Epoxy and urethane compositions and methods based on the controllable stretching of flexible oligomeric diols

Abstract

This invention provides a flexible oligomeric diol composition. [Solution] An extended diol composition is provided, which comprises a first component comprising an α,ω-hydroxyl-terminated diol oligomer having a number average molecular weight Mn of about 500 Da to about 100,000 Da, a polyfunctional isocyanate species, and a polyfunctional alcohol species or amine species. Another extended diol composition is provided, which comprises a first component comprising an α,ω-hydroxyl-terminated diol oligomer having a number average molecular weight Mn of about 500 Da to about 100,000 Da, a polyfunctional isocyanate species, and a polyfunctional species comprising an alcohol functional group and an epoxy functional group.

Description

Technical Field

[0001] Cross - reference to Related Applications This application claims priority to U.S. Provisional Patent Application No. 63 / 730,288, filed on December 10, 2024, which is hereby incorporated by reference in its entirety.

[0002] Technical Field The teachings of this application generally relate to the production of epoxy and urethane polymers using flexible oligomer - type diol compositions, and specifically to controlling and expanding the molecular weight of such compositions.

Background Art

[0003] Many commercially available oligomer - type diols are produced in the range of 500 - 5,000 daltons. Extending these oligomer - type diols to higher molecular weight diols is desirable to produce materials with lower cross - link density and higher flexibility. Flexible oligomer - type diol compositions can be used in various materials or material compositions in the aerospace industry, such as coatings, seals, linings, adhesives, sealants, and elastomers. Although precursors are available and relatively inexpensive, some precursors may be limited by the maximum molecular weight that can be prepared.

[0004] Due to the limitations in the available molecular weights of many commercially available oligomer - type diols, such materials can be prohibitively expensive and may be difficult to synthesize directly. The higher molecular weight species of these materials can provide formulators with a wider range of options in the production of coatings, adhesives, elastomers, and sealants, due to the low modulus materials achievable by the reduction in cross - link density caused by longer diol precursors. Producing other polymer systems with variable functional chemistry using commercially available oligomer - type diols and other oligomer - type diols is a desirable advantage.

[0005] Therefore, there is a need for a method to provide a stretched material that maintains flexibility and low cost while achieving a wide molecular weight range from these precursors, while maintaining the functionality of the diol terminal groups for further modification of the functional chemical groups and limiting modifications to the main chain properties. [Overview of the project]

[0006] The following is a simplified overview to provide a basic understanding of some aspects of one or more embodiments of this teaching. This overview is not a comprehensive overview, nor is it intended to identify the main or important elements of this teaching or to define the scope of this disclosure. Rather, its primary purpose is to briefly present one or more concepts as an introduction to the more detailed explanations that will follow.

[0007] An extended diol composition is disclosed. The extended diol composition also comprises a first component containing an α,ω-hydroxyl-terminated diol oligomer having a number average molecular weight Mn of about 500 g / mol to about 100,000 g / mol, a polyfunctional isocyanate species, and a polyfunctional alcohol species or amine species, wherein the α,ω-hydroxyl-terminated diol oligomer has the following structure: TIFF2026113412000001.tif41170.

[0008] Embodiments of the stretched diol composition may include cases where the R2 and R3 groups of the α,ω-hydroxyl-terminated diol oligomer may contain a methyl group, an ethyl group, a propyl group, an isopropyl group, a phenyl group, or a combination thereof, and where n is about 1 to about 100. The R1 group may contain a polyether, polyester, or polysiloxane. The R1 group may include the following structures: TIFF2026113412000002.tif22170. In the above formula representing an example of R1, m is defined to be approximately 1 to 20, q to be approximately 5 to 200, and p to be 5 to 200. Polyfunctional isocyanate species may include toluene diisocyanate, isophorone diisocyanate, 4,4'-methylenebis(phenyl isocyanate), 4,4'-methylene-bis(cyclohexyl isocyanate), hexamethylene diisocyanate, poly(hexamethylene diisocyanate), poly(isophorone diisocyanate), or combinations thereof. The molar ratio of polyfunctional isocyanate species to the stretched diol oligomer is approximately 1.1 to approximately 10. The stretched diol composition may include a catalyst such as a tin-based catalyst. The catalyst may include dibutyltin dilaurate or stannous octanoate. The stretched diol composition may contain UV stabilizers, antioxidants, pigments, or combinations thereof. The polyfunctional alcohol species or amine species may include amines such as triethylenetetraamine, diethylenetriamine, tetraethylenepentamine, triaminononane, aspartic acid esters, polycarbamide curing agents, or combinations thereof.

[0009] Another stretched diol composition is disclosed. This stretched diol composition also comprises a first component which may include an α,ω-hydroxyl-terminated diol oligomer having a number average molecular weight Mn from about 500 g / mol to about 100,000 g / mol, a polyfunctional isocyanate species, and a polyfunctional species which may include an alcohol functional group and an epoxy functional group, the α,ω-hydroxyl-terminated diol oligomer having the following structure: TIFF2026113412000003.tif41170.

[0010] Embodiments of the stretched diol composition are as described above for the α,ω-hydroxyl-terminated diol oligomer structure, where the R2 and R3 groups of the α,ω-hydroxyl-terminated diol oligomer may include a methyl group, an ethyl group, a propyl group, an isopropyl group, a phenyl group, or a combination thereof. The R1 group may include a polyether, polyester, or polysiloxane. The R1 group has the following structure: The formula may include TIFF2026113412000004.tif22170, where m is approximately 1 to approximately 20, p is approximately 5 to approximately 200, q is approximately 5 to approximately 200, and Mn is approximately 1,000 Da to approximately 10,000 Da. The polyfunctional isocyanate species may include toluene diisocyanate, isophorone diisocyanate, 4,4'-methylenebis(phenyl isocyanate), 4,4'-methylene-bis(cyclohexyl isocyanate), hexamethylene diisocyanate, poly(hexamethylene diisocyanate), poly(isophorone diisocyanate), or combinations thereof. The stretched diol composition may contain reactive diluents that may contain epoxy functional groups. The stretched diol composition may contain curing agents such as polyfunctional amine groups. The molar ratio of polyfunctional isocyanate species to the extended diol oligomer is approximately 1.1 to 10.

[0011] A method for producing a resin is disclosed. The method also comprises providing a diol oligomer to a reaction vessel, the diol oligomer may include an α,ω-hydroxyl-terminated diol oligomer having a number-average molecular weight Mn of about 500 g / mol to about 100,000 g / mol. The method also comprises adding a diisocyanate compound to the reaction vessel such that the molar ratio of the diisocyanate compound to the α,ω-hydroxyl-terminated diol oligomer is about 1.1 to about 10. The method also comprises heating the diol oligomer and the diisocyanate compound in an inert atmosphere at a temperature of about 50 to about 110°C for about 1 to about 2 hours. The method also includes cases where the diol oligomer contains [-O-Si(R2,R3)-O-] (wherein the formula R2 and R3 groups may include a methyl group, an ethyl group, a propyl group, an isopropyl group, a phenyl group, or a combination thereof).

[0012] Embodiments of a method for producing a resin may include dissolving a diol oligomer in a solvent. The polyfunctional alcohol may contain at least three alcohol functional groups. A method for producing a resin may include adding a reactive epoxy diluent to a reaction vessel. A method for producing a resin may include adding polyfunctional species, such as alcohol functional groups and epoxy functional groups, to a reaction vessel.

[0013] The features, functions, and advantages described above can be realized individually or in combination in various embodiments, and further details therein can be found in the following description. [Brief explanation of the drawing]

[0014] The accompanying drawings, incorporated into this specification and constituting part of this specification, illustrate embodiments of this teaching and, together with the explanatory parts, are useful for illustrating the principles of this disclosure.

[0015] [Figure 1]Figure 1A illustrates an application of a structural component comprising an exemplary stretched diol composition applied to an aerospace vehicle. Figure 1B is an exploded view of a portion of the aerospace vehicle shown in Figure 1A, as disclosed herein.

[0016] It should be noted that some of the details in the drawings are simplified to facilitate understanding of this disclosure, rather than to preserve strict structural precision, detail, and scale. [Modes for carrying out the invention]

[0017] Many commercially available oligomeric diols are produced in the range of 500 to 5,000 daltons and can be used in coatings, adhesives, seals, linings, occlusions, and elastomers. Stretching diols to larger molecular weights is desirable to produce materials with higher flexibility at lower crosslinking densities. This disclosure provides an improved synthetic strategy for controllingly increasing the number-average molecular weight (Mn) of oligomeric diols, Fluorolink TM This relates to examples involving the use of (Telekek) precursors having a structure similar to E10H and a weight-average molecular weight of approximately 1800 daltons, with functional groups at both ends. Diols with larger number-average molecular weights (Mn), e.g., about 500 to about 100,000 daltons, or about 1,000 to about 100,000 daltons, about 2,000 to about 100,000, or about 5,000 to about 100,000 daltons, can be incorporated into urethane or urea systems through reaction with isocyanates. Epoxyamine networks can be fabricated by reacting stretched diols with diisocyanates, followed by modification of epoxy end groups. Some oligomeric diols within a desired range for use in coatings, adhesives, sealants, and elastomers are either not commercially available or are only offered at high prices. This disclosure provides alternative compositions that can be stretched while controlling the molecular weight and structure of oligomeric diols and materials obtained therefrom.

[0018] The stretched diol composition also comprises a first component containing an α,ω-hydroxyl-terminated diol oligomer having a number average molecular weight Mn of about 500 g / mol to about 100,000 g / mol, a polyfunctional isocyanate species, and a polyfunctional alcohol species or amine species, wherein the α,ω-hydroxyl-terminated diol oligomer has the following structure (represented by structure A): TIFF2026113412000005.tif41170 Structure A.

[0019] Examples of stretched diol compositions include cases where the R2 and R3 groups of structure A may contain methyl, ethyl, propyl, isopropyl, phenyl, or combinations thereof. Structure A includes cases where n is about 1 to about 20 and Mn is about 1,000 to about 100,000 daltons. The R1 group may contain a polyether, polyester, or polysiloxane. The R1 group may contain the following structure (represented by structure B): TIFF2026113412000006.tif22170 Structure B.

[0020] In the above formula, m is from 1 to about 20, p is from about 5 to about 200, and q is from about 5 to about 200. The polyfunctional isocyanate species may include toluene diisocyanate, isophorone diisocyanate, 4,4'-methylenebis(phenyl isocyanate), 4,4'-methylene-bis(cyclohexyl isocyanate), hexamethylene diisocyanate, poly(hexamethylene diisocyanate), poly(isophorone diisocyanate), or combinations thereof. The stretched diol composition may contain reactive diluents that may contain epoxy functional groups. The stretched diol composition may contain curing agents such as polyfunctional amine groups. The molar ratio of the polyfunctional isocyanate species to the stretched diol oligomer is from about 1.1 to about 10. Throughout this disclosure, for clarity, the R1, R2, and R3 groups are consistently defined as those described above with reference to Structure A.

[0021] In the present disclosure, siloxane bonds as linkages generated during the implementation of the methods herein preserve the flexibility in the resulting chain backbone. The method includes the production of an extended diol oligomer composed of one or more first components selected from diol oligomers having an average Mn of from 500 to 5,000 g / mol, the polyoligomer being terminated with α,ω hydroxyl groups. A second component selected from diisocyanate species is also included.

[0022] Due to the limitations in the available molecular weights of many commercially available oligomeric diols, strategies are needed to achieve a greater molecular weight range in these materials while maintaining the functionality of the diol end groups and limiting modifications to the backbone properties. These larger molecular weight species can provide formulators with a wider range of options in the production of coatings, adhesives, elastomers, and sealants, which are low modulus materials that can be achieved through a reduction in the crosslink density resulting from longer diol precursors.

[0023] Molecular weight is a measure of the sum of the atomic weight values of the atoms in one molecule. Molecular weight is used in chemistry to determine chemical reactions and the stoichiometry of chemical formulas. Molecular weight, abbreviated as M.W. or MW, can be expressed in g / mol, atomic mass units (amu), or Daltons (Da). Molecular weight can also be expressed as Mn (number average molecular weight), which is calculated from the mole fraction distribution of molecules of different sizes in a sample, or as Mw (weight average molecular weight), which is calculated from the weight fraction distribution of molecules of different sizes.

[0024] Recent research has provided a comprehensive strategy for controllably increasing the number average molecular weight (Mn) of oligomeric diols, specifically in relation to a first component that is a diol oligomer, and a second component that is a bisdimethylaminosilane having a molecular weight (Mn) of from about 500 to about 5,000 Da. This disclosure describes the use of these extended oligomeric diols in epoxy and urethane compositions for generating elastomeric films. An example in this strategy is the use of a commercially available telechelic precursor having a structure of HO-PEG-PFPE-PEG-OH (Fluorolink TM E10H, Synesqo), generally MW = 1,800 Da. Extension of this structure can achieve a range of precursor weights from about 1,800 to about 100,000 daltons by the structure HO-(PEG-PFPE-PEG-O-X-O-PEG-PFPE-PEG)n-OH where X = -Si(CH3)2- or X represents silicon having other constituents described herein, PEG refers to poly(ethylene glycol) repeating units, PFPE refers to perfluoropolyether repeating units, and n is a number from about 1 to about 50, or about 1 to about 12, or about 1 to about 6).

[0025] Such larger molecular weight diols having an average Mn of from about 2,000 to about 100,000 Da can be incorporated into urethanes or ureas through reaction with isocyanates. Further, epoxyamine networks are possible through reacting the extended diol with a diisocyanate followed by modification of the epoxy end groups. Many commercially available oligomeric diols are produced in the range of 500 - 5,000 daltons and these precursors are often used in coatings, adhesives, sealants and elastomers, but extension to larger molecular weight diols is desirable to produce more flexible materials through a reduction in crosslink density that cannot be achieved with the unextended precursors.

[0026] Because many commercially available oligomeric diols have limited molecular weights, strategies are needed to achieve a larger molecular weight range in these materials while maintaining the functionality of the diol terminal groups and limiting modifications to the main chain properties. These larger molecular weight species can provide compounders with a wider range of options in the production of coatings, adhesives, elastomers, and sealants, which are low modulus materials that can be achieved by reducing the crosslink density resulting from longer diol precursors. As shown in Reaction Scheme 1 below, the broad scope of this study includes the use of the extended oligomer ol products of Scheme 1 for formulation into compositions incorporating urethane / urea and epoxy / amine functional polymer networks. TIFF2026113412000007.tif32170 Scheme 1 - Basic reactions that generate extended diol oligomers

[0027] The broadest scope of this disclosure is the use of the extended oligomer ol products of Scheme 1 for formulation into urethane / urea and epoxy / amine polymer networks. R1, R2, R3, and n have already been defined and described with respect to Structure A. Another exemplary example may include the use of a commercially available telekek precursor, also called a linear oligomer or low molecular weight linear polymer, based on the HO-PEG-PFPE-PEG-OH structure shown in Scheme 2 (wherein m is about 1 to about 20 or about 1 to about 18, p=q, p is about 5 to about 50 or about 5 to about 45, and having a molecular weight range of about 1000 to about 10000 daltons), having functional groups at both chain ends. TIFF2026113412000008.tif22170 Scheme 2 - (Telekec) PEG-PFPE-PEG structure with functional groups at both ends

[0028] Figure 1A shows the application of structural components, including an exemplary stretched diol composition, to an aerospace vehicle. Figure 1B is an exploded view of a portion of the aerospace vehicle of Figure 1A according to the present disclosure. An example of the application of the methods and compositions disclosed herein is shown on an aerospace vehicle 100, to which the stretched diol composition disclosed herein is applied to the vehicle substrate 130. An exploded view Figure 1B is shown, in the figure, of the vehicle substrate 130 or its surface having an optional anodized substrate or undercoat layer 132 and a sealing layer 134 on the surface of the substrate 130 and / or on a structural component or portion of the vehicle. In one embodiment, the application of the coating composition disclosed herein is made to the outer surface of the aerospace vehicle 100. In the embodiment, an additional coating layer, such as a paint, coating, or other protective coating, can be applied internally or externally on the sealing layer 134. One embodiment of the external substrate or surface of the aerospace vehicle 100 is shown herein, but this is intended to be a non-limiting embodiment. Other structural applications or areas in the aerospace vehicle 100 or other structures or vehicles where the stretched diol composition or its coating may be used, such as seals or gaskets, such as O-rings, or similar applications.

[0029] Application to urethane / urea polymer networks Furthermore, the linkage between the stretched diol oligomers and isocyanates described herein, which may also feature α,ω-hydroxyl-terminated diol oligomers, forms polyurethane bonds. Diisocyanates with two functional isocyanate-terminated groups (f=2) linked to the stretched diol oligomer form linear chains, while isocyanates with three or more functional groups (f≧3) tend to generate branched crosslinking networks. The linkage between diols and diisocyanates can produce thermoplastic materials with characteristic ability to flow and melt under appropriate temperatures and stresses. By incorporating branched species (f≧3) into the formulation, thermosetting materials that resist flow and deformation at higher temperatures and stresses can be formed or produced.

[0030] The overall network topology of the polymer network described may depend on the functionality of the precursor species and the order of addition. This can take the form of a "one-shot" approach in which all precursors are mixed and reacted at once. Alternatively, a prepolymer strategy is often used, in which case the linear chain segments are synthesized using the surplus of diols and diisocyanates. These surplus isocyanate groups are then combined with stoichiometric equivalents of alcohol groups, as shown in Scheme 3 below, to fully react with the functional groups in the system.

[0031] Common isocyanate species used in these systems may include toluene diisocyanate, isophorone diisocyanate, 4,4'-methylenebis(phenyl isocyanate), 4,4'-methylene-bis(cyclohexyl isocyanate), and hexamethylene diisocyanate, or combinations thereof, or may be diisocyanates (f=2), or may contain such diisocyanates. Higher functional isocyanates may also be incorporated (f≧3), including poly(hexamethylene diisocyanate), poly(isophorone diisocyanate), and poly(methylenediphenyl isocyanate), or combinations thereof. The polyfunctionality of these diisocyanates can be achieved through various chemical structures and molecular configurations that enable reaction with multiple functional groups on the stretched diol oligomer, thereby forming a complex network, and improved thermal stability and mechanical strength may be provided by the incorporated rigid molecular structure. In addition to these specific examples, other polyfunctional diisocyanate species may be used to provide improved chemical resistance and thermal stability. TIFF2026113412000009.tif18170 Scheme 3: A common prepolymer reaction in which diisocyanate is in excess relative to the diol.

[0032] The curing of one-shot or prepolymer precursors having isocyanate reactive groups can be achieved using polyfunctional (f≧2) alcohols to produce urethane bonds. Alternatively, polyfunctional amines (f≧2) can be used to produce urea bonds. However, the rapid reaction rate of this reaction limits its practicality. In Scheme 3, R1 represents the aforementioned polyfunctional diol oligomer, and R4 represents diisocyanates (f=2) including intramolecular diisocyanates described herein, such as toluene diisocyanate, isophorone diisocyanate, 4,4'-methylenebis(phenyl isocyanate), 4,4'-methylene-bis(cyclohexyl isocyanate), and hexamethylene diisocyanate, or combinations thereof. Higher functional isocyanates can also be incorporated (f≧3), including poly(hexamethylene diisocyanate), poly(isophorone diisocyanate), and poly(methylenediphenyl isocyanate), or combinations thereof, in which case n in scheme 3 above is from 2 to about 100, or from about 2 to 200.

[0033] Application to epoxy / amine polymer networks The epoxy / amine polymer network can be generated starting from a similar prepolymer strategy described above (Scheme 3). Following this initiation step, the isocyanate end groups are then converted to epoxy through a reaction with an epoxide reagent containing R5, as shown in Scheme 4 below. In Scheme 4, R5 is, for example, a primary alcohol group, 2,2-di(oxiran-2-yl)ethane-1-ol, 2,2,2-tri(oxiran-2-yl)ethane-1-ol, (4-(oxiran-2-yl)phenyl)methanol, (7-oxabicyclo[4.1.0]heptan-3-yl)methanol, 6-(oxiran-2-yl)hexane-1-ol, 2,2-bis((oxiran-2-ylmethoxy)methyl)butan-1-ol, 2-methyl-3-(oxiran-2-ylmethoxy)-2-((oxiran-2-ylmethoxy)methyl)propan-1-ol, glycidol, glycidamide, or a combination thereof, where n is from 2 to about 100, or from about 2 to about 200. TIFF2026113412000010.tif53170 Scheme 4 - Epoxy End Capping of Prepolymer Mixtures

[0034] R1, R4, and R5 were described above in Scheme 3. In Scheme 4 above, n is from about 2 to about 100. Following the conversion using an epoxy reactive diluent, low viscosity epoxy functional molecules having about 1 to about 6 functional groups (f=1-6) can be optionally added to reduce the viscosity of the network and increase crosslinking. Examples include n-butyl glycidyl ether, n-butyl glycidyl ether, cresyl glycidyl ether, 2-ethylhexyl glycidyl ether, alkyl (C8-C13) glycidyl ether, p-tertiary butylphenol glycidyl ether, neodecanoate glycidyl ether, neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, cyclohexane dimethylol diglycidyl ether, propylene glycol diglycidyl ether, resorcinol diglycidyl ether, glycerol triglycidyl ether, and trimethylolpropane triglycidyl ether, or combinations thereof. Alternatively, the curing of epoxyamine networks can be carried out using polyfunctional amines. Examples of polyfunctional amines include triethylenetetraamine, diethylenetriamine, tetraethylenepentamine, and triaminononane (Hexatran), or combinations thereof.

[0035] In another embodiment, the stretched diol oligomer can be synthesized using a combination of a PEG-PFPE-PEG segment and a siloxane unit. This approach offers greater flexibility in adjusting the molecular weight distribution and the functionality of the end groups. For example, fluctuating reaction conditions such as temperature or catalyst type can also affect chain length and branching pattern. In yet another embodiment, the stretched diol oligomer can be synthesized using a combination of a PEG-PFPE-PEG segment and a polyester unit containing hydroxyl groups at both ends. This approach can form a telekek precursor having multiple functional end groups. Such properties and applications of these materials can be further adjusted by incorporating additional components such as a siloxane or polysiloxane moiety. In some embodiments described herein, the diol is described as a telekek oligomer or material, but the diol does not have to be telekek. In some embodiments, the stretched diol composition may include cases where the R1 group shown in structure A contains a polyether, polyester, or polysiloxane. Commercially available polyesters, polyethers, or polysiloxanes having alcohol-terminated groups can be similarly stretched in reactions similar to those described herein in some examples, when combined with diaminesilane-bonding groups. In the aforementioned examples, the molar ratio of the second component to the first component is about 0.01:1 to about 0.99:1 in the final stretched diol composition. In other examples, ratios of about 0.7 to about 0.9 are applicable. Exemplary stretched diol compositions having the first and second components may have number-average molecular weights Mn of about 1,000 to about 10,000, or about 1,000 to about 20,000, and about 1,000 to about 100,000, where n (of structure A) is about 1 to about 10, or about 1 to about 20, or about 1 to about 100, where n corresponds to an appropriate Mn.

[0036] In one embodiment, polyoxypropylene glycol (POP) is used as an exemplary polyfunctional aliphatic diol having two hydroxyl groups per molecule to form a branched or crosslinked network upon reaction with an isocyanate. Another embodiment includes a polyester diol oligomer synthesized through a condensation reaction between a polyethylene terephthalate (PET) main chain and an ethylene glycol chain extender, resulting in a molecule containing multiple hydroxyl groups per molecule.

[0037] The stretched diol composition may contain one or more catalysts. As used herein, the term “catalyst” may refer to any component, compound, or substance that can increase the rate of a chemical reaction related to the crosslinking of a sealant without requiring a permanent chemical change. The catalyst may be, but is not limited to, a tin-based compound such as dibutyltin dilaurate, which has been found to promote a faster curing rate while maintaining good mechanical properties. In another embodiment, stannous octanoate, a catalyst commonly used in the synthesis of polyurethanes exhibiting similar advantages, is used. In addition, metal-free initiators such as zinc acetate and titanium dioxide may be used because of their ability to accelerate the reaction without introducing undesirable impurities. In another embodiment, organometallic compounds such as ferrocene or cobaltocene are useful alternatives due to their high reactivity with isocyanates. In some embodiments, a combination of a tin-based initiator and a metal-free initiator may be used. In another embodiment, the reaction mixture may contain small amounts of additives such as triphenylphosphine or tris(triphenylphosphite) to enhance catalytic activity while minimizing unwanted by-reactants.

[0038] In some embodiments, reaction conditions can be optimized by adjusting factors such as the temperature, pressure, and stoichiometry of the reactants. For example, improved reactivity can be obtained while maintaining good mechanical properties by increasing the concentration of the catalyst or by modifying its structure through chemical modification. Similarly, the reaction rate can be affected without impairing material properties by changing the type and amount of solvent used in the stretching process.

[0039] By adding useful UV stabilizers to these stretched diol oligomers, their thermal stability and resistance to degradation caused by exposure to ultraviolet light can be further enhanced. In one embodiment, UV stabilizers can be incorporated into the formulation as additives in amounts ranging from 0.1% to 5%, preferably from 0.2% to 3%. Useful examples of such additives include hindered amine compounds such as bis(2a-ethyl-hexyl-p-cresol)piperidine, octadecanoic acid (C18), and diisooctyl phthalate; phenolic antioxidants such as butylhydroxytoluene (BHT); and sulfur-containing additives such as diphenyldithiophosphate or dilaurylthiodipropionate. In another embodiment, the UV stabilizer can be covalently bonded to the telekek precursor through a reaction between an epoxy group at one end of the molecule and an amine functional group at the other end, which is an approach that can enhance stability against degradation caused by exposure to heat or light. In another embodiment, the UV stabilizer may include a metal complex containing a transition metal such as copper (Cu), zinc (Zn), or iron (Fe); these compounds have been shown to exhibit useful photostabilization properties. For example, Cu-based complexes including 2-(4-methoxyphenyl)-5-tert-butylimidazole and its derivatives have shown excellent UV stability in various applications. The UV stabilizer can be incorporated into the formulation as part of an oligomer or polymer structure, thereby increasing thermal resistance to degradation caused by exposure to heat.

[0040] In another embodiment, the UV stabilizer may be used in combination with other additives such as antioxidants or fillers, which can enhance thermal stability against degradation caused by exposure to heat. The optional addition of antioxidant species to these materials may be useful to enhance their thermal stability and resistance to degradation over time. In one embodiment, the antioxidant may include phenolic compounds such as BHT or Irganox 1010, which are commonly used in polyurethane formulations due to their ability to remove free radicals and prevent chain reactions that lead to material degradation. Another useful antioxidant may include hindered amine light stabilizers (HALS), particularly those with a molecular weight of about 500 Da or less, such as Tinuvin P or Cyasorb UV5411, which can effectively absorb ultraviolet radiation and neutralize free radicals before they can damage the material under adverse conditions. In some cases, antioxidants may be incorporated into formulations in combination with other additives such as UV stabilizers (e.g., benzophenone compounds) to enhance protection against degradation caused by exposure to light or heat. In another embodiment, the antioxidant may include ferrocene derivatives and metal chelates such as phosphites (e.g., tris(2-chloroethyl)phosphite). Alternative antioxidants may include plant-derived extracts or oils such as rosemary extract, green tea extract, or pomegranate oil. Any combination of the above antioxidants or stabilizers can be used.

[0041] Coloring of stretched diol oligomer materials can be achieved through various methods and examples to produce useful coloring effects for coatings, adhesives, sealants, or elastomers. One example involves incorporating pigment particles into one or more precursor solutions before the stretching reaction with monomers, thereby enabling uniform dispersion throughout the material matrix. Another approach involves adding the pigment after the synthesis of the stretched diol oligomer but before the curing reaction, thereby enabling targeting of coloring to specific areas of the composite structure or during the film formation process. Useful coloring methods include dispersion techniques for nanoscale particles, such as dispersions, emulsions, suspensions, or, in some cases, ultrasonic-assisted mixing of solvent systems. For example, titanium dioxide (TiO2) can be used to produce white colorants, while carbon black and iron oxide can produce gray or red. Other pigments, such as ultramarine, cadmium sulfide red, and chromium yellow, or combinations thereof, can be used.

[0042] In another embodiment, graphene sheets or other conductive materials are used as fillers to improve the conductivity of these stretched diol oligomers. Graphene, with its high surface area-to-volume ratio, allows for efficient charge transfer between particles, resulting in improved thermal stability and reduced resistivity of the final material. In this case, graphene flakes may be added during the stretching or curing process. Alternatively, MWNTs or other conductive fillers can be used. By combining different types of conductive filler particles in various ratios, optimal performance characteristics can be achieved according to the requirements of a particular application. For example, a combination of carbon-based fillers and metal oxide nanoparticles can provide both high conductivity and thermal stability. In the embodiment, the aforementioned thermally conductive or conductive fillers may be added to the stretched diol composition at levels of about 0.5% to about 50% by weight, or about 1% to about 30% by weight, about 5% to about 20% by weight, or about 10% to about 15% by weight, based on the weight of the filler relative to the total weight of the stretched diol composition.

[0043] The process of forming a polyurethane network by reacting an extended diol oligomer with a polyfunctional isocyanate species involves several steps and considerations. First, it may be desirable to dissolve the Telekek precursor in a suitable solvent or a mixture thereof before adding one or more polyfunctional isocyanates. The molar ratio of the diisocyanate components can vary considerably depending on the desired properties such as curing rate, viscosity, and mechanical strength; for example, in some examples, using a molar ratio of 1:1.1 to 10 with an excess of diisocyanate in the reaction has been found useful. In some cases, it may be advantageous to add a catalyst or initiator compound to accelerate the reaction process.

[0044] The extended diol composition of this disclosure may comprise a first component comprising an α,ω-hydroxyl-terminated diol oligomer having a number average molecular weight Mn of about 500 g / mol to about 100,000 g / mol or about 1,000 to about 100,000 or about 1,000 to about 10,000, a polyfunctional isocyanate species, and a polyfunctional alcohol species or amine species, wherein the α,ω-hydroxyl-terminated diol oligomer has the following structure (structure A): TIFF2026113412000011.tif30170.

[0045] In the examples, the R2 and R3 groups include a methyl group, an ethyl group, a propyl group, an isopropyl group, a phenyl group, or a combination thereof, and the R1 group includes a polyether, polyester, or polysiloxane. n is defined by the molecular weight and depends on the molecular weight of the R1 unit. A reasonable range is n=1 to about 10, n=1 to about 20, or n=1 to about 100, or, assuming the molecular weight of R1 is, for example, 1000 Da, n is about 2 to about 200. In other examples, the R1 group of the stretched diol composition includes the following structure: TIFF2026113412000012.tif22170.

[0046] In the above formula, m is approximately 1 to approximately 20, p is approximately 5 to approximately 200, and q is approximately 5 to approximately 200. In the examples, the polyfunctional isocyanate species include toluene diisocyanate, isophorone diisocyanate, 4,4'-methylenebis(phenyl isocyanate), 4,4'-methylene-bis(cyclohexyl isocyanate), hexamethylene diisocyanate, poly(hexamethylene diisocyanate), poly(isophorone diisocyanate), or combinations thereof. The molar ratio of the polyfunctional isocyanate species to the stretched diol oligomer is approximately 1.1 to approximately 10, or approximately 1.1 to approximately 5. Optional catalysts may be included in any of the compositions described herein, for example, tin-based catalysts, such as dibutyltin dilaurate or stannous octanoate. In some examples, the stretched diol composition may include UV stabilizers, antioxidants, pigments, or combinations thereof. The polyfunctional alcohol species or amine species may include amines, which include triethylenetetraamine, diethylenetriamine, tetraethylenepentamine, triaminononane, aspartic acid esters, polycarbamide curing agents, or combinations thereof.

[0047] Alternative examples of the stretched diol composition of this disclosure may include a first component comprising an α,ω-hydroxyl-terminated diol oligomer having a number average molecular weight Mn of about 500 Da to about 100,000 Da or about 1,000 Da to about 100,000 Da or about 2,000 Da to about 100,000 Da, a polyfunctional isocyanate species, and a polyfunctional species comprising an alcohol functional group and an epoxy functional group, wherein the α,ω-hydroxyl-terminated diol oligomer has the following structure (Structure A): TIFF2026113412000013.tif34170.

[0048] In examples of the stretched diol composition of structure A, the R2 and R3 groups include a methyl group, an ethyl group, a propyl group, an isopropyl group, a phenyl group, or a combination thereof, and the R1 group may include a polyether, a polyester, or a polysiloxane. n is defined by the molecular weight and depends on the molecular weight of the R1 unit. A reasonable range is n=1 to about 10, n=1 to about 20, or n=1 to about 100, or, assuming the molecular weight of R1 is, for example, 1000, n is about 2 to about 200. In the examples, the R1 group includes the following structure: TIFF2026113412000014.tif22170.

[0049] In the above formula, m is approximately 1 to approximately 20, p is approximately 5 to approximately 200, and q is approximately 5 to approximately 200. The polyfunctional isocyanate species of the stretched diol composition may include toluene diisocyanate, isophorone diisocyanate, 4,4'-methylenebis(phenyl isocyanate), 4,4'-methylene-bis(cyclohexyl isocyanate), hexamethylene diisocyanate, poly(hexamethylene diisocyanate), poly(isophorone diisocyanate), or combinations thereof. In the examples, the stretched diol composition may include a diluent containing an epoxy functional group or a curing agent containing a polyfunctional amine group. The molar ratio of the polyfunctional isocyanate species to the stretched diol oligomer is approximately 1.1 to approximately 10, or approximately 1.1 to approximately 5.

[0050] A method for producing a resin as described herein may include providing a diol oligomer to a reaction vessel, wherein the diol oligomer comprises an α,ω-hydroxyl-terminated diol oligomer having a number average molecular weight Mn of about 500 g / mol to about 100,000 g / mol or 1,000 to about 100,000 or 2,000 to about 100,000; adding a diisocyanate compound to the reaction vessel such that the molar ratio of the diisocyanate compound to the α,ω-hydroxyl-terminated diol oligomer is about 1.1 to about 10; and heating the diol oligomer and the diisocyanate compound in an inert atmosphere at a temperature of about 50 to about 110°C for about 1 to about 2 hours, wherein the diol oligomer comprises [-O-Si(R2,R3)-O-]. The diol oligomer may include cases where R2 and R3 are similar to or the same as those described above with respect to structure A. In the examples, the diol oligomer can be dissolved in the solvent at any stage of the process. The method may further include adding a polyfunctional alcohol to the reaction vessel at a temperature of 100°C, the polyfunctional alcohol containing at least three alcohol functional groups. In the examples, the method may include adding a reactive epoxy or reactive diluent to the reaction vessel, or adding a polyfunctional species containing alcohol functional groups and epoxy functional groups to the reaction vessel.

[0051] Polymer networks based on stretched diol compositions can be alternatively constructed from stretched diol oligomers having an average Mn of 2,000 to 100,000 Da, wherein the oligomers are terminated with α,ω hydroxyl groups having the following structure (structure A): TIFF2026113412000015.tif33170.

[0052] The stretched diol composition may include cases where the R2 and R3 groups of structure A contain a methyl group, an ethyl group, a propyl group, an isopropyl group, a phenyl group, or a combination thereof, and where n is from 1 to about 20. The R1 group may contain a polyether, polyester, or polysiloxane. The R1 group has structure: The composition may include TIFF2026113412000016.tif22170 (wherein m is approximately 1 to approximately 20, and p and q are approximately 5 to approximately 200). In addition, one or more polyfunctional isocyanate species, one or more polyfunctional alcohol species, or amine species may be included in the composition. Optionally, the composition may include catalysts, such as triethylenetetraamine, diethylenetriamine, tetraethylenepentamine, triaminononane (Hexatran), or catalysts belonging to the class of aspartic acid esters or polycarbamide curing agents, or combinations thereof. Optionally, one or more species of reactive epoxy diluents or polyfunctional amine curing agents may also be incorporated into the polymer network. Exemplary species containing alcohols and epoxy groups may include glycidol or other similar materials. Polyfunctional amine curing agents may include triethylenetetraamine, diethylenetriamine, tetraethylenepentamine, triaminononane (Hexatran), or combinations thereof. In the embodiments, the resin or polymer network can be provided or manufactured as a two-piece kit that is mixed at the time of fabrication or compounding.

[0053] While this teaching has been illustrated with respect to one or more embodiments, modifications and / or alterations can be made to the illustrated embodiments without departing from the spirit and scope of the claims. For example, while the process is described as a series of actions or events, it should be understood that this teaching is not limited by the order of such actions or events. Some actions may occur in a different order than those described herein and / or concurrently with actions or events not described herein. Furthermore, not all process steps are required to carry out the methodology according to one or more aspects or embodiments of this disclosure. It will be recognized that structural objects and / or processing steps may be added, or existing structural objects and / or processing steps may be removed or modified. In addition, one or more of the actions described herein may be performed in one or more other actions and / or phases. Furthermore, to the extent that “including,” “includes,” “having,” “has,” “with,” or variations thereof are used in any of the detailed description and claims, these terms are intended to be as comprehensive as the term “comprising.” The expression “at least one of the following” is used to mean that one or more of the enumerated items may be selected. Furthermore, in the description and claims herein, the term “on” used with respect to two materials, such as one being “on top of” the other, means that there is at least some contact between the materials, whereas “over” means that multiple materials are close to each other, but may be accompanied by one or more additional intervening materials, and contact is possible but not required. Neither “on” nor “over” as used herein implies any direction. The term “conformal” refers to a coating material in which the angle of the underlying material is protected by the conformal material. The term "approximately" indicates that the listed values ​​may be modified to some extent, provided that it does not result in a process or structural incompatibility with the illustrated embodiment.The terms “couple,” “couple,” “connect,” “connection,” “connected,” “in connection with,” and “connecting” refer to being “directly connected” or “connected via one or more intermediate elements or members.” Finally, “exemplary / illustrative” indicates that the description is used as an example rather than suggesting that it is ideal. Other embodiments of this teaching will become apparent to those skilled in the art by examining the specifications and practices of the disclosure herein. This specification and the examples are intended to be considered illustrative only, and the true scope and spirit of this teaching are indicated by the claims.

Claims

1. A stretched diol composition, The first component contains an α,ω-hydroxyl-terminated diol oligomer with a number-average molecular weight Mn of approximately 500 Da to approximately 100,000 Da. Polyfunctional isocyanate species, and Polyfunctional alcohol species or amine species Includes, The aforementioned α,ω-hydroxyl-terminated diol oligomer has the following structure: [In the above formula: R １ It contains polyether, polyester, or polysiloxane. R ２ Base and R ３ The group includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a phenyl group, or a combination thereof. n is approximately 1 to approximately 100. An extended diol composition having the following characteristics.

2. R １ The base, structure: m is approximately 1 to approximately 20. p is approximately 5 to approximately 200. q is approximately 5 to approximately 200. The stretched diol composition according to claim 1, comprising:

3. The stretched diol composition according to claim 1, wherein the polyfunctional isocyanate species includes toluene diisocyanate, isophorone diisocyanate, 4,4'-methylenebis(phenyl isocyanate), 4,4'-methylene-bis(cyclohexyl isocyanate), hexamethylene diisocyanate, poly(hexamethylene diisocyanate), poly(isophorone diisocyanate), or a combination thereof.

4. The stretched diol composition according to claim 1, wherein the molar ratio of the polyfunctional isocyanate species to the stretched diol oligomer is about 1.1 to about 10.

5. The stretched diol composition according to claim 1, further comprising a catalyst.

6. The stretched diol composition according to claim 5, wherein the catalyst comprises a tin-based catalyst.

7. The stretched diol composition according to claim 5, wherein the catalyst comprises dibutyltin dilaurate or stannous octanoate.

8. The stretched diol composition according to claim 1, further comprising a UV stabilizer, an antioxidant, a pigment, or a combination thereof.

9. The stretched diol composition according to claim 1, wherein the polyfunctional alcohol species or amine species comprises an amine, and the amine comprises triethylenetetraamine, diethylenetriamine, tetraethylenepentamine, triaminononane, aspartic acid ester, polycarbamide curing agent, or a combination thereof.

10. A stretched diol composition, The first component contains an α,ω-hydroxyl-terminated diol oligomer with a number-average molecular weight Mn of approximately 500 Da to approximately 100,000 Da. Polyfunctional isocyanate species, and Polyfunctional species containing alcohol and epoxy functional groups Includes, The aforementioned α,ω-hydroxyl-terminated diol oligomer has the following structure: [In the above formula: R １ It contains polyether, polyester, or polysiloxane. R ２ Base and R ３ The group includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a phenyl group, or a combination thereof. n is approximately 1 to approximately 100. An extended diol composition having the following characteristics.

11. R １ The base, structure: m is approximately 1 to approximately 20. p is approximately 5 to approximately 200. q is approximately 5 to approximately 200. The stretched diol composition according to claim 10, comprising

12. The stretched diol composition according to claim 10, wherein the Mn is approximately 1,000 Da to approximately 10,000 Da.

13. The stretched diol composition according to claim 10, wherein the polyfunctional isocyanate species includes toluene diisocyanate, isophorone diisocyanate, 4,4'-methylenebis(phenyl isocyanate), 4,4'-methylene-bis(cyclohexyl isocyanate), hexamethylene diisocyanate, poly(hexamethylene diisocyanate), poly(isophorone diisocyanate), or a combination thereof.

14. The stretched diol composition according to claim 10, further comprising a reactive diluent containing an epoxy functional group.

15. The stretched diol composition according to claim 10, further comprising a curing agent containing a polyfunctional amine group.

16. The stretched diol composition according to claim 10, wherein the molar ratio of the polyfunctional isocyanate species to the stretched diol oligomer is about 1.1 to about 10.

17. A method for producing resin, The method involves providing a diol oligomer containing an α,ω-hydroxyl-terminated diol oligomer having a number-average molecular weight Mn of approximately 500 Da to approximately 100,000 Da to a reaction vessel, The diisocyanate compound is added to the reaction vessel such that the molar ratio of the diisocyanate compound to the α,ω-hydroxyl-terminated diol oligomer is approximately 1.1 to approximately 10. The diol oligomer and the diisocyanate compound are heated in an inert atmosphere at a temperature of about 50 to about 110°C for about 1 to 2 hours. Includes, The diol oligomer contains [-O-Si(R ２ , R ３ )-O-]. R ２ Base and R ３ A method for producing a resin in which the group may include a methyl group, an ethyl group, a propyl group, an isopropyl group, a phenyl group, or a combination thereof.

18. A method for producing the resin according to claim 17, further comprising dissolving the diol oligomer in a solvent.

19. A method for producing the resin according to claim 17, further comprising adding a polyfunctional alcohol to the reaction vessel at a temperature of 100°C, wherein the polyfunctional alcohol comprises at least three alcohol functional groups.

20. A method for producing a resin according to claim 17, further comprising adding a reactive epoxy diluent to the reaction vessel.

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