Hybrid coatings using ring-opening metathesis polymerizable monomers and epoxy resins

Abstract

A coating composition comprising an epoxy resin, a ring-opening metathesis polymerizable monomer, an amine curing agent, and a metathesis catalyst. The coating method includes forming the coating composition, depositing the coating composition on a substrate, evaporating solvent from the deposited coating composition, and curing the coating composition. The article includes a substrate and a coating layer formed from the coating composition.

Description

[Technical Field]

[0001] This application claims priority to U.S. Provisional Application No. 63 / 433,552, filed December 19, 2022, U.S. Provisional Application No. 63 / 433,553, filed December 19, 2022, and U.S. Provisional Application No. 63 / 446,401, filed February 17, 2023, the contents of which are incorporated herein by reference. [Background technology]

[0002] This embodiment relates to a hybrid coating composition containing both a ring-opening metathesis polymerizable monomer and an epoxy resin. Curing can be achieved at ambient temperature using both an amine curing agent and a ruthenium-based Grubbs catalyst. The hybrid coating exhibits excellent flexibility, high gloss, chemical resistance, adhesion, and compatibility between the epoxy and the monomer, providing cure times and rheological properties that allow for airless spray application. It is particularly applicable in applications requiring ambient cure, flexibility, and chemical resistance. However, it should be understood that this exemplary embodiment is also applicable to other similar applications.

[0003] It is desirable to develop new coatings that have high flexibility and gloss, good adhesion, and excellent chemical resistance, cure at room temperature in a short time, and exhibit compatibility between the ring-opening metathesis polymerizable monomer and the epoxy resin. It is also desirable to develop coatings with the above properties that can be applied by airless spraying. Furthermore, to reduce costs and improve properties, coatings that meet the outlined requirements and have a high filler content (e.g., >30 wt. %, >40 wt. %) are desirable. Summary of the Invention

[0004] The coating composition includes an epoxy resin, a ring-opening metathesis polymerizable monomer, an amine curing agent (e.g., a polyamide-based curing agent), and a metathesis catalyst (e.g., a ruthenium-based Grubbs catalyst). The composition may further include a solvent, a filler, and one or more other additives.

[0005] The coating composition may include, but is not limited to, any epoxy resin that can be polymerized by an amine catalyst. Preferred epoxy resins are novolac-type epoxy resins with a functionality greater than 2.

[0006] The coating composition further comprises a monomer capable of ring-opening metathesis polymerization. The monomer may comprise one or more cyclic olefins. Preferred examples include, but are not limited to, dicyclopentadiene, tricyclopentadiene, norbornene, and functional norbornene monomers.

[0007] Additionally, the coating can include a solvent that dissolves both the epoxy resin and the ring-opening metathesis polymerizable monomer. Examples of such solvents include, but are not limited to, aromatic solvents such as xylene, toluene, and Solvent 150, or glycol ether solvents such as Dowonal DPM.

[0008] Additionally, the coating includes an amine curing agent that improves compatibility between the epoxy resin and the ring-opening metathesis polymerizable monomer without reducing the efficiency of the ring-opening metathesis catalyst. Examples include, but are not limited to, polyamide curing agents and phenalkamine curing agents.

[0009] Additionally, the coating composition may contain fillers. Examples include, but are not limited to, silica (e.g., crystalline silica), barium sulfate, and wollastonite. Other non-limiting examples of fillers include alumina, silicates, talc, aluminosilicates, mica, diatomaceous earth, calcium carbonate, calcium sulfate, aluminum hydroxide, magnesium hydroxide, zinc oxide, and carbon black.

[0010] Additionally, the coating composition may include a rheology modifier, examples of which include, but are not limited to, hydrophobic fumed silica.

[0011] Additionally, the coating may contain additional additives such as adhesion promoters, flow improvers and leveling agents.

[0012] The coating can be cured at room temperature in less than 12 hours, or the coating can be further cured with heat to improve properties.

[0013] Additionally, methods of applying the coating are disclosed that include depositing a coating composition comprising the described composition, evaporating the solvent, and curing the epoxy resin.

[0014] These and other non-limiting features are described in more detail below. [Brief explanation of the drawings]

[0015] [Figure 1] FIG. 1 is a flow chart illustrating a non-limiting example of a coating method according to some embodiments of the present disclosure.

[0016] [Figure 2] FIG. 2 is a cross-sectional side view of a coated article according to some embodiments of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0017] Detailed Description The present disclosure may be understood more readily by reference to the following detailed description of the preferred embodiments contained herein. In the following specification and claims, reference will be made to certain terms that shall be defined to have the following meanings.

[0018] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art. In case of conflict, the present specification, including definitions, will prevail. Preferred methods and materials are described below, but similar or equivalent methods and materials can be used in the practice or testing of this disclosure. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety. The materials, methods, and articles disclosed herein are for illustrative purposes only and are not intended to be limiting.

[0019] The singular forms "a," "an," and "the" are intended to include plural referents unless the context clearly dictates otherwise.

[0020] As used in this specification and claims, the term "comprising" can include the embodiments of "consisting of" and "consisting essentially of." As used herein, the terms "comprise(s)," "include(s)," "having," "has," "can," "contain(s)," and variations thereof are intended to be open-ended transitional phrases that require the presence of the specified ingredients / steps and permit the presence of other ingredients / steps. However, such descriptions should also be interpreted as describing compositions, mixtures, or methods that "consist of" and "consist essentially of" the listed ingredients / steps, which permit only the specified ingredients / steps and any impurities that may result therefrom to be present, and exclude other ingredients / steps.

[0021] Unless otherwise specified, numerical values ​​herein should be understood to include values ​​that would be the same when subtracted to the same number of significant figures, and values ​​that differ from the stated value by no more than the experimental error of conventional measuring techniques of the type being used to determine the particular value.

[0022] All ranges disclosed herein are inclusive of the recited endpoints and are independently combinable (e.g., the range "2 to 10" includes the endpoints 2 and 10, and all intermediate values). The endpoints of ranges and any values ​​disclosed herein are not limited to the exact range or value; they are sufficiently imprecise to include values ​​that approximate those ranges and / or values.

[0023] As used herein, approximations may be used to modify any quantitative expression that may vary without resulting in a change in the fundamental function to which it pertains. Thus, values ​​modified by one or more terms such as "about" and "substantially" may not necessarily be limited to the exact value specified. The modifier "about" should also be interpreted as revealing a range defined by the absolute values ​​of the two endpoints. For example, the expression "about 2 to about 4" also discloses a range of "2 to 4." The term "about" may refer to plus or minus 10% of the indicated numerical value. For example, "about 10%" may indicate a range of 9% to 11%, and "about 1" may mean 0.9 to 1.1.

[0024] In the recitation of numerical ranges herein, each intervening number is expressly contemplated with the same degree of precision, e.g., in the range 6 to 9, the numbers 7 and 8 are contemplated in addition to 6 and 9, and in the range 6.0 to 7.0, the numbers 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, and 7.0 are expressly contemplated.

[0025] The present disclosure relates to a coating composition comprising an epoxy resin, a monomer capable of ring-opening metathesis polymerization, an amine curing agent, and a catalyst capable of initiating ring-opening metathesis polymerization.

[0026] The coating composition has a dual cure mechanism: the epoxy is cured with an amine curing agent, and the monomer capable of ring-opening metathesis polymerization is cured with an appropriate initiator, such as a ruthenium-based Grubbs catalyst. Combining the two resin systems allows for a hybrid coating that combines the advantages of each technology. Amine-cured epoxy-based coatings have excellent mechanical properties, good chemical resistance, and adhesion to substrates, but tend to be less flexible and not highly hydrophobic. Coatings prepared from ring-opening metathesis polymerization have excellent flexibility and good hydrophobicity, but tend to have poor chemical resistance to the epoxy resin and poor adhesion to substrates. Combining the two cure mechanisms allows the benefits of both systems to be realized in a single coating, resulting in a coating with high chemical resistance, good adhesion, high flexibility, hydrophobicity, and excellent mechanical properties. The formulation components can be selected to provide a good blend. Epoxy resins and monomers capable of ring-opening metathesis polymerization are typically incompatible, and when mixed together in a coating composition, they tend to separate, resulting in an inhomogeneous coating. The present coating overcomes this problem by using a solvent that can compatibilize the epoxy resin and the monomers capable of ring-opening metathesis polymerization. Examples include aromatic solvents such as xylene, toluene, and Solvent 150, and glycol ether solvents such as Dowanol DPM. The solvent must be added in an amount sufficient to compatibilize the coating formulation, but not so high that it adversely affects the overall solids content of the formulation. Catalysts capable of initiating ring-opening metathesis polymerization, such as Grubbs' catalyst, can be reduced in efficiency by reaction with amines. Therefore, the amine should be selected so as not to poison the Grubbs' catalyst. Furthermore, amines may provide additional compatibility for the epoxy resin and the monomers capable of ring-opening metathesis polymerization. Examples of amines that accomplish both goals include compounded polyamide curing agents and phenalkamine curing agents.Amine curing agents should also provide a dry time of less than 12 hours for applications requiring rapid return to service. When combined with a Grubbs catalyst, coating compositions with good dry times are achievable. Coating compositions also contain a high degree of filler to reduce overall coating costs and improve coating properties. These fillers are commonly known in the industry, and examples include, but are not limited to, silica, barium sulfate, and wollastonite. Formulations can also contain other coating additives, such as fumed silica, adhesion promoters, flow agents, and leveling agents. Coatings made solely from ring-opening metathesis polymerizable monomers typically have very short pot lives, typically on the order of 5 to 15 minutes, making this technique unsuitable for airless spray-applied coatings, which require working times of 30 minutes or more. By combining two curing techniques, working times of more than 30 minutes and viscosities suitable for airless spray-applied coatings can be achieved. Coatings should also be formulated in a way that does not cause the components to react with each other, contaminate the catalyst, and limit the number of components that need to be mixed together. To achieve this, the Grubbs catalyst should be compounded in one component of the formulation, and the monomer capable of ring-opening metathesis polymerization should be mixed with the amine catalyst in the formulation. By separating the amine and Grubbs catalyst, the activity of the Grubbs catalyst is maintained and the formulation is limited to only two components that must be mixed together before application.

[0027] The coating composition can be provided in two parts, A and B. Formulating the composition in parts A and B can have advantages such as avoiding premature reactions. Non-limiting examples of compositions for parts A and B are shown in Tables 1 and 2 below.

[0028] [Table 1]

[0029] [Table 2]

[0030] The A:B ratio depends on the type of amine and epoxy used, which dictates the stoichiometric ratio. The A:B ratio may also depend on the filler and solvent content. In some embodiments, the stoichiometric ratio of epoxy to amine ranges from about 0.8 to about 1.2, including ranges from about 0.9 to about 1.1 and about 0.95 to about 1.05. Formulations can be performed at a stoichiometric ratio of 1.0.

[0031] It should be understood that Part A and Part B are not limited to the specific materials or types of materials described above. Furthermore, various additives may be transferred from Part A to Part B, or vice versa. However, generally, the metathesis catalyst and the monomer capable of ring-opening metathesis polymerization are provided in separate parts. Similarly, the epoxy resin and the amine curing agent are also provided in separate parts. Furthermore, the amine and metathesis catalyst may be provided in separate parts to avoid contamination of the metathesis catalyst by the amine. When both Part A and Part B contain a specific type of additive, the specific additives included in Part A and Part B may be the same or different. Part A and Part B may be provided separately in a shelf-stable kit. In some embodiments, the kit has a size ranging from 1 quart to 5 gallons.

[0032] Non-limiting examples of metathesis catalysts are disclosed in U.S. Patent Nos. 5,728,917, 5,831,108, 7,132,503, and 7,294,717; and U.S. Patent Application Publication Nos. 2020 / 0362273 and 2022 / 0162351. The contents of these patents and publications are incorporated herein by reference in their entireties.

[0033] Some additional non-limiting examples of ring-opening metathesis polymerization catalysts include [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(2-isopropoxybenzylidene)ruthenium(II) (CAS No. 301224-40-8); dichloro(benzylidene)bis(tricyclohexylphosphine)ruthenium(II) (CAS No. 172222-30-9); [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]-[2-[[(2-methylphenyl)imino]methyl]-phenolyl]-[3-phenyl-1H-inden-1-ylidene](chloro)ruthenium(II) (CAS No. 934538-12-2; Bis[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(3-phenyl-1H-inden-1-ylidene)ruthenium(II) (CAS No. 1383684-54-5); Dichlorobis(isobutylphoban)(3-phenyl-1H-indenylidene)ruthenium(II) (CAS No. 894423-99-5); [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(benzylidene)(tricyclohexylphosphine)ruthenium(II) (CAS No. 246047-72-3;[1,3-Bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(3-methyl-2-butenylidene)(tricyclohexylphosphine)ruthenium(II) (CAS No. 253688-91-4);[1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(3-phenyl-1H-inden-1-ylidene)(pyridyl)ruthenium(II) (CAS No. 1031262-76-6);[1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(3-phenyl-1H-inden-1-ylidene)(triphenylphosphine)ruthenium(II) (CAS No. 340810-50-6; dichloro(2-isopropoxybenzylidene)(tricyclohexylphosphine)ruthenium(II) (CAS No.203714-71-0); [1,3-bis(2-tolyl)-2-imidazolidinylidene]dichloro(2-isopropoxybenzylidene)ruthenium(II) (CAS No. 927429-61-6); and [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(3-methyl-2-butenylidene)(tricyclohexylphosphine)ruthenium(II) (CAS No. 253688-91-4).

[0034] 1 is a flowchart illustrating a non-limiting example of a coating process 100 according to some embodiments of the present disclosure. The process 100 includes forming a coating composition 110, depositing the coating composition on a substrate 120, evaporating solvent (if present in the coating composition) 130, and curing the deposited coating composition 140.

[0035] In some embodiments, the coating composition is formed (110) by mixing a first part (A) and a second part (B).

[0036] The coating composition is deposited 120 onto the substrate using any suitable application process. In certain embodiments, airless spray application is used.

[0037] If the coating composition includes a solvent, the solvent may be partially or completely evaporated (130).

[0038] Curing (140) includes both amine curing and ring-opening metathesis polymerization of the epoxy resin.

[0039] It should be noted that one or more steps may be repeated to form a coating of a desired thickness.

[0040] 2 is a cross-sectional side view of a coated article 250 according to some embodiments of the present disclosure. The article includes a substrate 260 having a coating layer 270 deposited thereon. The substrate 260 may be a single-layer substrate or a multi-layer substrate. The substrate may include at least one metallic element and / or at least one semi-metallic element, including metal alloys. Metals include Li, Be, Na, Mg, Al, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Rb, Sr, Y, Zr, Nb, M o, Tc, Ru, Rh, Pd, Ag, Cd, In, Sn, Cs, Ba, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Tl, Pb, Bi, Po, Fr, Ra, Ac, Th, Pa, Np, Pu, Am, Cm, Bk, Can be selected from Cf, Es, Fm, Md, No, Lr, Rf, Db, Sg, Bh, Hs, Mt, Ds, Rg, Cn, Nh, Fl, Mc, and Lv. The metalloid can be selected from B, Si, Ge, As, Sb, and Te. Coating layer 270 is formed from a coating composition described herein and may be formed in a single coating or multiple coatings.

[0041] The following examples are provided to illustrate the apparatus and methods of the present disclosure. These examples are merely illustrative and are not intended to limit the disclosure to the materials, conditions, or process parameters described in the examples. [Example]

[0042] Example 1: Enhanced coating composition containing a dual cure mechanism

[0043] [Table 3]

[0044] Solvent 150, EXP-2020A, and YDF-173 were mixed in a suitable container equipped with a Cowles mixing blade. The ingredients were mixed for approximately 5 minutes until uniform. The mixing speed was then increased, Cimbar XF was slowly added, and the mixture was mixed at high shear for 10-15 minutes. The adhesion promoter and titanium dioxide were then added and mixed at high shear for 2-3 minutes. Aerosil R202 was then added, and the mixture was mixed at high shear for 10 minutes. Finally, iron oxide was added, and the mixture was mixed for an additional 2-3 minutes.

[0045] [Table 4]

[0046] Ankamide 2353 and EXP-1961-NI were added to a mixing vessel equipped with a Cowles mixing blade and mixed until uniform. Next, Cimbar XF was slowly added to the mixture at high shear and mixed for 10 minutes. Finally, Aerosil R202 was slowly added and mixed at high shear for an additional 10 minutes.

[0047] Part A and Part B were then thoroughly mixed to provide an airless sprayable coating composition having the following properties: Gel time (Shyodu gel timer): 348 minutes Sag resistance 60 mils+ Drying time (circular drying time recorder) 8 hours Tg of cured film (second heat by DSC) 91°C

[0048] It will be appreciated that variations of the above-disclosed and other features and functions, or alternatives thereof, may be combined into many other different systems or applications. Various presently unforeseen or unanticipated alternatives, modifications, variations, or improvements thereon may occur to those skilled in the art, and are also intended to be encompassed by the following claims.

Claims

1. Epoxy resin; ring-opening metathesis polymerizable monomers; an amine curing agent; and metathesis catalyst 1. A coating composition comprising:

2. moreover, solvent; Filler; adhesion promoters; a rheology modifier; and pigment The coating composition of claim 1 comprising:

3. (A) a first portion comprising: epoxy resin; and a metathesis catalyst; and (B) a second portion comprising: a ring-opening metathesis polymerizable monomer; and Amine hardener.

1. A coating composition kit comprising:

4. The first portion (A) further comprises: a solvent; and Optionally, at least one additive selected from the group consisting of fillers, adhesion promoters, rheology modifiers, and pigments. The coating composition kit of claim 3 , comprising:

5. The coating composition kit of claim 4 , wherein the solvent comprises an aromatic hydrocarbon.

6. 4. The coating composition kit of claim 3, wherein the second part (B) further comprises at least one additive selected from the group consisting of fillers and rheology modifiers.

7. The first portion (A) is 0.01 to 5 wt. % of a metathesis catalyst; 20 to 50 wt. % of an epoxy resin; 30 to 70 wt. % of a filler; 0-30% by weight of a solvent; 0-5 wt. % adhesion promoter; 0 to 5 wt. % of a first pigment; 0 to 5% by weight of a second pigment; and 0-5 wt. % rheology modifier The coating composition kit of claim 3 , comprising:

8. The first portion (A) is 0.1 to 2 wt. % of a metathesis catalyst; 25 to 45 wt. % epoxy resin; 40 to 60 wt. % filler; 3 to 20 wt. % of a solvent; 0.01 to 2 wt. % of an adhesion promoter; 0.01 to 2 wt. % of a first pigment; 0.5 to 3% by weight of a second pigment; and 0.5 to 3 wt. % of a rheology modifier; The coating composition kit of claim 3 , comprising:

9. The first portion (A) is 0.25 to 0.75 wt. % of a metathesis catalyst; 30 to 40 wt. % of an epoxy resin; 45-55 wt. % filler; 5 to 15 wt. % solvent; 0.1 to 0.7 wt. % of an adhesion promoter; 0.1 to 0.7 wt. % of a first pigment; 1 to 1.5 wt. % of a second pigment; and 1.5 to 2 wt. % of a rheology modifier; The coating composition kit of claim 3 , comprising:

10. The second portion (B) is 20 to 70 wt. % of an amine curing agent; 10 to 60 wt. % of a ring-opening metathesis polymerizable monomer; 0 to 30% by weight of a filler; and 0-10 wt. % of a rheology modifier; The coating composition kit of claim 3 , comprising:

11. The second portion (B) is 30 to 60 wt. % of an amine curing agent; 20 to 50 wt. % of a ring-opening metathesis polymerizable monomer; 10 to 25% by weight of a filler; and 1 to 7 wt. % of a rheology modifier; The coating composition kit of claim 3 , comprising:

12. The second portion (B) is 40-50 wt. % amine curing agent; 30 to 40 wt. % of a ring-opening metathesis polymerizable monomer; 15-20% by weight of a filler; and 2-5 wt. % of a rheology modifier; The coating composition kit of claim 3 , comprising:

13. Forming a coating composition by mixing: (A) a first portion comprising: epoxy resin; and a metathesis catalyst; and (B) a second portion comprising: a ring-opening metathesis polymerizable monomer; and amine curing agents; depositing the coating composition on a substrate; and curing the coating composition; A coating method comprising:

14. At least one of the first part (A) and the second part (B) further contains a solvent, The method further comprises:

14. The method of coating of claim 13, comprising evaporating the solvent after the deposition and before the curing.

15. The coating method of claim 13 , wherein the deposition comprises airless spray deposition.

16. 14. The coating method of claim 13, wherein the curing is carried out at ambient or elevated temperatures to improve properties and / or increase the cure rate.

17. A coated article formed by the method of claim 13.

18. The coating method of claim 14, wherein the solvent comprises an aromatic hydrocarbon.

19. The first portion (A) is 0.01 to 5 wt. % of a metathesis catalyst; 20 to 50 wt. % of an epoxy resin; 30 to 70 wt. % of a filler; 0 to 30 wt. % of a solvent; 0-5 wt. % adhesion promoter; 0 to 5 wt. % of a first pigment; 0 to 5% by weight of a second pigment; and 0-5 wt. % of a rheology modifier; The coating method of claim 13, comprising:

20. The second portion (B) is 20 to 70 wt. % of an amine curing agent; 10 to 60 wt. % of a ring-opening metathesis polymerizable monomer; 0 to 30% by weight of a filler; and 0-10 wt. % of a rheology modifier; The coating method of claim 13, comprising:

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