Polycaprolactone polyols, polyurethanes, and methods for making and using them

Abstract

Described herein are caprolactone polyols and polyurethane materials or adhesives containing them. The caprolactone polyols are made by the process of mixing an initiator and caprolactone monomers 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 monomers in the reaction mixture to form a caprolactone polyol. The initiator includes hydroquinone bis(2-hydroxyethyl) ether, dodecanediol, pentaspiroglycol, or a combination thereof. The polyurethane materials or adhesives described herein have reduced open time, reduced viscosity, improved adhesion, and improved tensile strength compared to caprolactone polyols prepared without the disclosed initiators. Methods for making and using the caprolactone polyols and polyurethane materials or adhesives are also described herein.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to and the benefit of U.S. Provisional Patent Application No. 63 / 484,265, filed February 10, 2023, and U.S. Provisional Patent Application No. 63 / 490,692, filed March 16, 2023, each of which is incorporated by reference in its entirety for all purposes.

[0002] The present disclosure relates to caprolactone polyols, compositions comprising the caprolactone polyols of the present disclosure, such as polyurethane compositions and adhesives (e.g., hot melt adhesives and reactive hot melt adhesives), as well as methods of preparing and using the caprolactone polyols and compositions comprising same. [Background technology]

[0003] Reactive hot melt adhesives (RHMA) are an important sub-segment of the adhesives market, predicted to be worth $1.8 billion by 2025. Typical end uses for RHMA include flat lamination (wood bonding to decorative substrates), flooring applications (such as cork, nonwovens, and various plastics), edge banding, and bookbinding.

[0004] RHMA is a component of polyurethane adhesive formulations and is typically formulated with 1-5% excess monomeric isocyanate (NCO), but more commonly with 2-3% excess NCO content. Depending on the end use, the adhesive is applied at about 120°C to about 160°C (e.g., about 120°C to about 130°C) via a hot melt dispensing gun or nozzle connected to a melt tank. As the adhesive cools from the elevated temperature to ambient temperature, the rate of crystallization governs the initial bond strength (often referred to as green strength), while the rate of solidification determines the adhesive's "open time." Open time is the period from when the adhesive is applied to a substrate to when it is no longer capable of adhering to a second substrate.

[0005] After physical cooling and resulting solidification of the adhesive, a secondary moisture-cure mechanism occurs when excess NCO in the adhesive formulation reacts with moisture to convert the polymer into a thermoset material. The NCO reacts with moisture to form carbamic acids, which release CO2 and are converted to amines. The amines further react with the NCO to form urea bonds.

[0006] Adhesives made with alternatives to polyester polyols, such as current caprolactone-based polyol chemistries, have significantly longer open times than polyester polyols. Thus, there is a need in the adhesives market for alternatives to currently available polyester polyols and caprolactone polyols.

[0007] Polyurethane materials, or adhesives, are formed by reacting a hydroxyl-containing moiety (polyol) with an isocyanate-functional material. The structure of polyurethanes is segmented and can be described in terms of hard and soft domains / segments. In reactive hot melt adhesives (RHMAs), the hard domains, containing the isocyanate molecules, are often dimethrimethane-4,4'-diisocyanate (MDI), while the soft domains are dominated by the chemistry of a polyol, often a polyether, polyester, or caprolactone-based polyol.

[0008] RHMA is typically produced by adding polyol to a reactor and drying the product to remove residual moisture, then adding MDI to the polyol and reacting under vacuum to obtain the final polyurethane prepolymer with the desired excess NCO content.

[0009] The adhesive is applied to a first substrate at elevated temperature (about 120°C to about 130°C), and then a second substrate is brought into contact with the adhesive to bond the articles. The bonding mechanism is driven in two parts, with the initial bond strength (part 1) controlled by physical cooling of the adhesive, and the overall properties of the adhesive (part 2) determined by the outcome of the reaction between excess isocyanate and moisture present in the environment.

[0010] Thus, 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) with reduced open time, reduced viscosity, improved adhesion, and improved tensile strength compared to caprolactone polyols prepared without the disclosed initiators. The present disclosure further provides polyurethane compositions or adhesives comprising the disclosed caprolactone polyols, as well as methods for making the disclosed caprolactone polyols and the disclosed polyurethane compositions or adhesives. Summary of the Invention

[0011] Presently, multifunctional polyol resins, curable compositions containing multifunctional polyol resins, polyurethane resins, and melamine-based resins derived from multifunctional polyol resins, methods for their preparation, and their uses have been described.

[0012] Thus, in one embodiment, the present disclosure provides a caprolactone polyol made by a process comprising: mixing an initiator and caprolactone monomers 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 (e.g., ring-opening polymerization) the caprolactone monomers in the reaction mixture, thereby forming the caprolactone polyol; wherein the initiator comprises hydroquinone bis(2-hydroxyethyl) ether, dodecanediol (e.g., 1,12-dodecanediol), pentaspiroglycol, or a combination thereof.

[0013] Another aspect of the present disclosure provides a method for making the caprolactone polyol of the present disclosure, the method including: mixing an initiator and 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 (e.g., ring-opening polymerization) the caprolactone monomer in the reaction mixture to thereby form the caprolactone polyol, wherein the initiator includes hydroquinone bis(2-hydroxyethyl) ether, dodecanediol (e.g., 1,12-dodecanediol), pentaspiroglycol, or a combination thereof.

[0014] In any aspect or embodiment described herein, the process further includes (i) sparging the initiator-caprolactone mixture before adding the catalyst (e.g., sparging the initiator-caprolactone mixture with nitrogen), (ii) incubating the initiator-caprolactone mixture before adding the catalyst (e.g., incubating the initiator-caprolactone mixture 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 while sparking), (ii) 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.

[0015] In any aspect or embodiment described herein, the polymerization was carried out (i) using reflux, (ii) at about 150°C to about 190°C (e.g., about 150°C to about 180°C), (iii) for about 4 to about 6 hours, or (iv) a combination thereof.

[0016] In any aspect or embodiment described herein, the process further includes 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, e.g., to about 150°C to about 190°C, e.g., about 150°C to about 160°C), thereby forming a caprolactone polyol.

[0017] 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) (Irganox® 1010), a phosphite antioxidant and / or stabilizer, bis(2,4-di-tert-butylphenol)pentaerythritol diphosphate (such as Irgafos® 126), a hydrolysis inhibitor (Stabaxol® I), an acid scavenger (Stabaxol® I), a carbodiimide (such as a monomeric carbodiimide), or a combination thereof).

[0018] In any aspect or embodiment described herein, the caprolactone monomer is present in an amount of about 85% to about 98% by weight of the initiator-caprolactone mixture (e.g., about 90% to about 97% by weight, about 93% to about 97% by weight, or about 95% by weight), the initiator is present in an amount of about 2% to about 15% by weight of the initiator-caprolactone mixture (e.g., about 3% to about 10% by weight, about 3% to about 7% by weight, or about 5% by weight), and the caprolactone monomer is present in an amount of about 85% to about 98% by weight of the reaction mixture. % (e.g., about 90% to about 97% by weight, about 93% to about 97% by weight, or about 95% by weight) of the reaction mixture, the initiator is present in an amount of about 2% to about 13% by weight (e.g., about 3% to about 10% by weight, about 3% to about 7% by weight, or about 5% by weight) of the reaction mixture, and the catalyst is present in an amount of about 0.001% to about 5% by weight (e.g., about 0.001% to about 5% by weight, about 0.001% to about 4% by weight, about 0.001% to about 3% by weight, about 0.001% to about 2% by weight, or about 0.001% to about 1% by weight, approximately 0.001% to approximately 0.5% by weight, approximately 0.001% to approximately 0.25% by weight, approximately 0.1% to approximately 5% by weight, approximately 0.1% to approximately 4% by weight, approximately 0.1% to approximately 3% by weight, approximately 0.1% to approximately 2% by weight, approximately 0.1% to approximately 1% by weight, approximately 0.1% to about 0.5% by weight, about 0.1% to about 0.25% by weight, about 0.2% to about 5% by weight, about 0.2% to about 4% by weight, about 0.2% to about 3% by weight, about 0.2% to about 2% by weight, about 0.2% to about 1% by weight, about 0.2% to about 0.5% by weight Weight%, about 0.5% to about 5% by weight, about 0.5% to about 4% by weight, about 0.5% to about 3% by weight, about 0.5% to about 2% by weight, about 0.5% to about 1% by weight, about 0.75% to about 5% by weight, about 0.75% to about 4% by weight, about 0.75% to about 4% by weight 3% by weight, about 0.75% to about 2% by weight, about 0.75% to about 1% by weight, about 1% to about 5% by weight, about 1% to about 4% by weight, about 1% to about 3% by weight, about 1% to about 2% by weight, about 1.5% to about 5% by weight, about 1.5% to about 4% by weight, about 1.The antioxidant or stabilizer is present in an amount of up to about 2% by weight of the reaction mixture (e.g., up to about 1.5% by weight, up to about 1% by weight, up to about 0.5% by weight, up to about 0.25% by weight, about 0.1% by weight to about 2% by weight, about 0.1% by weight to about 1.5% by weight, about 0.1% by weight to about 1% by weight, about 0.1% by weight to about 0.75% by weight, about 0.1% by weight to about 0.5% by weight, or about 0.1% by weight to about 0.25% by weight), or combinations thereof.

[0019] In any aspect or embodiment described herein, the caprolactone polyol has a molecular weight of about 2,000 g / mol (MW) to about 4,500 MW (e.g., about 2,000 MW to about 4,000 MW or about 3,500 MW to about 4,000 MW).

[0020] 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.

[0021]

[0049] In any aspect or embodiment described herein, 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, propanoic acid, or tetrabutyl titanate, or a combination thereof).

[0022] A further aspect of the present disclosure provides a polyurethane material or adhesive (e.g., a caprolactone polyol-based polyurethane material or adhesive) made by a process comprising reacting a caprolactone polyol of the present disclosure with an isocyanate (e.g., a diisocyanate or polyisocyanate) containing two or more isocyanate groups, thereby forming a polyurethane material.

[0023] An additional aspect of the present disclosure provides a method of making a polyurethane material or adhesive of the present disclosure, the method comprising reacting a caprolactone polyol of the present disclosure with an isocyanate (e.g., a diisocyanate or polyisocyanate) containing two or more isocyanate groups, thereby forming a polyurethane material.

[0024] In any aspect or embodiment described herein, the process further includes (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) before 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) before reacting; or (iv) a combination thereof.

[0025] In any aspect or embodiment described herein, the reaction of the caprolactone polyol with the isocyanate is carried out with (i) sparging (e.g., sparging with nitrogen), (ii) heating (e.g., reacting the caprolactone polyol with 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.

[0026] In any aspect or embodiment describe herein, (i) the isocyanate is monomeric, oligomeric, polymeric, or a mixture thereof; (ii) the catalyst is a urethane catalyst (e.g., a tertiary amine compound, an amine having isocyanate-reactive group(s), an organometallic compound, or a mixture thereof); or (iii) a combination thereof.

[0027]

[0033] In any aspect or embodiment described herein, the isocyanate is selected from the group consisting of 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 3,3'-dimethyl-4,4'-biphenylene diisocyanate (TODI), toluene diisocyanate (TDI), polymeric MDI, modified liquid 4,4'-diphenylmethane diisocyanate, hexamethylene-diisocyanate ("HDI"), 4,4'-dicyclohexylmethane diisocyanate ("HDI"). 12MDI"), isophorone diisocyanate ("IPDI"), para-phenylene diisocyanate ("PPDI"), meta-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, isocyanatomethylcyclohexane isocyanate, isocyanatoethylcyclohexane isocyanate, bis(isocyanatomethyl)-cyclohexane 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, polyphenylpolymethylene polyisocyanate ("PMDI"), meta-tetramethylxylene diisocyanate ("m-TMXDI"), para-tetramethylxylene diisocyanate ("p-TMXDI"), or mixtures thereof.

[0028]

[0041] In any aspect or embodiment describe herein, the isocyanate comprises dimethrimethane-4,4'-diisocyanate (MDI).

[0029]

[0044] In any aspect or embodiment described herein, the catalyst is (i) a tertiary amine catalyst (e.g., a reaction catalyst) including 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, (ii) an organometallic catalyst (e.g., an organometallic catalyst present in an amount of about 0.001 to 1% by weight of the reaction mixture) including an organobismuth, organomercury, organolead, organoferric, or organotin catalyst, or a combination thereof (preferably an organotin catalyst); (iii) a tin catalyst including stannous chloride, a tin salt of a carboxylic acid (e.g., dibutyltin dilaurate), stannous octoate, or a combination thereof; (iv) a catalyst for the trimerization of polyisocyanates including an alkali metal alkoxide; or (v) a combination thereof.

[0030] In any aspect or embodiment described herein, the reactive polyurethane material or adhesive has an excess NCO (cyanate) 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%).

[0031] In any aspect or embodiment described herein, the polyurethane material is an adhesive (e.g., a hot melt adhesive) or a polyurethane reactive adhesive (e.g., a reactive hot melt adhesive).

[0032] An additional aspect of the present disclosure provides a method of bonding a first substrate and a second substrate, the method comprising applying a polyurethane material of the present disclosure to the first substrate, the second substrate, or the first and second substrates, and contacting the first substrate and the second substrate with the polyurethane material located therebetween.

[0033] In any aspect or embodiment described herein, the method further includes (i) applying pressure to the contacted first substrate and second substrate, (ii) incubating the contacted first substrate and second substrate, or (iii) a combination thereof.

[0034] The foregoing general fields of application are provided merely as examples and are not intended to limit the scope of the present disclosure and the appended claims. Additional objects and advantages associated with the compositions, methods, and processes of the present disclosure will be understood by those skilled in the art in light of the claims, description, and examples. For example, the various aspects and embodiments of the present disclosure can be utilized in numerous combinations, all of which are expressly contemplated by the present disclosure. These additional advantageous objects and embodiments are expressly included within the scope of the present disclosure. Publications and other materials used herein to clarify the background of the invention, particularly to provide additional details regarding its practice, are incorporated by reference.

[0035] The accompanying drawings, which are incorporated in and form 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 drawings are only for the purpose of illustrating embodiments of the present disclosure and are not to be construed as limiting the disclosure. Further objects, features, and advantages of the present disclosure will become apparent from the following detailed description taken in conjunction with the accompanying drawings showing exemplary embodiments of the present disclosure. [Brief explanation of the drawings]

[0036] [Figure 1]Measurement of open time of exemplary reactive hot melt adhesives formulated with 3% excess NCO. Time is expressed in minutes and seconds. [Figure 2] Fmax (N / mm2) lap shear bond of each adhesive investigated on aluminum, polycarbonate, and beech wood. [Figure 3] Viscosity (mPa·s) of various adhesives measured by Brookfield with spindle 27. [Figure 4] Tensile strength, Fmax (N / mm2) of each adhesive under test. DETAILED DESCRIPTION OF THE INVENTION

[0037] The present disclosure will now be described more fully below, although not all embodiments of the disclosure are shown. While the present disclosure has been described with reference to exemplary embodiments, it will be understood by those skilled in the art that various changes can be made and equivalents can be substituted for elements thereof without departing from the scope of the present disclosure. In addition, many modifications can be made to adapt a particular structure or material to the teachings of the present disclosure without departing from the essential scope of the present disclosure.

[0038] When a range of values ​​is provided, it is understood that each intervening value between the upper and lower limit of that range, and any other stated or intervening value in that stated range, is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included in the smaller ranges and are also encompassed within the invention, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the disclosure.

[0039] The following terms are used to describe the present invention. If a term is not specifically defined herein, the term is given its art-recognized meaning by those of ordinary skill in the art who apply the term in connection with its use in describing the present invention.

[0040] As used in this specification and the appended claims, the articles "a" and "an" are used herein to refer to one or to more than one (i.e., to at least one) of the grammatical object of the article, unless the context clearly indicates otherwise. By way of example, "an element" means one element or more than one element.

[0041] As used in this specification and the claims, the term "and / or" should be understood to mean "either or both" of the elements so conjoined, i.e., elements that are conjunctively present in some instances and disjunctively present in other instances. Multiple elements listed with "and / or" should be construed in the same manner, i.e., "one or more" of the elements so conjoined. Other elements, whether related or unrelated to the elements specifically identified in the "and / or" clause, may optionally be present other than those elements. Thus, as a non-limiting example, a reference to "A and / or B," when used in conjunction with open-ended language such as "comprising," may, in one embodiment, refer to A only (optionally including elements other than B); in another embodiment, refer to B only (optionally including elements other than A); in yet another embodiment, refer to both A and B (optionally including other elements); and so forth.

[0042] As used herein and in the claims, "or" should be understood to have the same meaning as "and / or" as defined above. For example, when separating items in a list, "or" or "and / or" should be interpreted as being inclusive, i.e., including at least one element, but also including two or more of a number or list of elements, and possibly additional unlisted items. Only terms clearly indicated to the contrary, such as "only one of" or "exactly one of," or, when used in the claims, "consisting of," will refer to the inclusion of exactly one element of a number or list. Generally, as used herein, the term "or" will be interpreted as indicating exclusive alternatives ("either / or, "either / or," "only one of," "exactly either / or," etc.) only when preceded by a condition of exclusivity (e.g., "either / or," "either / or," "exactly either / or," etc.).

[0043] As used herein in the specification and claims, "at least one" in reference to a list of one or more elements should be understood to mean at least one element selected from any one or more of the elements in the list of elements, but not necessarily including at least one of each and every element specifically listed within the list of elements, and not excluding any combinations of elements in the list of elements. This definition also allows for elements to optionally be present other than those specifically identified in the list of elements to which the phrase "at least one" refers, whether related or unrelated to the specifically identified elements. Thus, as a non-limiting example, "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" can refer in one embodiment to at least one A (or optionally more than one) with no B (which may include elements other than B); in another embodiment to at least one B (or optionally more than one) and no A (optionally including elements other than A); and in yet another embodiment to at least one A (or optionally more than one) and at least one B (or optionally more than one) (optionally including other elements).

[0044] In the claims and the above specification, all transitional phrases such as "comprise," "include," "mount," "have," "contain," "accompany," "hold," "consisting of," and the like, should be understood to be open-ended, i.e., to mean "including, but not limited to." As set forth in Section 2111.03 of the United States Patent Office Manual of Examining Procedures, only the transitional phrases "consisting of" and "consisting essentially of" are exclusive or semi-exclusive transitional phrases, respectively.

[0045] As used herein in the specification and claims, the phrase "at least one" in reference to a list of one or more elements should be understood to mean at least one element selected from one or more of the elements in the list of elements, but not necessarily including at least one of each and every element specifically listed within the list of elements, and not excluding any combinations of elements in the list of elements. This definition also allows for the optional presence of elements other than those specifically identified in the list of elements to which the phrase "at least one" refers, whether related or unrelated to the specifically identified elements. Thus, as a non-limiting example, "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" can refer, in one embodiment, to at least one A (or optionally more than one) with no B (which may include elements other than B); in another embodiment, to at least one B (or optionally more than one) and no A (optionally including elements other than A); and in yet another embodiment, to at least one A (or optionally more than one) and at least one B (or optionally more than one) (optionally including other elements). It should also be understood that, unless expressly stated to the contrary, for any method claimed herein that includes multiple steps or actions, the order of the method steps or actions is not necessarily limited to the order in which the method steps or actions are recited.

[0046] Surprisingly and unexpectedly, the inventors have discovered that the caprolactone polyols of the present disclosure provide polyurethane materials or adhesives having reduced open time, reduced viscosity, improved adhesion, and improved tensile strength compared to caprolactone polyols prepared without the initiators of the present disclosure. In any aspect or embodiment described herein, the caprolactone polyol is made by a process including mixing an initiator and 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 (e.g., ring-opening polymerization) the caprolactone monomer in the reaction mixture to thereby form the caprolactone polyol, wherein the initiator includes hydroquinone bis(2-hydroxyethyl) ether, dodecanediol (e.g., 1,12-dodecanediol), pentaspiroglycol, or a combination thereof.

[0047] Caprolactone polyol and method for producing the same disclosed herein One aspect of the present disclosure provides a caprolactone polyol made by a process including mixing an initiator and 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 (e.g., ring-opening polymerization) the caprolactone monomer in the reaction mixture, thereby forming the caprolactone polyol, wherein the initiator includes hydroquinone bis(2-hydroxyethyl) ether, dodecanediol (e.g., 1,12-dodecanediol), pentaspiroglycol, or a combination thereof.

[0048] Another aspect of the present disclosure provides a method for making the caprolactone polyol of the present disclosure, the method including: mixing an initiator and 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 (e.g., ring-opening polymerization) the caprolactone monomer in the reaction mixture to thereby form the caprolactone polyol, wherein the initiator includes hydroquinone bis(2-hydroxyethyl) ether, dodecanediol (e.g., 1,12-dodecanediol), pentaspiroglycol, or a combination thereof.

[0049] In any aspect or embodiment described herein, the process further includes (i) sparging the initiator-caprolactone mixture before adding the catalyst (e.g., sparging the initiator-caprolactone mixture with nitrogen), (ii) incubating the initiator-caprolactone mixture before adding the catalyst (e.g., incubating the initiator-caprolactone mixture 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 while sparking), (ii) 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.

[0050] In any aspect or embodiment described herein, the polymerization was carried out (i) using reflux, (ii) at about 150°C to about 190°C (e.g., about 150°C to about 180°C), (iii) for about 4 to about 6 hours, or (iv) a combination thereof.

[0051] In any aspect or embodiment described herein, the process further includes 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, e.g., to about 150°C to about 190°C, e.g., about 150°C to about 160°C), thereby forming a caprolactone polyol.

[0052] 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) (Irganox® 1010), a phosphite antioxidant and / or stabilizer, bis(2,4-di-tert-butylphenol)pentaerythritol diphosphate (such as Irgafos® 126), a hydrolysis inhibitor (Stabaxol® I), an acid scavenger (Stabaxol® I), a carbodiimide (such as a monomeric carbodiimide), or a combination thereof).

[0053] In any aspect or embodiment described herein, the caprolactone monomer is present in an amount of about 85% to about 98% by weight of the initiator-caprolactone mixture (e.g., about 90% to about 97% by weight, about 93% to about 97% by weight, or about 95% by weight), the initiator is present in an amount of about 2% to about 15% by weight of the initiator-caprolactone mixture (e.g., about 3% to about 10% by weight, about 3% to about 7% by weight, or about 5% by weight), and the caprolactone monomer is present in an amount of about 85% to about 98% by weight of the reaction mixture. % (e.g., about 90% to about 97% by weight, about 93% to about 97% by weight, or about 95% by weight) of the reaction mixture, the initiator is present in an amount of about 2% to about 13% by weight (e.g., about 3% to about 10% by weight, about 3% to about 7% by weight, or about 5% by weight) of the reaction mixture, and the catalyst is present in an amount of about 0.001% to about 5% by weight (e.g., about 0.001% to about 5% by weight, about 0.001% to about 4% by weight, about 0.001% to about 3% by weight, about 0.001% to about 2% by weight, or about 0.001% to about 1% by weight, approximately 0.001% to approximately 0.5% by weight, approximately 0.001% to approximately 0.25% by weight, approximately 0.1% to approximately 5% by weight, approximately 0.1% to approximately 4% by weight, approximately 0.1% to approximately 3% by weight, approximately 0.1% to approximately 2% by weight, approximately 0.1% to approximately 1% by weight, approximately 0.1% to about 0.5% by weight, about 0.1% to about 0.25% by weight, about 0.2% to about 5% by weight, about 0.2% to about 4% by weight, about 0.2% to about 3% by weight, about 0.2% to about 2% by weight, about 0.2% to about 1% by weight, about 0.2% to about 0.5% by weight Weight%, about 0.5% to about 5% by weight, about 0.5% to about 4% by weight, about 0.5% to about 3% by weight, about 0.5% to about 2% by weight, about 0.5% to about 1% by weight, about 0.75% to about 5% by weight, about 0.75% to about 4% by weight, about 0.75% to about 4% by weight 3% by weight, about 0.75% to about 2% by weight, about 0.75% to about 1% by weight, about 1% to about 5% by weight, about 1% to about 4% by weight, about 1% to about 3% by weight, about 1% to about 2% by weight, about 1.5% to about 5% by weight, about 1.5% to about 4% by weight, about 1.The antioxidant or stabilizer is present in an amount of up to about 2% by weight of the reaction mixture (e.g., up to about 1.5% by weight, up to about 1% by weight, up to about 0.5% by weight, up to about 0.25% by weight, about 0.1% by weight to about 2% by weight, about 0.1% by weight to about 1.5% by weight, about 0.1% by weight to about 1% by weight, about 0.1% by weight to about 0.75% by weight, about 0.1% by weight to about 0.5% by weight, or about 0.1% by weight to about 0.25% by weight), or combinations thereof.

[0054] In any aspect or embodiment described herein, the caprolactone polyol has a molecular weight of about 2,000 g / mol (MW) to about 4,500 MW (e.g., about 2,000 MW to about 4,000 MW or about 3,500 MW to about 4,000 MW).

[0055] 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.

[0056]

[0049] In any aspect or embodiment described herein, 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, propanoic acid, or tetrabutyl titanate, or a combination thereof).

[0057] As used herein, the term "caprolactone" is intended to encompass unsubstituted and substituted caprolactone. The term "ε-caprolactone" is intended to encompass unsubstituted and substituted ε-caprolactone. Unsubstituted ε-caprolactone is particularly preferred.

[0058] In any aspect or embodiment described herein, the copolymerization can include copolymerization of caprolactone, particularly ε-caprolactone, with a mixture of different caprolactones, such as a mixture of substituted and unsubstituted caprolactones, or a mixture of caprolactones with different substituents.

[0059] In any aspect or embodiment described herein, substituted ε-caprolactone monomers that may be used to prepare caprolactone polyols include C 1-12 Alkyl-substituted ε-caprolactone, C 1-12 Alkenyl-substituted ε-caprolactone, C 1-12 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.

[0060] In any aspect or embodiment described herein, substituted ε-caprolactone monomers that can be used to produce the auxiliary caprolactone polyol include mono-, di-, or tri-substituted 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.

[0061] Polyurethane materials or adhesives of the present disclosure and methods of making same A further aspect of the present disclosure provides a polyurethane material or adhesive (e.g., a caprolactone polyol-based polyurethane material or adhesive) made by a process comprising reacting a caprolactone polyol of the present disclosure with an isocyanate (e.g., a diisocyanate or polyisocyanate) containing two or more isocyanate groups, thereby forming a polyurethane material.

[0062] An additional aspect of the present disclosure provides a method of making a polyurethane material or adhesive of the present disclosure, the method comprising reacting a caprolactone polyol of the present disclosure with an isocyanate (e.g., a diisocyanate or polyisocyanate) containing two or more isocyanate groups, thereby forming a polyurethane material.

[0063] In any aspect or embodiment described herein, the process further includes (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) before 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) before reacting; or (iv) a combination thereof.

[0064] In any aspect or embodiment described herein, the reaction of the caprolactone polyol with the isocyanate is carried out with (i) sparging (e.g., sparging with nitrogen), (ii) heating (e.g., reacting the caprolactone polyol with 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.

[0065] In any aspect or embodiment describe herein, (i) the isocyanate is monomeric, oligomeric, polymeric, or a mixture thereof; (ii) the catalyst is a urethane catalyst (e.g., a tertiary amine compound, an amine having isocyanate-reactive group(s), an organometallic compound, or a mixture thereof); or (iii) a combination thereof.

[0066]

[0033] In any aspect or embodiment described herein, the isocyanate is selected from the group consisting of 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 3,3'-dimethyl-4,4'-biphenylene diisocyanate (TODI), toluene diisocyanate (TDI), polymeric MDI, modified liquid 4,4'-diphenylmethane diisocyanate, hexamethylene-diisocyanate ("HDI"), 4,4'-dicyclohexylmethane diisocyanate ("HDI"). 12MDI"), isophorone diisocyanate ("IPDI"), para-phenylene diisocyanate ("PPDI"), meta-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, isocyanatomethylcyclohexane isocyanate, isocyanatoethylcyclohexane isocyanate, bis(isocyanatomethyl)-cyclohexane 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, polyphenylpolymethylene polyisocyanate ("PMDI"), meta-tetramethylxylene diisocyanate ("m-TMXDI"), para-tetramethylxylene diisocyanate ("p-TMXDI"), or mixtures thereof.

[0067]

[0041] In any aspect or embodiment describe herein, the isocyanate comprises dimethrimethane-4,4'-diisocyanate (MDI).

[0068]

[0044] In any aspect or embodiment described herein, the catalyst is (i) a tertiary amine catalyst (e.g., a reaction catalyst) including 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, (ii) an organometallic catalyst (e.g., an organometallic catalyst present in an amount of about 0.001 to 1% by weight of the reaction mixture) including an organobismuth, organomercury, organolead, organoferric, or organotin catalyst, or a combination thereof (preferably an organotin catalyst); (iii) a tin catalyst including stannous chloride, a tin salt of a carboxylic acid (e.g., dibutyltin dilaurate), stannous octoate, or a combination thereof; (iv) a catalyst for the trimerization of polyisocyanates including an alkali metal alkoxide; or (v) a combination thereof.

[0069] In any aspect or embodiment described herein, the reactive polyurethane material or adhesive has an excess NCO (cyanate) 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%).

[0070] In any aspect or embodiment described herein, the polyurethane material is an adhesive (e.g., a hot melt adhesive) or a polyurethane reactive adhesive (e.g., a reactive hot melt adhesive).

[0071] As used herein, "hot melt adhesive" refers to a reactive hot melt adhesive composition that is heated to obtain a liquid of flowable viscosity and cooled to obtain a solid after application to a substrate. After the hot melt adhesive is cooled below its melting temperature or below its solidification transition temperature and solidifies, an adhesive bond is formed between the substrate and the adhesive material.

[0072] Hot melt adhesives are often used to bond two substrates together and maintain them in a fixed relationship to one another. Hot melt adhesives are also used in articles that include nonwoven layers to bond the nonwoven layer to a polymeric film layer. Hot melt adhesives are further used to bond packaging structures (e.g., bags, boxes, cartons, cases, and trays) together to construct the package, close the package, or both. They are also used as pressure-sensitive adhesives for tapes and labels.

[0073] Properties that may be generally required of hot melt adhesives in commercial applications are adhesive properties, open time, setting time, and open time. The adhesive properties of a hot melt adhesive during use must be good, because loss of adhesion can lead to, for example, unacceptable package opening during and after production. Therefore, the adhesion of a hot melt adhesive should be good over time and over a wide range of conditions.

[0074] A further characteristic of hot melt adhesives is their set time, which is the time required for the adhesive to form a bond with a substrate. The set time can be important in commercial operations to control the time required to press two substrates together to sandwich the adhesive. In any aspect or embodiment described herein, the set time can be on the order of seconds. For example, in any aspect or embodiment described herein, the set time can be 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, between about 5 seconds and about 60 seconds, between about 5 seconds and about 50 seconds, between about 5 seconds and about 40 seconds, between about 5 seconds and about 30 seconds, between about 5 seconds and about 20 seconds, between about 5 seconds and about 10 seconds, between about 10 seconds and about 60 seconds, or between about 5 seconds and about 60 seconds. 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.

[0075] While the set time may preferably be very short, hot melt adhesives also exhibit some open time, which is the time after application of the adhesive at an elevated temperature during which the adhesive still has flow properties. As noted above, this period (open time) is the time from when the adhesive is applied to a substrate to when adhesion to a second substrate is no longer possible. For example, in any aspect or embodiment described herein, the open time may be 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, between about 3 minutes and about 7 minutes, between about 3 minutes and about 6.5 minutes, between about 3 minutes and about 6 minutes, between about 3 minutes and about 5 minutes, between about 3 minutes and about 4 minutes, between about 4 minutes and about 7 minutes, between about 4 minutes and about 6.5 minutes, between about 4 minutes and about 6 minutes, between about 4 minutes and about 5 minutes, between about 5 minutes and about 7 minutes, between about 5 minutes and about 6.5 minutes, between about 5 minutes and about 6 minutes, or between about 6 minutes and about 7 minutes.

[0076] Methods of using the polyurethane materials or adhesives of the present disclosure One aspect of the present disclosure provides a method of bonding a first substrate and a second substrate, the method comprising applying a polyurethane material of the present disclosure to the first substrate, the second substrate, or the first and second substrates, and contacting the first substrate and the second substrate with the polyurethane material located therebetween. In any aspect or embodiment described herein, the method further includes (i) applying pressure to the contacted first substrate and second substrate, (ii) incubating the contacted first substrate and second substrate, or (iii) a combination thereof.

[0077] In any aspect or embodiment described herein, the method is for performing flat lamination (wood bonding to decorative substrates), flooring application (cork, nonwoven fabrics, various plastics, etc.), edge banding, and bookbinding. In any aspect or embodiment described herein, the method is a method of flat lamination, a method of applying flooring, a method of edge banding, or a method of bookbinding.

[0078] Example The details of the examples are intended as further embodiments of the described methods and compositions. Accordingly, the details described herein are incorporated into the detailed description as alternative embodiments. It was a surprising and unexpected discovery that the caprolactone polyols of the present disclosure produce polyurethane materials or adhesives with reduced viscosity, improved adhesion, and improved tensile strength, while also having reduced open time, compared to caprolactone polyols prepared without the initiators of the present disclosure.

[0079] A commercially available caprolactone product, Capa™ 2403D, containing three novel caprolactone diols of the same molecular weight (4000 g / mol), was investigated and benchmarked against DYNACOLL® 7360, a 3500 molecular weight polyester polyol (HDO / AA). The characteristics of the compositions investigated are shown in Table 1. [Table 1]

[0080] Example 1. Synthesis of hydroquinone bis(2-hydroxyethyl) ether (HQEE) polyol, pentaspiroglycol (PSG) polyol, and dodecanediol polyol Hydroquinone bis(2-hydroxyethyl) ether (HQEE), pentaspiroglycol (PSG), and dodecanediol were investigated 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. RHMAs were prepared and characterized using the exemplary caprolactone polyols, as discussed in more detail below. [Table 2]

[0081] Approximately 4000 MW caprolactone polyol was prepared using the initiator HQEE. The reagents for the reaction are shown in Table 3 below. Briefly, HQEE, antioxidant, and caprolactone monomer were combined, charged, and sparged at 90°C / 15 mbar. The water content was measured at 0.010%. After 60 minutes of incubation, the mixture was heated to 160°C (240 mbar). T9 catalyst (8 ppm) was added to the mixture, and the temperature was increased to 180°C (240 mbar). After 4.5 hours of incubation, refluxing was terminated. The monomer content was measured as 0.041%. The mixture was cooled and decanted for testing / characterization (data shown below). [Table 3] *Pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate). **Bis(2,4-di-tert-butylphenol)pentaerythritol diphosphite.

[0082] An exemplary HQEE-initiated caprolactone polyol had the following characteristics: 0.017% water, 3988 MW (g / mol), 28.13 mg KOH / g hydroxyl value (OHV), 0.05 mg KOH / g acid value (AV), 28.183 mg KOH / g corrected OHV (COHV), 10 HU color, and 0.41% monomer content.

[0083] During the synthesis of HQEE-initiated caprolactone polyols, Irganox® 1010 (a sterically hindered phenol primary antioxidant and co-stabilizer) and Irgafos® 126 (bis(2,4-di-tert-butylphenol) pentaerythritol diphosphate) were utilized. The combination of these additives was demonstrated to provide thermo-oxidative stability and prevent discoloration during ring-opening polymerization.

[0084] Approximately 4000 nm of caprolactone polyol was prepared using the initiator pentaspiroglycol (PSG). The reagents for the reaction are listed in Table 4 below. Caprolactone monomer and PSG were charged to a clean 20 L reactor under a positive flow of N2. After 2 hours, the mixture was heated to 80°C and full vacuum was applied to induce sparging. After 4 hours, the vacuum and heat were removed, and the mixture was left in the reactor overnight. After overnight incubation, the mixture was heated to 160°C. After 2 hours at 160°C, 6 ppm equivalent of catalyst solution was added to the mixture, and the reactor was heated to 180°C for reaction. The pressure was reduced until a light reflux was observed at 160 mbar. After 3 hours and 10 minutes, the pressure was released, and the reactor was cooled to 80°C and incubated overnight. After overnight incubation, 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 and tested for acid number. The acid number was 0.23 mg KOH / g. The reactor was set to 140°C, Stabaxol® I was added, and full vacuum was applied for a 30-minute acid treatment. The vacuum was removed and the heat was set to 80°C. After an overnight incubation, 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. [Table 4]

[0085] An exemplary PSG-initiated caprolactone polyol had the following characteristics: 0.061% water, hydroxyl number (OHV) of 27.53 mg KOH / g, acid number (AV) of 0.022 mg KOH / g, color of 28 HU, and monomer content of 0.26%.

[0086] Approximately 4000 MW caprolactone polyol was prepared using the initiator 1,12-dodecanediol. The reagents for the reaction are shown in Table 5 below. Briefly, caprolactone monomer and 1,12-dodecanediol were charged to a 3 L reaction vessel under a N2 flow. The temperature was set to 80°C. Sparging was initiated at 80°C under full vacuum. The water content was measured to be 0.019%. T9 catalyst (6 ppm) was added and reflux was initiated at 173°C (148 mbar). The vacuum was removed and the temperature was allowed to cool overnight.

[0087] Reflux was resumed at 155°C (73 mbar) and an additional 6 ppm of T9 catalyst (12 ppm total) was added. Full vacuum was achieved. The vacuum was removed and the mixture was allowed to cool overnight. The monomer content was measured as 0.226%. The product was discharged at 80°C for testing / characterization (data shown below). [Table 5]

[0088] An exemplary 1,12-dodecanediol-initiated caprolactone polyol had the following characteristics: waxy solid at room temperature, slightly yellow viscous liquid at 80°C, 0.019% water, MW (g / mol), hydroxyl number (OHV) of 26.88 mg KOH / g, acid number (AV) of 0.132 mg KOH / g, corrected OHV (COHV) of 27.01 mg KOH / g, color of 49 HU, and monomer content of 0.226%.

[0089] Example 2. Synthesis of reactive hot melt adhesive A reactive hot melt adhesive with an excess content of 3% NCO was prepared using Capa™ 2403D, a 4000 MW HQEE-initiated caprolactone polyol, a 4000 MW PSG-initiated caprolactone polyol, and a 4000 MW dodecanediol-initiated caprolactone polyol. Briefly, the polyols, a pressure-equalizing dropping funnel, and methylene diphenyl diisocyanate (MDI) were preheated to 85° C. in an oven.

[0090] One mL of pre-dissolved polyol was added to a Karl Fisher titration vessel (hereafter "vessel"). Polyol (650 g) was weighed back into the round-bottom flask using a funnel. Nitrogen was turned on at an inlet below the polyol surface, the stir bar was set at 100 revolutions per minute (RPM) at 120 °C or 130 °C (depending on the given temperature), and vacuum was applied for 1 hour.

[0091] MDI (117.09 g) at 85°C was weighed into a preheated addition funnel. The addition funnel was added to the vessel, and the addition funnel valve was fully opened to rapidly add the MDI. The addition funnel was then removed once the MDI addition was complete. The mixture was allowed to react at 200 RPM for 1 hour 45 minutes to 2 hours 15 minutes.

[0092] The stir bar was turned off and a vacuum was applied to degas the prepolymer using the same method as discussed above. Once degassing was complete, the vacuum was turned off, the stir bar was stopped, the vessel was removed from the apparatus, and the isocyanate prepolymer was dispensed into a 250 mL storage canister. The isocyanate prepolymer was blanketed with nitrogen, the storage canister was capped, and stored at room temperature in a moisture-proof bag.

[0093] The NCO of the isocyanate prepolymer was determined via an autotitrator procedure.

[0094] As mentioned above, PSG, HQEE, and dodecanediol were selected as exemplary initiators in the ring-opening polymerization of caprolactone polyols.

[0095] Their presence in the polyol backbone enhances the recrystallization rate and thus reduces the open time of adhesives formulated with the caprolactone polyols of the present disclosure. As shown in Table 2, exemplary initiators contain either aromatic or rigid ring structures, or, in the case of dodecanediol, longer carbon chains (12 carbons), which may promote symmetry and improve crystallization rates.

[0096] Example 3. Open time of reactive hot melt adhesive Open Time Measurement (Wooden Tongue Depressor Method). Many methods for determining open time have been discussed and published in the adhesives field, so a widely practiced and accepted method using a wooden tongue depressor was utilized. RHMA contained in an aluminum 310 mL cartridge was placed in a 120°C oven for 4 hours. Once at temperature (measured by a thermometer placed in the adhesive), the sealed tube was placed in a Reka TR 70 hot melt cartridge extruder gun set at 120°C, and a bead of adhesive was dispensed from the gun with air assistance (6 bar).

[0097] An adhesive bead (0.2 g) is placed on the wooden tongue depressor and the open time is defined as the moment when the second wooden tongue can no longer form a bond with the adhesive bead.

[0098] Results. As shown in Figure 1, a difference is observable between (1) the market-leading hexanediol and adipic acid-based polyester polyol-containing adhesive (DYNAOCOLL® 7360), which has an open time of 3 minutes 45 seconds, and (2) the currently commercially available caprolactone polyol-containing adhesive, Capa™ 2403D (butanediol-initiated), which has an open time of 7 minutes 30 seconds.

[0099] The open time of the adhesive was decreased by incorporating PSG (6 min 15 s), HQEE (5 min 30 s), and dodecanediol (4 min 45 s). Figure 1 shows that the initiator molecules decreased the open time of adhesives with varying caprolactone polyol backbones.

[0100] Example 4. Differential Scanning Calorimetry (DSC) of Polyols and Reactive Hot Melt Adhesives Differential Scanning Calorimetry (DSC). A DSC 25 (TA® Instruments) was used to collect the thermal behavior of both the polyol and the formulated RHMA. A temperature ramp of 10°C / min was used to measure the glass transition temperature (T g ), melting temperature (T m), and recrystallization temperature (T c ) was won.

[0101] Results. DSC data was collected to establish a relationship between the thermal events measured via DSC and the open time measurements discussed herein. DSC data was collected on the polyol and the final cured adhesive. The glass transition temperature (T g ) and recrystallization temperature (T c ) data are presented in Table 6 below. [Table 6]

[0102] Example 5. Lap shear adhesion of reactive hot melt adhesives Lap Shear Measurement. German National Standard DIN EN 1465:2009-07 (Adhesives—Determination of Tensile Lap-shear Strength of Bonded Assemblies. 7 January 2009) was utilized to measure lap shear, including the determination of lap shear dimensions. Briefly, lap shear samples were cleaned with a microfiber cloth and isopropyl alcohol (IPA) and then placed in a temperature-controlled humidity cabinet (23°C and 50% relative humidity). To maintain a 0.2 mm bondline gap, a calibrated wire was attached to one lower specimen (substrate) located within the mold, and adhesive was applied via a hot melt gun.

[0103] The adhesive was spread over the shear area using a stick. The adhesive-covered shear area was bonded to the upper specimen (substrate) and pressure was applied with a suitable block. Excess specimen was wiped off with a cotton swab. The sample was allowed to cool and set. The sample was then placed in a temperature-controlled humidity cabinet.

[0104] Lap shear articles were pulled on a ZwickRoell tensile tester using a 10 kilonewton (KN) load cell with asymmetric grips. The bonded articles were pulled at a force-controlled rate of 0.16 millipascals per second (mPa / s). The force reported as adhesion is the maximum force. Different types of failure modes were recorded for each experiment. Interfacial failure is failure between the adhesive film and the substrate, cohesive failure is failure within the adhesive film itself, and material failure is failure seen in the substrate during the test.

[0105] Results. Lap shear adhesion was measured as described above. Substrates bonded included aluminum (2 mm thick) alloy 5005A (AlMg 1), polycarbonate (6 mm thick) markoform 099, and beechwood (6 mm thick) with a dampened, milled surface. All substrates were purchased from Rocholl GmbH (Eschelbronn, Germany).

[0106] The results contained in Table 7 below are in N / mm 2 The Fmax value (peak separation force) is included. The failure mechanism is indicated in parentheses: AF indicates interfacial failure between the adhesive and the substrate, CF indicates cohesive failure within the adhesive film itself, and SF indicates material failure where the substrate ruptures before bond failure. [Table 7]

[0107] Figure 2 shows the shear adhesion data (Fmax N / mm) for each substrate and adhesive investigated. 2 When bonded to aluminum, all adhesives failed by interfacial failure. The HQEE-initiated caprolactone polyol adhesive had a strength of 3.8 N / mm 2 The polycarbonate substrate yielded a maximum force of 11.4 N / mm for the PSG-initiated caprolactone polyol adhesive. 2 , 14.6 N / mm for HQEE-initiated caprolactone polyol adhesives 2This resulted in the greatest spread of data. This can be explained by the substrate (polycarbonate) itself being less stiff than the other substrates tested. During the lap shear measurements, the strained polycarbonate substrate changed due to the force and the geometry of the bonded area.

[0108] Beech wood substrates fractured and broke during testing of HQEE-initiated caprolactone polyol adhesives and dodecanediol-initiated caprolactone polyol adhesives. As a result, the beech wood results are not a true reflection of adhesion strength. PSG-initiated caprolactone polyol adhesives exhibited a 13.9 N / mm 2 The Capa™ 2403D adhesive yielded the lowest recorded Fmax value of 16.4 N / mm 2 yielded the highest Fmax value.

[0109] Within this data set, the HQEE-initiated caprolactone polyol adhesive provided the best adhesion results, while the PSG-initiated caprolactone polyol adhesive appears to be the poorest performing adhesive examined. The substrate failure seen with the beechwood and dodecanediol- and HQEE-initiated caprolactone polyol adhesives can be explained by a better substrate in the wet state, provided by the lower viscosity adhesive compared to the polyester polyol.

[0110] Example 6. Viscosity of reactive hot melt adhesives Viscosity Measurement (Brookfield). Rotational viscosity was measured using a Brookfield DVNext viscometer and thermosel. Test material (10.2 grams) was placed in a disposable container and the test material was added to the thermosel. The temperature was set to 120°C, the torque was 20%-80%, and spindle 27 was selected. The final viscosity was recorded after 30 minutes under test.

[0111] Results. The viscosity of the adhesives was measured as described herein via a Brookfield viscometer. Table 8 shows viscosity measurements taken with a 27 spindle after 30 minutes at 130°C unless otherwise specified. The polyester polyol-based adhesives recorded the highest viscosities at 120°C, at 4100 mPa·s for the 2.5% NCO adhesive and 2775 mPa·s for the 3% NCO adhesive. [Table 8]

[0112] All caprolactone-based adhesives have lower viscosities than the polyester polyol-based adhesives when compared at 120°C. The Capa™ 2403D-based adhesive had the lowest viscosity reading of 2260 mPa·s, while the PSG-initiated caprolactone polyol-based adhesive yielded the highest caprolactone-based viscosity of 3435 mPa·s. Viscosity data is also shown graphically in Figure 3.

[0113] In the reactive hot melt adhesive market, lower viscosities may be considered desirable because they allow the adhesive to flow over the substrate, enhancing the surface interaction between the adhesive and the substrate, especially when the shapes of the joined substrates are more complex.

[0114] The lower viscosity of caprolactone-based adhesives results from the lower polydispersity of the ring-opening polymerization than condensation polyesters.

[0115] Example 7. Tensile strength of reactive hot melt adhesives Measurement of adhesive film tensile strength. Test sheets were made by applying 20 grams of adhesive to a flat piece of siliconized release liner paper (80 gsm Kraft). A 0.5 mm K bar was used to pull the adhesive prepolymer 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).

[0116] After 1 week in the humidity oven, the adhesive film and release liner were removed and tensile specimens were punched out to the dimensions specified in ISO 37:2005, Type 2, with a film thickness of 0.5 mm. Tensile measurements were taken using a ZwickRoell tensile machine.

[0117] Results. The tension of 0.5 mm adhesive films was measured as described herein. Figure 4 and Table 9 below show the Fmax (N / mm) recorded for each adhesive tested. 2 ) is shown. [Table 9]

[0118] Tensile force testing of the films demonstrates the effect of varying the chemistry of the initiator molecules within the caprolactone polyols. The linear initiators dodecanediol and butanediol produced results similar to those for the polyester polyols. The ring-structured initiators HQEE and PSG increased Fmax. This may be explained by the steric hindrance of these bulkier structures, resulting in the need for more force to overcome the obstacles.

[0119] Discussion of Examples The data show that there is a structure-property relationship when the initiator molecule is varied in the production of caprolactone polyols.

[0120] The primary motivation for changing the starting molecule was to decrease the open time of caprolactone-based adhesives, which are needed in the marketplace as an alternative to polyester chemistry. While the short open time (3 minutes 45 seconds) of adhesives containing crystalline DYNACOLL® 7360 was not matched by caprolactone-based alternatives, the data show that by incorporating dodecanediol into the caprolactone backbone, the open time of caprolactone polyol-based adhesives can be reduced to 4 minutes 45 seconds.

[0121] Here, additional adhesive characterization techniques were investigated to understand the performance profile of caprolactone polyol-based adhesives compared to alternative polyester polyols, such as those exhibiting lower viscosity, improved adhesion to aluminum, and improved induced material failure in beech wood.

[0122] The tensile properties of the films showed a clear structure-property relationship between the nature of the initiating molecule and the final Fmax value: "bulky" and sterically hindered initiating molecules resulted in higher tensile strength for the adhered films.

[0123] While several embodiments of the invention of the present disclosure have been shown and described herein, it will be understood that such embodiments are provided by way of example only. Numerous variations, changes, and substitutions will occur to those skilled in the art without departing from the spirit of the invention. Rather, the present disclosure covers all modifications, equivalents, and alternatives that are within the scope of the present disclosure, as defined by the following appended claims and their legal equivalents. Accordingly, the description and appended claims are intended to cover all such variations that fall within the spirit and scope of the invention.

[0124] The contents of all references, patents, pending patent applications and published patents, cited throughout this application are hereby expressly incorporated by reference.

[0125] Those skilled in the art will recognize or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the invention described herein. Such equivalents are intended to be encompassed by the following claims. It is understood that the detailed examples and embodiments described herein are provided for illustrative purposes only and are not to be construed as limiting the invention in any way. Various modifications or variations therein will be suggested to those skilled in the art and are 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 ingredients can be varied to optimize the desired effect, additional ingredients can be added, and / or similar ingredients can be substituted for one or more of the described ingredients. Additional advantageous features and functions associated with the systems, methods, and processes of the present invention will be apparent from the appended claims. Moreover, those skilled in the art will recognize or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the invention described herein. Such equivalents are intended to be encompassed by the following claims.

Claims

1. mixing an initiator and 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; polymerizing (e.g., ring-opening polymerizing) the caprolactone monomers in the reaction mixture, thereby forming the caprolactone polyol; The initiator comprises a caprolactone polyol, such as hydroquinone bis(2-hydroxyethyl) ether, a dodecanediol (eg, 1,12-dodecanediol), a pentaspiroglycol, or a combination thereof.

2. 10. The caprolactone polyol of claim 1, wherein the process further comprises: (i) preserving the initiator-caprolactone mixture before adding the catalyst (e.g., sparging the initiator-caprolactone mixture with nitrogen); (ii) incubating the initiator-caprolactone mixture before adding the catalyst (e.g., preserving the initiator-caprolactone mixture 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 while sparking the initiator-caprolactone mixture); (ii) 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.

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

4. 4. The caprolactone polyol of any one of claims 1 to 3, wherein the process 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, e.g., to about 150°C to about 190°C, e.g., about 150°C to about 160°C), thereby forming the caprolactone polyol.

5. 5. The caprolactone polyol of claim 1, wherein 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) (Irganox® 1010), a phosphite antioxidant and / or stabilizer, bis(2,4-di-tert-butylphenol)pentaerythritol diphosphate (e.g., Irgafos® 126), a hydrolysis inhibitor (Stabaxol® I), an acid scavenger (Stabaxol® I), a carbodiimide (e.g., a monomeric carbodiimide), or a combination thereof).

6. the caprolactone monomer is present in an amount of about 85% to about 98% by weight (e.g., about 90% to about 97%, about 93% to about 97%, or about 95% by weight) of the initiator-caprolactone mixture; the initiator is present in an amount of about 2% to about 15% by weight (e.g., about 3% to about 10% by weight, about 3% to about 7% by weight, or about 5% by weight) of the initiator-caprolactone mixture; the caprolactone monomer is present in an amount of about 85% to about 98% by weight (e.g., about 90% to about 97% by weight, about 93% to about 97% by weight, or about 95% by weight) of the reaction mixture; the initiator is present in an amount of about 2% to about 13% by weight (e.g., about 3% to about 10% by weight, about 3% to about 7% by weight, or about 5% by weight) of the reaction mixture; The catalyst is present in an amount of from about 0.001% to about 5% by weight of the reaction mixture (e.g., from about 0.001% to about 5% by weight, from about 0.001% to about 4% by weight, from about 0.001% to about 3% by weight, from about 0.001% to about 2% by weight, from about 0.001% to about 1% by weight, from about 0.001% to about 0.5% by weight, from about 0.001% to about 0.25% by weight, from about 0.1% to about 5% by weight). , about 0.1% to about 4%, about 0.1% to about 3%, about 0.1% to about 2%, about 0.1% to about 1%, about 0.1% to about 0.5%, about 0.1% to about 0.25% by weight, about 0.2% to about 5% by weight, about 0.2% to about 4% by weight, about 0.2% to about 3% by weight, about 0.2% to about 2% by weight, about 0.2% to about 1% by weight, about 0.2% by weight % to about 0.5% by weight, about 0.5% to about 5% by weight, about 0.5% to about 4% by weight, about 0.5% to about 3% by weight, about 0.5% to about 2% by weight, about 0.5% to about 1% by weight, about 0.75% to about 5%, about 0.75% to about 4%, about 0.75% to about 3%, about 0.75% to about 2%, about 0.75% to about 1%, about 1% to about 5% by weight %, 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% by weight of the reaction mixture (e.g., up to about 1.5%, up to about 1%, up to about 0.5%, up to about 0.25%, about 0.1% to about 2%, about 0.1% to about 1.5%, about 0.1% to about 1%, about 0.1% to about 0.75%, about 0.1% to about 0.5%, or about 0.1% to about 0.25%); or The caprolactone polyol according to any one of claims 1 to 5, which is at least one of the combinations thereof.

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

8. 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, propanoic acid or tetrabutyl titanate, or a combination thereof).

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

11. 11. The polyurethane material or adhesive of claim 10, wherein the process 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. 12. The polyurethane material or adhesive of claim 10 or 11, wherein the reaction between the caprolactone polyol and the isocyanate was carried out with: (i) sparging (e.g., sparging with nitrogen); (ii) 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. 13. The polyurethane material or adhesive of any one of claims 10 to 12, wherein (i) the isocyanate is monomeric, oligomeric, polymeric, or a mixture thereof, (ii) the catalyst is a urethane catalyst (e.g., a tertiary amine compound, an amine having isocyanate-reactive group(s), an organometallic compound, or a mixture thereof), or (iii) a combination thereof.

14. The isocyanate may be 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 3,3'-dimethyl-4,4'-biphenylene diisocyanate (TODI), toluene diisocyanate (TDI), polymeric MDI, modified liquid 4,4'-diphenylmethane diisocyanate, hexamethylene-diisocyanate ("HDI"), 4,4'-dicyclohexylmethane diisocyanate ("HDI"). １２ MDI"), isophorone diisocyanate ("IPDI"), para-phenylene diisocyanate ("PPDI"), meta-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, Diisocyanate, 2,4-methylcyclohexane diisocyanate, 2,6-methylcyclohexane diisocyanate, 4,4'-dicyclohexyl diisocyanate, 2,4'-dicyclohexyl diisocyanate, 1,3,5-cyclohexane triisocyanate, isocyanatomethylcyclohexane 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 14. The polyurethane material or adhesive of any one of claims 10 to 13, comprising an isocyanate selected from the group consisting of 2,4'-biphenyl diisocyanate, 4,4'-biphenyl diisocyanate, 2,2-biphenyl diisocyanate, polyphenylpolymethylene polyisocyanate ("PMDI"), meta-tetramethylxylene diisocyanate ("m-TMXDI"), para-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 dimethrimethane-4,4'-diisocyanate (MDI).

16. The catalyst is (i) a 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 (e.g., a tertiary amine catalyst present in an amount from about 0.02% to about 5% by weight of the reaction mixture), or mixtures thereof; (ii) an organometallic catalyst (e.g., an organometallic catalyst present in an amount of about 0.001 to 1% by weight of the reaction mixture) including an organobismuth, organomercury, organolead, organoferric, or organotin catalyst, or a combination thereof (preferably an organotin catalyst); (iii) tin catalysts, including stannous chloride, stannous salts of carboxylic acids (e.g., dibutyltin dilaurate), stannous octoate, or combinations thereof; (iv) a catalyst for the trimerization of polyisocyanates, including an alkali metal alkoxide; or (v) A polyurethane material or adhesive according to any one of claims 10 to 15, which is a combination thereof.

17. 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) content of at least about 1% (e.g., from about 1% to about 5% or from about 2% to about 3%).

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

19. 1. A method for making a caprolactone polyol, comprising: mixing an initiator and 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; polymerizing (e.g., ring-opening polymerizing) the caprolactone monomers in the reaction mixture, thereby forming the caprolactone polyol; The method, wherein the initiator comprises hydroquinone bis(2-hydroxyethyl) ether, dodecanediol (eg, 1,12-dodecanediol), pentaspiroglycol, or a combination thereof.

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

21. 1. A method for bonding a first substrate to a second substrate, comprising: applying a polyurethane material or adhesive according to any one of claims 10 to 18 to the first substrate, the second substrate, or the first substrate and the second substrate; contacting the first substrate and the second substrate with the polyurethane material or adhesive located therebetween.

22. The method of claim 21 , wherein the application of the polyurethane material or adhesive is carried out at about 120° C. to about 160° C. (e.g., about 120° C. to about 130° C.).

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

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