the catalyst is a urethane catalyst (e.g., a tertiary amine compound, an amine having an isocyanate-reactive group, an organometallic compound, or a mixture thereof); or (iii) a combination thereof.

14. The polyurethane material or adhesive according to any one of claims 10 to 13, wherein the isocyanate comprises 2,2'-diphenylmethane diisocyanate; 2,4'-diphenylmethane diisocyanate; 4,4'-diphenylmethane diisocyanate (MDI); 3,3'-dimethyl-4,4'-diphenylidene diisocyanate (TODI); toluene diisocyanate (TDI); polymer MDI; modified liquid 4,4'-diphenylmethane diisocyanate; hexamethylene diisocyanate ("HDI"); 4,4'-dicyclohexylmethane diisocyanate ("HDI"); MDI”); isophorone diisocyanate ("IPDI"); p-phenylene diisocyanate ("PPDI"); m-phenylene diisocyanate ("MPDI"); tetramethylene diisocyanate; dodecane diisocyanate; octamethylene diisocyanate; decamethylene diisocyanate; cyclobutane-1,3-diisocyanate; 1,2-cyclohexane diisocyanate; 1,3-cyclohexane diisocyanate; 1,4-cyclohexane diisocyanate; 2,4-methylcyclohexane diisocyanate; 2,6-methylcyclohexane diisocyanate; 4,4'-dicyclohexyl diisocyanate; 2,4'-dicyclohexyl diisocyanate; 1,3,5-cyclohexane triisocyanate; isocyanato-methylcyclohexane isocyanate; isocyanatoethylcyclohexane isocyanate; bis(isocyanatomethyl)-cyclohexane diisocyanate; 4,4'-bis(isocyanatomethyl)dicyclohexane; 2,4'-bis(isocyanatomethyl)dicyclohexane; isophorone diisocyanate; 2,4-hexahydrotoluene diisocyanate; 2,6-hexahydrotoluene diisocyanate; 1,2-phenylene diisocyanate; 1,3-phenylene diisocyanate; 1,4-phenylene diisocyanate; triphenylmethane-4,4',4"-triisocyanate; naphthylene-1,5-diisocyanate; 2,4'-biphenyl diisocyanate; 4,4'-biphenyl diisocyanate; 2,2-biphenyl diisocyanate; polyphenylene polymethylene polyisocyanate ("PMDI"); m-tetramethylxylene diisocyanate ("m-TMXDI"); p-tetramethylxylene diisocyanate ("p-TMXDI"); or mixtures thereof.

15. The polyurethane material or adhesive of any one of claims 10 to 13, wherein the isocyanate comprises dimethylmethane-4,4'-diisocyanate (MDI).

16. The polyurethane material or adhesive according to any one of claims 10 to 15, wherein the catalyst is: (i) a tertiary amine catalyst (e.g., a tertiary amine catalyst present in an amount of about 0.02 wt % to about 5 wt % of the reaction mixture), the tertiary amine catalyst comprising triethylenediamine, N-methylmorpholine, N,N-dimethylcyclohexylamine, pentamethyldiethylenetriamine, tetramethylethylenediamine, bis(dimethylaminoethyl) ether, 1-methyl-4-dimethylaminoethyl-piperazine, 3-methoxy-N-dimethylpropylamine, N-ethylmorpholine; dimethylethanolamine, N-cocomorpholine, N,N-dimethyl-N',N'-dimethylisopropylpropylenediamine, N,N-diethyl-3-diethylamino-propylamine, dimethylbenzylamine, or a mixture thereof; (ii) an organometallic catalyst (e.g., an organometallic catalyst present in an amount of about 0.001 wt % to 1 wt % of the reaction mixture), the organometallic catalyst comprising an organobismuth, organomercury, organolead, organoferric, organotin catalyst, or a combination thereof (preferably, an organotin catalyst); (iii) a tin catalyst comprising stannous chloride, a tin carboxylate salt (e.g., dibutyltin dilaurate), stannous octoate, or a combination thereof; (iv) a catalyst comprising an alkali metal alkoxide, said catalyst being used to trimerize a polyisocyanate; or (v) combinations thereof.

17. The polyurethane material or adhesive of any one of claims 10 to 16, wherein the reactive polyurethane material or adhesive has an excess NCO (cyanate ester) content of at least about 1% (e.g., about 1% to about 5% or about 2% to about 3%).

18. The polyurethane material or adhesive according to any one of claims 10 to 17, wherein the polyurethane material is an adhesive (eg, a hot melt adhesive) or a polyurethane reactive adhesive (eg, a reactive hot melt adhesive).

19. A method for preparing caprolactone polyol, the method comprising: combining an initiator and a caprolactone monomer to form an initiator-caprolactone mixture or reaction mixture; adding a catalyst (e.g., a stannous octoate catalyst such as T-9) to the initiator-caprolactone mixture to form a reaction mixture; and polymerizing (e.g., ring-opening polymerization) the caprolactone monomers in the reaction mixture to thereby form the caprolactone polyol, The initiator comprises hydroquinone bis(2-hydroxyethyl) ether, dodecanediol (eg, 1,12-dodecanediol), pentaspirodiol, or a combination thereof.

20. A method of preparing a polyurethane material or adhesive, the method comprising reacting a caprolactone polyol according to any one of claims 1 to 9 and an isocyanate comprising two or more isocyanate groups (e.g., a diisocyanate or a polyisocyanate), thereby forming the polyurethane material.

21. A method of bonding a first substrate to a second substrate, the method comprising: applying the polyurethane material or adhesive according to any one of claims 10 to 18 to the first substrate, the second substrate, or both; and The first substrate and the second substrate are contacted with the polyurethane material or adhesive therebetween.

22. The method of claim 21, wherein applying the polyurethane material or adhesive is performed at about 120°C to about 160°C (eg, about 120°C to about 130°C).

23. The method of claim 21 or 22, further comprising: (i) applying pressure to the contacted first and second substrates; (ii) incubating the contacted first and second substrates; or (iii) a combination thereof.

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