WO2019213092A1 - Binder compositions and processes for making and using same - Google Patents

Abstract

Binder compositions and processes for making and using same. In some examples, the binder composition can include a first oligomer that can include a polyalcohol-monoether group covalently bonded thereto, a second oligomer that can include a polyalcohol-polyether group covalently bonded thereto, or a mixture thereof. The first oligomer can have the chemical formula (I) and the second oligomer can have the chemical formula (II).

Description

BINDER COMPOSITIONS AND PROCESSES FOR MAKING AND USING SAME

BACKGROUND

Field

[0001] Embodiments described generally relate to binder compositions and processes for making and using same. More particularly, such embodiments relate to binder compositions that can be or include an oligomer that can include a polyalcohol-monoether and/or a polyalcohol-polyether group covalently bonded thereto and processes for making and using same. Other embodiments relate to polyalcohol-monoethers and polyalcohol-polyethers.

Description of the Related Art

[0002] Sheets or mats of non-woven fibers, e.g ., glass fibers or“fiberglass", are finding increasing application in the building materials industry. Fiberglass mats are typically used as or in, among others, insulation materials, flooring products, wall panel products, and roofing products. Fiberglass mats are usually made commercially by a wet-laid process that involves the addition of a binder or adhesive solution to the glass fiber mat to bind and hold the fibers together. Depending on the particular fiberglass product and its particular application, different mechanical properties are desirable, such as tear strength, dry tensile strength, and/or wet tensile strength. Different binder compositions yield fiberglass and other products having differing properties.

[0003] There is a need, therefore, for new binder compositions and processes for making and using same.

SUMMARY

[0004] Binder compositions and processes for making and using same are provided. In some examples, the binder composition can include a first oligomer that can include a polyalcohol- monoether group covalently bonded thereto, a second oligomer that can include a polyalcohol- polyether group covalently bonded thereto, or a mixture thereof. The first oligomer can have a chemical formula (I) of:

first oligomer In chemical formula (I), A and F can independently be CH₂, O, or NH; B, C, D, and E can independently be CH₂ or O; I, J, K, L, and M can independently be CH₃ or H; X and Z can independently be OH, NH₂, or NH; Y can be O or NH; n, o, p, q, r, s, t, and u can independently be an integer of 0 to 6; at least one of n, u, and t can be an integer of 1 to 6; and the first oligomer can be selected from the group consisting of: a phenol-aldehyde oligomer; a urea-aldehyde oligomer; a melamine- aldehyde oligomer; a phenol-urea-aldehyde oligomer; a melamine-urea-aldehyde oligomer; a biuret-aldehyde oligomer; an adipamide-aldehyde oligomer; a 2-cyano-guanidine-aldehyde oligomer; a thiourea-aldehyde oligomer; a cyanurate-aldehyde oligomer; a bis-phenol alcohol- aldehyde oligomer; a 4-/t 7-butylphenol -aldehyde oligomer; and a 2,4-di-tert-butylphenol- aldehyde oligomer or

[0005] The second oligomer can have a chemical formula (II) of:

second oligomer j_n chemical formula (II), A’ and F’ can independently be CH₂, O, or NH; B’, C’, D’, and E’ can independently be CFh or O; F, J’, K’, L’, and M’ can independently be CFh or H; X’ and Z’ can independently be OH, NH₂, or NH; Y’ can be O or NH; n’, o’, p’, q’, r’, s’, f , and u’ can independently be an integer of 0 to 6; at least one of n’, u’, and f can be an integer of 1 to 6; and the second oligomer can be selected from the group consisting of: a phenol-aldehyde oligomer; a urea-aldehyde oligomer; a melamine-aldehyde oligomer; a phenol-urea-aldehyde oligomer; a melamine-urea- aldehyde oligomer; a biuret-aldehyde oligomer; an adipamide-aldehyde oligomer; a 2-cyano- guanidine-aldehyde oligomer; a thiourea-aldehyde oligomer; a cyanurate-aldehyde oligomer; a bis-phenol alcohol-aldehyde oligomer; a 4-/t'/7-butyl phenol -aldehyde oligomer; and a 2,4-di-tert- butylphenol-aldehyde oligomer.

[0006] In some examples, a process for making a binder composition can include reacting a first mixture that can include a polyamine, a polyol, or a mixture thereof and an aldehyde to produce a first intermediate. In some examples, an epihalohydrin compound can be combined with the first intermediate to produce a second mixture that can include the first intermediate and the epihalohydrin compound. The second mixture that can include the first intermediate and the epihalohydrin compound can be reacted to produce a second intermediate. In some examples, an amide compound, a phenolic compound, or a mixture thereof can be combined with the second intermediate to produce a third mixture that can include the second intermediate and the amide compound, the phenolic compound, or the mixture of the amide compound and the phenolic compound. Third mixture that can include the second intermediate and the amide compound, the phenolic compound, or the mixture of the amide compound and the phenolic compound can be reacted to produce a first oligomer that can include a polyalcohol-monoether group covalently bonded thereto, a second oligomer that can include a polyalcohol-polyether group covalently bonded thereto, or a mixture thereof. The first oligomer can have the chemical formula (I). The second oligomer can have the chemical formula (II).

[0007] In some examples, a process for making a composite product can include contacting a plurality of substrates with a binder composition that can include a first oligomer that can include a polyalcohol-monoether group covalently bonded thereto, a second oligomer that can include a polyalcohol-polyether group covalently bonded, or a mixture thereof to produce a resinated furnish. The first oligomer that can include the polyalcohol-monoether group covalently bonded thereto can have chemical formula (I). The second oligomer that can include the polyalcohol- polyether group covalently bonded thereto can have chemical formula (II). The process can also include at least partially curing the binder composition in the resinated furnish to produce a composite product. [0008] Polyalcohol-monoethers and polyalcohol-polyethers are also provided. In some examples, a polyalcohol-monoether can have a chemical formula (III) of:

[0009] In chemical formula (III), A and F can be independently CH₂, O, or NH; B, C, D, and E can be independently CH₂ or O; I, J, K, L, and M can be independently C¾ or H; X and Z can be independently OH, NH₂, or NH; Y can be O or NH; n, o, p, q, r, s, t, and u can be independently an integer of 0 to 6, at least one of n, u, and t can be an integer of 1 to 6; and R can be CL, Br, or I.

[0010] In some examples, a polyalcohol -poly ether can have a chemical formula (IV) of:

[0011] In chemical formula (IV), A and F can be independently CH₂, O, or NH; B, C, D, and E can be independently CH₂ or O; I, J, K, L, and M can be independently CEE or H; X and Z can be independently OH, NH₂, or NH; Y can be O or NH; n, o, p, q, r, s, t, and u can be independently an integer of 0 to 6; at least one of n, u, and t can be an integer of 1 to 6; and R can be Cl, Br, or I. DETAILED DESCRIPTION

[0012] The binder composition can be or include an oligomer having (1) one or more polyalcohol- monoether groups covalently bonded thereto, (2) one or more polyalcohol-polyether groups covalently bonded thereto, or (3) one or more polyalcohol-monoether groups and one or more polyalcohol-polyether groups covalently bonded thereto. It has been surprisingly and unexpectedly discovered that the binder composition can be used to produce composite products having sufficient tensile properties even when the binder composition is over cured. For example, it has been discovered that fiberglass mats made by contacting a plurality of glass fibers with the binder composition and curing the binder composition can have acceptable tensile properties even when the binder composition is over cured, e.g ., by heating to an elevated temperature greater than necessary and/or longer than necessary to cure the binder composition sufficiently to produce the fiberglass mat.

[0013] The oligomer having a polyalcohol-monoether group covalently bonded thereto can have a chemical formula (I) of:

oligomer

(I),

[0014] In chemical formula (I), A and F can independently be CFh, O, or NH; B, C, D, and E can independently be CFb or O; G. I, J, K, L, and M can independently be CFE or H; X and Z can independently be OH, NH₂, or NH; Y can be O, NH, or N; n, o, p, q, r, s, t, and u can independently be an integer of 0 to 6, at least one of n, u and t can be an integer of 1 to 6; and the oligomer can be a phenol-aldehyde oligomer; a urea-aldehyde oligomer; a melamine-aldehyde oligomer; a biuret-aldehyde oligomer; an adipamide-aldehyde oligomer; a 2-cyano-guanidine-aldehyde oligomer; a thiourea-aldehyde oligomer; a cyanurate-aldehyde oligomer; a bis-phenol alcohol- aldehyde oligomer; a 4-/tW-butylphenol -aldehyde oligomer; or a 2,4-di-tert-butylphenol-aldehyde oligomer. [0015] In some examples, in chemical formula (I), X and Z can be NH; n and u can be 1; G and M can be H; o, p, q, r s, and t can be 0; and the oligomer can be the phenol-aldehyde oligomer; the urea-aldehyde oligomer; the melamine-aldehyde oligomer; the phenol-urea-aldehyde oligomer; the melamine-urea-aldehyde oligomer; the biuret-aldehyde oligomer; the adipamide-aldehyde oligomer; the 2-cyano-guanidine-aldehyde oligomer; the thiourea-aldehyde oligomer; the cyanurate-aldehyde oligomer; the bis-phenol alcohol-aldehyde oligomer; the 4-te/V-butyl phenol - aldehyde oligomer; or the 2,4-di-tert-butylphenol-aldehyde oligomer. In one example, in chemical formula (I), X and Z can be NH; n and u can be 1; G and M can be H; o, p, q, r s, and t can be 0; and the oligomer can be the urea-formaldehyde oligomer. In another example, in chemical formula (I), X and Z can be NH; n and u can be 1 ; G and M can be H; o, p, q, r s, and t can be 0, and the oligomer can be the phenol-formaldehyde oligomer. In another example, in chemical formula (I), X and Z can be NH; n and u can be 1; G and M can be H; o, p, q, r s, and t can be 0, and the oligomer can be the melamine-formaldehyde oligomer.

[0016] In some examples, in chemical formula (I), X and Z can be NH; o, p, s, t, and u can be 1; n, q, and r can be 0; A, B, E, and F can be CH₂; I, L and M can be H; Y can be N; and the oligomer can be the urea-formaldehyde oligomer. In some examples, X and Z can be NH; o, p, s, t, and u can be 1; n, q, and r can be 0; A, B, E, and F can be CH₂; I, L and M can be H; Y can be N; and the oligomer can be the phenol-formaldehyde oligomer. In some examples, X and Z can be NH; o, p, s, t, and u can be 1; n, q, and r can be 0; A, B, E, and F can be CH₂; I, L and M can be H; Y can be N; and the oligomer can be the melamine-formaldehyde oligomer.

[0017] In some examples, in chemical formula (I), X, Z, and A can be NH; n, o, and u can be 1; p, q, r, s, and t can be 0; G, I, and M can be H; Y can be N; and the oligomer can be the phenol- aldehyde oligomer; the urea-aldehyde oligomer; the melamine-aldehyde oligomer; the phenol- urea-aldehyde oligomer; the melamine-urea-aldehyde oligomer; the biuret-aldehyde oligomer; the adipamide-aldehyde oligomer; the 2-cyano-guanidine-aldehyde oligomer; the thiourea-aldehyde oligomer; the cyanurate-aldehyde oligomer; the bis-phenol alcohol-aldehyde oligomer; the 4-tert- butylphenol-aldehyde oligomer; or the 2,4-di-tert-butylphenol-aldehyde oligomer. In one example, in chemical formula (I), X, Z, and A can be NH; n, o, and u can be 1; p, q, r, s, and t can be 0; G, I, and M can be H; Y can be N; and the oligomer can be the urea-formaldehyde oligomer. In another example, in chemical formula (I), X, Z, and A can be NH; n, o, and u can be 1; p, q, r, s, and t can be 0; G, I, and M can be H; Y can be N; and the oligomer can be the phenol- formaldehyde oligomer. In another example, in chemical formula (I), X, Z, and A can be NH; n, o, and u can be 1; p, q, r, s, and t can be 0; G, I, and M can be H; Y can be N; and the oligomer can be the melamine-formaldehyde oligomer.

[0018] In some examples, in chemical formula (I), X and Z can be O, n and u can be 1; o, p, q, r, s, and t can be 0; G and M can be H; Y can be N; and the oligomer can be the phenol-aldehyde oligomer; the urea-aldehyde oligomer; the melamine-aldehyde oligomer; the phenol-urea- aldehyde oligomer; the melamine-urea-aldehyde oligomer; the biuret-aldehyde oligomer; the adipamide-aldehyde oligomer; the 2-cyano-guanidine-aldehyde oligomer; the thiourea-aldehyde oligomer; the cyanurate-aldehyde oligomer; the bis-phenol alcohol-aldehyde oligomer; the 4-tert- butylphenol-aldehyde oligomer; or the 2,4-di-tert-butylphenol-aldehyde oligomer. In one example, in chemical formula (I), X and Z can be O, n and u can be 1; o, p, q, r, s, and t can be 0; G and M can be H; Y can be N; and the oligomer can be the urea-formaldehyde oligomer. In another example, in chemical formula (I), X and Z can be O, n and u can be 1; o, p, q, r, s, and t can be 0; G and M can be H; Y can be N; and the oligomer can be the phenol-formaldehyde oligomer. In another example, in chemical formula (I), X and Z can be O, n and u can be 1; o, p, q, r, s, and t can be 0; G and M can be H; Y can be N; and the oligomer can be the melamine- formaldehyde oligomer.

[0019] In some examples, in chemical formula (I), X and Z can be NH; n, o, t, and u can be 1; p, q, r, and s can be 0; A and F can be NH; G, I, L, and M can be H; Y can be N; and the oligomer can be the phenol-aldehyde oligomer; the urea-aldehyde oligomer; the melamine-aldehyde oligomer; the phenol-urea-aldehyde oligomer; the melamine-urea-aldehyde oligomer; the biuret- aldehyde oligomer; the adipamide-aldehyde oligomer; the 2-cyano-guanidine-aldehyde oligomer; the thiourea-aldehyde oligomer; the cyanurate-aldehyde oligomer; the bis-phenol alcohol- aldehyde oligomer; the 4-te/V-butyl phenol -aldehyde oligomer; or the 2,4-di-tert-butylphenol- aldehyde oligomer. In one example, in chemical formula (I), X and Z can be NH; n, o, t, and u can be 1; p, q, r, and s can be 0; A and F can be NH; G, I, L, and M can be H; Y can be N; and the oligomer can be the urea-formaldehyde oligomer. In another example, in chemical formula (I), X and Z can be NH; n, o, t, and u can be 1; p, q, r, and s can be 0; A and F can be NH; G, I, L, and M can be H; Y can be N; and the oligomer can be the phenol-formaldehyde oligomer. In another example, in chemical formula (I), X and Z can be NH; n, o, t, and u can be 1; p, q, r, and s can be 0; A and F can be NH; G, I, L, and M can be H; Y can be N; and the oligomer can be the melamine- formaldehyde oligomer.

[0020] The oligomer having a polyalcohol-polyether group covalently bonded thereto can have a chemical formula (II) of:

[0021] In chemical formula (II), A and F can independently be CH₂, O, or NH; B, C, D, and E can independently be CH₂ or O; G, I, J, K, L, and M can independently be CEE or H; X and Z can independently be OH, NH₂, or NH; Y can be O or NH; n, o, p, q, r, s, t, and u can be independently an integer of 0 to 6, at least one of n, u, and t can be an integer of 1 to 6; and the oligomer can be selected from the group consisting of: a phenol-aldehyde oligomer; a urea-aldehyde oligomer; a melamine-aldehyde oligomer; a phenol-urea-aldehyde oligomer; a melamine-urea-aldehyde oligomer; a biuret-aldehyde oligomer; an adipamide-aldehyde oligomer; a 2-cyano-guanidine- aldehyde oligomer; a thiourea-aldehyde oligomer; a cyanurate-aldehyde oligomer; a bis-phenol alcohol-aldehyde oligomer; a 4-/tvV-butyl phenol -aldehyde oligomer; and a 2,4-di-tert- butylphenol-aldehyde oligomer.

[0022] In some examples, in chemical formula (II), X and Z can be NH; n and u can be 1; o, p, q, r, s, and t can be 0; G and M can be H; Y can be N; and the oligomer can be the urea-aldehyde oligomer; the melamine-aldehyde oligomer; the phenol-urea-aldehyde oligomer; the melamine- urea-aldehyde oligomer; the biuret-aldehyde oligomer; the adipamide-aldehyde oligomer; the 2- cyano-guanidine-aldehyde oligomer; the thiourea-aldehyde oligomer; the cyanurate-aldehyde oligomer; the bis-phenol alcohol-aldehyde oligomer; the 4-/tvV-butyl phenol -aldehyde oligomer; or the 2,4-di-tert-butylphenol-aldehyde oligomer. In one example, in chemical formula (II), X and Z can be NH; n and u can be 1 ; o, p, q, r, s, and t can be 0; G and M can be H; Y can be N; and the oligomer can be the urea-formaldehyde oligomer. In another example, in chemical formula (II), X and Z can be NH; n and u can be 1; o, p, q, r, s, and t can be 0; G and M can be H; Y can be N; and the oligomer can be the phenol-formaldehyde oligomer. In another example, in chemical formula (II), X and Z can be NH; n and u can be 1; o, p, q, r, s, and t can be 0; G and M can be H; Y can be N; and the oligomer can be the melamine-formaldehyde oligomer.

[0023] In some examples, in chemical formula (II), A, B, E, and F can be CH₂; I, L, and M can be H; X and Z can be NH; Y can be N, o, p, s, and t can be 1; n, q, r, and u can be 0; and the oligomer can be the urea-aldehyde oligomer; the melamine-aldehyde oligomer; the phenol-urea-aldehyde oligomer; the melamine-urea-aldehyde oligomer; the biuret-aldehyde oligomer; the adipamide- aldehyde oligomer; the 2-cyano-guanidine-aldehyde oligomer; the thiourea-aldehyde oligomer; the cyanurate-aldehyde oligomer; the bis-phenol alcohol-aldehyde oligomer; the 4-tert- butylphenol-aldehyde oligomer; or the 2,4-di-tert-butylphenol-aldehyde oligomer. In one examples, in chemical formula (II), A, B, E, and F can be CH₂; I, L, and M can be H; X and Z can be NH; Y can be N, o, p, s, and t can be 1; n, q, r, and u can be 0; and the oligomer can be the urea- aldehyde oligomer. In another example, in chemical formula (II), A, B, E, and F can be CH₂; I, L, and M can be H; X and Z can be NH; Y can be N, o, p, s, and t can be 1; n, q, r, and u can be 0; and the oligomer can be the phenol-aldehyde oligomer. In another example, in chemical formula (II), A, B, E, and F can be CH₂; I, L, and M can be H; X and Z can be NH; Y can be N, o, p, s, and t can be 1; n, q, r, and u can be 0; and the oligomer can be the melamine-aldehyde oligomer.

[0024] In some examples, in chemical formula (II), X and Z can be NH; n, o and u can be 1; p, q, r, s, and t can be 0; A can be NH; G, I, and M can be H; Y can be N; and the oligomer can be the urea-aldehyde oligomer; the melamine-aldehyde oligomer; the phenol-urea-aldehyde oligomer; the melamine-urea-aldehyde oligomer; the biuret-aldehyde oligomer; the adipamide-aldehyde oligomer; the 2-cyano-guanidine-aldehyde oligomer; the thiourea-aldehyde oligomer; the cyanurate-aldehyde oligomer; the bis-phenol alcohol-aldehyde oligomer; the 4-te/V-butyl phenol - aldehyde oligomer; or the 2,4-di-tert-butylphenol-aldehyde oligomer. In one example, in chemical formula (II), X and Z can be NH; n, o and u can be 1; p, q, r, s, and t can be 0; A can be NH; G, I, and M can be H; Y can be N; and the oligomer can be the urea-formaldehyde oligomer. In another example, in chemical formula (II), X and Z can be NH; n, o and u can be 1; p, q, r, s, and t can be 0; A can be NH; G, I, and M can be H; Y can be N; and the oligomer can be the phenol- formaldehyde oligomer. In another example, in chemical formula (II), X and Z can be NH; n, o and u can be 1; p, q, r, s, and t can be 0; A can be NH; G, I, and M can be H; Y can be N; and the oligomer can be the melamine-formaldehyde oligomer.

[0025] In some examples, in chemical formula (II), X and Z can be O; n and u can be 1; o, p, q, r, s, and t can be 0; G and M can be H; Y can be N; and the oligomer can be the urea-aldehyde oligomer; the melamine-aldehyde oligomer; the phenol-urea-aldehyde oligomer; the melamine- urea-aldehyde oligomer; the biuret-aldehyde oligomer; the adipamide-aldehyde oligomer; the 2- cyano-guanidine-aldehyde oligomer; the thiourea-aldehyde oligomer; the cyanurate-aldehyde oligomer; the bis-phenol alcohol-aldehyde oligomer; the 4-/c/V-butyl phenol -aldehyde oligomer; or the 2,4-di-tert-butylphenol-aldehyde oligomer. In one example, in chemical formula (II), X and Z can be O; n and u can be 1; o, p, q, r, s, and t can be 0; G and M can be H; Y can be N; and the oligomer can be the urea-formaldehyde oligomer. In another example, in chemical formula (II), X and Z can be O; n and u can be 1; o, p, q, r, s, and t can be 0; G and M can be H; Y can be N; and the oligomer can be the phenol-formaldehyde oligomer. In another example, in chemical formula (II), X and Z can be O; n and u can be 1; o, p, q, r, s, and t can be 0; G and M can be H; Y can be N; and the oligomer can be the melamine-formaldehyde oligomer.

[0026] In some examples, in chemical formula (II), X and Z can be NH; n, o, t, and u can be 1; p, q, r, and s can be 0; A and F can be NH; G, I, L, and M can be H; Y can be N; and the oligomer can be the urea-aldehyde oligomer; the melamine-aldehyde oligomer; the phenol-urea-aldehyde oligomer; the melamine-urea-aldehyde oligomer; the biuret-aldehyde oligomer; the adipamide- aldehyde oligomer; the 2-cyano-guanidine-aldehyde oligomer; the thiourea-aldehyde oligomer; the cyanurate-aldehyde oligomer; the bis-phenol alcohol-aldehyde oligomer; the 4-tert- butylphenol-aldehyde oligomer; or the 2,4-di-tert-butylphenol-aldehyde oligomer. In another example, in chemical formula (II), X and Z can be NH; n, o, t, and u can be 1; p, q, r, and s can be 0; A and F can be NH; G, I, L, and M can be H; Y can be N; and the oligomer can be the urea- formaldehyde oligomer. In another example, in chemical formula (II), X and Z can be NH; n, o, t, and u can be 1; p, q, r, and s can be 0; A and F can be NH; G, I, L, and M can be H; Y can be N; and the oligomer can be the phenol-formaldehyde oligomer. In another example, in chemical formula (II), X and Z can be NH; n, o, t, and u can be 1; p, q, r, and s can be 0; A and F can be NH; G, I, L, and M can be H; Y can be N; and the oligomer can be the melamine-formaldehyde oligomer. [0027] In some examples the oligomer having chemical formula (I) and/or the oligomer having chemical formula (II) can have a weight average molecular weight of about 200, about 225, or about 250 to about 350, about 400, about 500, about 600, about 700, about 800, about 900, or about 1,000. In other examples, the oligomer having chemical formula (I) and/or the oligomer having chemical formula (II) can have a weight average molecular weight of less than 1000, less than 900, less than 800, less than 700, less than 600, less than 500, or less than 450. It should be noted that the weight average molecular weight of the oligomer having chemical formula I and/or the oligomer having chemical formula II does not take into account any contribution from the polyalcohol-monoether group or the polyalcohol-polyether group covalently bonded thereto, respectively.

[0028] In some examples, the binder composition can be or include a first oligomer having the polyalcohol-monoether group covalently bonded thereto and having chemical formula (I), a second oligomer having the polyalcohol-polyether group covalently bonded thereto and having chemical formula (II), or a mixture thereof, where the first oligomer and the second oligomer, if both present, can be the same or different with respect to one another. In some examples, the first oligomer and the second oligomer, if present, can be different from one another by having different weight average molecular weights, different chemical structures, of a combination thereof.

[0029] In other examples, the binder composition can be or include a first oligomer having a first polyalcohol-monoether group covalently bonded thereto and having chemical formula (I), a second oligomer having a second polyalcohol-monoether group covalently bonded thereto and having chemical formula (I), where at least one of the first oligomer and the second oligomer or at least one of the first polyalcohol-monoether and the second polyalcohol-monoether are different with respect to one another. In other examples, the binder composition can be or include a first oligomer having a first polyalcohol-polyether group covalently bonded thereto and having chemical formula (II), a second oligomer having a second polyalcohol-polyether group covalently bonded thereto and having the chemical formula (II), where at least one of the first oligomer and the second oligomer or at least one of the first polyalcohol-polyether and the second polyalcohol- polyether are different with respect to one another. It should be noted that the binder composition can include any number of oligomers each having one or more polyalcohol-monoethers covalently bonded thereto and having chemical formula (I), any number of oligomers each having one more polyalcohol -polyethers covalently bonded thereto and having chemical formula 1, and/or any number of oligomers having one or more polyalcohol-monoethers and one or more polyalcohol- polyethers (chemical formula not shown) covalently bonded thereto.

[0030] In some examples, the oligomer in chemical formula (I) and/or chemical formula (II) can be or include a reaction product of one or more aldehyde compounds and one or more amide compounds. In some examples, the oligomer in chemical formula (I) and/or chemical formula (II) can be or include a reaction product of one or more aldehyde compounds and one or more phenolic compounds. In other examples, the oligomer in chemical formula (I) and/or chemical formula (II) can be or include a reaction product of one or more aldehyde compounds, one or more amide compounds, and one or more phenolic compounds.

[0031] Illustrative aldehyde compounds can be or include, but are not limited to, formaldehyde, acetaldehyde, propanal (propionaldehyde), butanal (butyraldehyde), furan-2-carbaldehyde (furfuraldehyde), benzaldehyde, (2£)-3 -phenyl prop-2-enal (cinnamaldehyde), oxaldehyde (glyoxal), propanedial (malondialdehyde), butanedial (succindialdehyde), pentanedial (glutaraldehyde), benzene- l,2-dicarbaldehyde (phthalaldehyde), or any mixture thereof. In some examples, the aldehyde compound can be or include formaldehyde. Formaldehyde, as the other components, can be available in many forms. For example, formaldehyde can be supplied as an aqueous solution, such as formalin. In some examples, the formalin can contain about 37 wt % to about 50 wt % of formaldehyde. Other forms of formaldehyde such as paraformaldehyde and/or urea-formaldehyde concentrate 85 (UFC 85) can also be used in lieu of or in addition to aqueous formaldehyde solutions.

[0032] Illustrative amide compounds can be or include, but are not limited to, urea, l,3,5-triazine- 2, 4, 6-triamine (melamine), 2-Imidodicarbonic diamide (biuret), adipamide, 2-cyanoguanidine, thiourea, l,3,5-Triazinane-2,4,6-trione (cyanurate), or any mixture thereof. In some examples, the amide compound can be or include urea, melamine, or a mixture thereof. In at least one example, the amide compound can be or include urea. Illustrative phenolic compounds can be or include, but are not limited to, phenol, benzene- 1, 3 -diol (resorcinol), benzene- l,2-diol (catechol), benzene- l,4-diol (hydroquinone), or any mixture thereof. In at least one example, the phenolic compound can be or include phenol, benzene-l,3-diol, or a mixture thereof. In at least one other example, the phenolic compound can be or include phenol. [0033] In some examples, the oligomer in chemical formula (I) and/or chemical formula (II) can be or include the reaction product of one or more aldehyde compounds, one or more amide compounds, and one or more phenolic compounds. In some examples, the aldehyde compound can be or include formaldehyde, the amid compound can be or include urea, melamine, or a mixture thereof, and the phenolic compound can be or include phenol, benzene-l,3-diol, or a mixture thereof. In at least one example, the aldehyde compound can be or include formaldehyde, the amide compound can be or include urea, and the phenolic compound can be or include phenol.

[0034] The oligomer having the polyalcohol-monoether group covalently bonded thereto and having chemical formula (I) and/or the oligomer having the polyalcohol-polyether group covalently bonded thereto and having chemical formula (II) can be synthesized, made, or otherwise produced by reacting one or more aldehydes, one or more polyamine compounds, one or more polyol compounds, and/or one or more polyamine/polyol compounds, one or more epihalohydrin compounds, and one or more amide compounds and/or one or more phenolic compounds. For example, the oligomer can be produced by reacting the aldehyde compound and the amide compound and/or the phenolic compound. The polyalcohol-monoether and/or the polyalcohol- polyether can be produced by reacting the aldehyde compound, the polyamine compound, the polyol compound, and/or the polyamine/polyol compound, and the epihalohydrin compound. The oligomer having the polyalcohol-monoether group covalently bonded thereto and having chemical formula (I) and/or the oligomer having the polyalcohol-polyether group covalently bonded thereto and having chemical formula (II) can be produced by reacting the oligomer and the polyalcohol- monoether and/or the polyalcohol-polyether.

[0035] Illustrative polyamine compounds can be or include, but are not limited to, diethylenetriamine (DETA), bis(hexamethylene)triamine, hexamethylenediamine, tetram ethyl enetetramine, tris(2-aminoethyle)amine, ethylene diamine, polyether amines, or any mixture thereof. Illustrative polyol compounds can be or include but are not limited to, diethylene glycol, polyvinyl alcohol, polyethylene glycol, pentaerythritol, sorbitol, triglycerol, or any mixture thereof. In some examples, rather than using what can be referred to as a polyamine compound or a polyol compound, a compound that can be considered as being both a polyamine compound and a polyol (“polyamine/polyol”) compound (“polyamine/polyol compound”) can be used. Illustrative polyamine/polyol compounds can be or include, but are not limited to, diethanolamine, triethanolamine, N-(2-hydroxyethyl)ethylenediamine, 2-(2-aminoethoxy)ethanol, or any mixture thereof. Illustrative epihalohydrin compounds can be or include, but are not limited to, epichlorohydrin, epibromohydrin, epiiodohydrin, or any mixture thereof.

[0036] In some examples, the aldehyde compound and the polyamine compound and/or polyol compound can be introduced into a reaction vessel to produce a first reaction mixture or first mixture. In one example, the aldehyde compound can be introduced to the reaction vessel followed by the polyamine compound and/or polyol compound. In another example, the polyamine compound and/or the polyol compound can be introduced to the reaction vessel followed by the aldehyde compound. In another example, the aldehyde compound and the polyamine compound and/or the polyol compound can be introduced into the reaction vessel at the same time or substantially the same time. The aldehyde compound and the polyamine compound and/or polyol compound can be allowed to exotherm and react within the reaction vessel to produce a fist intermediate.

[0037] An illustrative reaction between formaldehyde (aldehyde compound) and the polyamine compound and/or the polyol compound to produce the first intermediate is shown in the following Scheme I:

[0038] where A and F can independently be CH₂, O, or NH; B, C, D, and E can independently be CFb or O; G, I, J, K, L, and M can independently be CEE or H; X and Z can independently be OH, NH₂, or NH; Y can be O or NH; n, o, p, q, r, s, t, and u can independently be an integer of 0 to 6; and at least one of n, u, and t can be an integer of 1 to 6; where A and F can independently be CH₂, O, or NH; B , C , D , and E can independently be CH₂ or O; G , I , J , K , L , and M can independently be C¾ or H; X and Z can independently be OH, NH₂, or NH; Y can be O or NH; n , o^’, p , q , r , s^’, t , and u can independently be an integer of 0 to 6; at least one of n , u , and t can be an integer of 1 to 6; and where a can be an integer of 2 or 3.

[0039] In some examples, once the exotherm stops or at least begins to decrease from a maxim rate of heat liberation, the epihalohydrin compound can be introduced to the reaction vessel to produce a second reaction mixture or second mixture that can include the first intermediate and the epihalohydrin compound. The second mixture can be stirred for about 1 minute, about 3 minutes, or about 5 minutes to about 10 minutes, about 15 minutes, about 30 minutes, or more. The mixture can be heated to a temperature of about 50°C, about 53°C, about 55°C, or about 57°C to about 63°C, about 65°C, about 67°C, about 70°C, about 75°C, or about 80°C to produce a second intermediate.

[0040] An illustrative reaction between the first intermediate and the epihalohydrin compound to produce the second intermediate is shown in the following Scheme II:

[0041] where A and F can independently be CH₂, O, or NH; B, C, D, and E can independently be CFb or O; G, I, J, K, L, and M can independently be CEE or H; X and Z can independently OH, NH₂, or NH; Y can be O, NH, or N; n, o, p, q, r, s, t, and u can independently be an integer of 0 to 6, and at least one of n, u, and t can be an integer of 1 to 6; where A’ and F’ can independently be CFh, O, or NH; B’, C’, D’, and E’ can independently be CFb or O; G’, G, G, K’, L’, and M’ can independently be CH₃ or H; X’ and Z’ can independently OH, NH₂, or NH; Y’ can be O, NH, or N; n’, o’, p’, q’, r’, s’, t’, and u’ can independently be an integer of 0 to 6, and at least one of n’, u’, and t’ can be an integer of 1 to 6; and R can be Cl, Br, or I.

[0042] In some examples, the amide compound and/or the phenolic compound can be added to the heated second mixture to produce a third mixture. The third mixture can be heated to a temperature of about 85°C, about 87°C, about 90°C, or about 93°C to about 95°C, about 97°C, or about 99°C to produce the binder composition. The heated third mixture can be held at the temperature of about 85°C, about 87°C, about 90°C, or about 93°C to about 95°C, about 97°C, or about 99°C for about 5 minutes, about 10 minutes, about 15 minutes, or about 20 minutes to about 25 minutes, about 30 minutes, about 40 minutes, about 50 minutes, about 60 minutes, or more. The heated third mixture can then be cooled to a temperature of about 80°C, about 83 °C, or about 85°C to about 89°C, about 9l°C about 93°C, or about 95°C until a binder composition having a viscosity of about 100 cP to about 500 cP is obtained or otherwise produced. The binder composition having the desired viscosity can be distilled to produce a binder composition having a desired solids content.

[0043] The oligomer can form or otherwise be produced in the presence of the second intermediate. The formation of the oligomer can occur in the presence of the second intermediate due, at least in part, to the large amount of the aldehyde compound and amide compound and/or phenolic compound relative to the amount of the epihalohydrin compound and the polyamine compound, the polyol compound, and/or the polyamine/polyol compound used to produce the first intermediate and the second intermediate. The amount of each component or compound that can be used to produce the binder composition is further discussed and described below. Once the oligomer is produced the oligomer can react with the second intermediate to produce the binder composition.

[0044] An illustrative reaction between the second intermediate and the oligomer is shown in the following Scheme III:

oligomer [0045] where A and F can independently be CH₂, O, or NH; B, C, D, and E can independently be CFb or O; G, I, J, K, L, and M can independently be CEE or H; X and Z can independently be OH, NH₂, or NH; Y can be O, NH, or N; n, o, p, q, r, s, t, and u can independently be an integer of 0 to 6, at least one of n, u and t can be an integer of 1 to 6; where A’ and F’ can independently be CH₂, O, or NH; B’, C’, D’, and E’ can independently be CH₂ or O; G’, F, J’, K’, L’, and M’ can independently be C¾ or H; X’ and Z’ can independently be OH, NH₂, or NH; Y’ can be O, NH, or N; n’, o’, p’, q’, r’, s’, t’, and u’ can independently be an integer of 0 to 6, at least one of n’, u’ and t’ can be an integer of 1 to 6; and where the oligomer can be the urea-aldehyde oligomer; the melamine-aldehyde oligomer; the phenol-aldehyde oligomer; the biuret-aldehyde oligomer; the adipamide-aldehyde oligomer; the 2-cyano-guanidine-aldehyde oligomer; the thiourea-aldehyde oligomer; the cyanurate-aldehyde oligomer; the bis-phenol alcohol-aldehyde oligomer; the 4-tert- butylphenol-aldehyde oligomer; or the 2,4-di-tert-butylphenol-aldehyde oligomer.

[0046] The amount of the aldehyde compound used to produce the binder composition can be about 40 wt%, about 42 wt%, about 44 wt%, about 46 wt% or about 48 wt% to about 52 wt%, about 54 wt%, about 56 wt%, or about 58 wt%, based on a combined solids weight of the aldehyde compound, any polyamine compound, any polyol compound, any polyamine/polyol compound, the epihalohydrin compound, any amide compound, and any phenolic compound.

[0047] The amount of the polyamine compound used to produce the binder composition, if present, can be about 0.25 wt%, about 0.4 wt%, about 0.5 wt%, about 0.6 wt% or about 0.7 wt% to about 1 wt%, about 1.3 wt%, about 1.5 wt%, about 1.7 wt%, about 1.9 wt%, or about 2.1 wt%, based on a combined solids weight of the aldehyde compound, the polyamine compound, any polyol compound, any polyamine/polyol compound, the epihalohydrin compound, any amide compound, and any phenolic compound.

[0048] The amount of the polyol compound used to produce the binder composition, if present, can be about 0.25 wt%, about 0.4 wt%, about 0.5 wt%, about 0.6 wt% or about 0.7 wt% to about 1 wt%, about 1.3 wt%, about 1.5 wt%, about 1.7 wt%, about 1.9 wt%, or about 2.1 wt%, based on a combined solids weight of the aldehyde compound, any polyamine compound, the polyol compound, any polyamine/polyol compound, the epihalohydrin compound, any amide compound, and any phenolic compound. [0049] The amount of the polyamine/polyol compound used to produce the binder composition, if present, can be about 0.25 wt%, about 0.4 wt%, about 0.5 wt%, about 0.6 wt% or about 0.7 wt% to about 1 wt%, about 1.3 wt%, about 1.5 wt%, about 1.7 wt%, about 1.9 wt%, or about 2.1 wt%, based on a combined solids weight of the aldehyde compound, any polyamine compound, any polyol compound, the polyamine/polyol compound, the epihalohydrin compound, any amide compound, and any phenolic compound.

[0050] The combined amount of any polyamine compound and any polyol compound used to produce the binder composition can be about 0.25 wt%, about 0.4 wt%, about 0.5 wt%, about 0.6 wt% or about 0.7 wt% to about 1 wt%, about 1.3 wt%, about 1.5 wt%, about 1.7 wt%, about 1.9 wt%, or about 2.1 wt%, based on a combined solids weight of the aldehyde compound, any polyamine compound, any polyol compound, any polyamine/polyol compound, the epihalohydrin compound, any amide compound, and any phenolic compound.

[0051] The amount of the epihalohydrin compound used to produce the binder composition can be about 0.25 wt%, about 0.4 wt%, about 0.5 wt%, about 0.8 wt%, about 1 wt%, about 1.5 wt%, or about 2 wt% to about 3 wt%, about 4 wt%, about 5 wt%, about 6 wt%, about 7 wt%, about 8 wt%, about 9 wt%, or about 10 wt%, based on a combined solids weight of the aldehyde compound, any polyamine compound, any polyol compound, any polyamine/polyol compound, the epihalohydrin compound, any amide compound, and any phenolic compound.

[0052] The amount of the amide compound used to produce the binder composition, if present, can be about 40 wt%, about 42 wt%, about 44 wt%, about 46 wt% or about 48 wt% to about 52 wt%, about 54 wt%, about 56 wt%, or about 58 wt%, based on a combined solids weight of the aldehyde compound, any polyamine compound, any polyol compound, any polyamine/polyol compound, the epihalohydrin compound, the amide compound, and any phenolic compound.

[0053] The amount of the phenolic compound used to produce the binder composition, if present, can be about 40 wt%, about 42 wt%, about 44 wt%, about 46 wt% or about 48 wt% to about 52 wt%, about 54 wt%, about 56 wt%, or about 58 wt%, based on a combined solids weight of the aldehyde compound, any polyamine compound, any polyol compound, any polyamine/polyol compound, the epihalohydrin compound, any amide compound, and the phenolic compound.

[0054] The combined amount of any amide compound and any phenolic compound used to produce the binder composition can be about 40 wt%, about 42 wt%, about 44 wt%, about 46 wt% or about 48 wt% to about 52 wt%, about 54 wt%, about 56 wt%, or about 58 wt%, based on a combined solids weight of the aldehyde compound, any polyamine compound, any polyol compound, any polyamine/polyol compound, the epihalohydrin compound, any amide compound, and any phenolic compound.

[0055] In some examples, the amount of the components used to produce the binder composition can include about 40 wt% to about 58 wt% of the aldehyde compound, up to about 2.1 wt% of the polyamine compound, up to about 2.1 wt% of the polyol compound, up to about 2.1 wt% of the polyamine/polyol compound, about 0.25 wt% to about 10 wt% of the epihalohydrin compound, up to about 58 wt% of the amide compound, and up to about 58 wt% of the phenolic compound. In some examples, the amount of the components used to produce the binder composition can include about 40 wt% to about 58 wt% of the aldehyde compound, about 0.25 wt% to about 2.1 wt% of a combined amount of any polyamine compound, any polyol compound, and any polyamine/polyol compound, about 0.25 wt% to about 10 wt% of the epihalohydrin compound, and about 40 wt% to about 58 wt% of a combined amount of any amide compound and any phenolic compound, based on a combined weight of the aldehyde compound, any polyamine compound, any polyol compound, any polyamine/polyol compound, the epihalohydrin compound, any amide compound, and any phenolic compound.

[0056] In some examples, additional amide compound and/or phenolic compound can be mixed, blended, or otherwise combined with the binder composition either before, during, or after the binder composition is distilled to produce the binder having the desired solids content. The additional amide compound and/or phenolic compound can adjust the molar ratio of the aldehyde compound to the amide compound and/or the phenolic compound in the binder composition. It should be understood that if the binder composition is produced by adding additional amide compound and/or phenolic compound, the amount of the amide compound and/or the phenolic compound used to produce the binder composition can be as discussed and described above. For example, the combined amount of any amide compound and any phenolic compound used to produce the binder composition whether added in one or multiple additions during the synthesis of the binder composition can be about 40 wt%, about 42 wt%, about 44 wt%, about 46 wt% or about 48 wt% to about 52 wt%, about 54 wt%, about 56 wt%, or about 58 wt%, based on a combined solids weight of the aldehyde compound, any polyamine compound, any polyol compound, any polyamine/polyol compound, the epihalohydrin compound, any amide compound, and any phenolic compound.

[0057] In some examples, the binder composition made with the amide compound, after distillation, can have a molar ratio of the aldehyde compound to amide compound of about 2: 1, about 2.1 : 1, about 2.2: 1 or about 2.3: 1 to about 2.4: 1, about 2.5: l, about 2.6: 1, about 2.7: 1, about 2.8:1, about 2.9:1, or about 3:1. In some examples, adding additional amide compound to a binder composition having an aldehyde to amide compound molar ratio of about 2: 1 to about 3: 1 can produce a binder composition having a final aldehyde compound to amide compound molar ratio of about 1.7: 1, about 1.8: 1, about 1.9: 1 or about 2: 1 to about 2.1 : 1, about 2.2: 1, about 2.3: 1, about 2.4:1, or about 2.5: 1.

[0058] In some examples, the binder composition made with the phenolic compound, after distillation, can have a molar ratio of the aldehyde compound to phenolic compound of about 2: 1, about 2.1 : 1, about 2.2: 1 or about 2.3: 1 to about 2.4: 1, about 2.5: 1, about 2.6: 1, about 2.7: 1, about 2.8: 1, about 2.9: 1, or about 3: 1. In some examples, adding additional phenolic compound to a binder composition having an aldehyde to phenolic compound molar ratio of about 2: 1 to about 3 : 1 can produce a binder composition having a final aldehyde compound to phenolic compound molar ratio of about 1.7: 1, about 1.8: 1, about 1.9: 1 or about 2: l to about 2.1 : 1, about 2.2: 1, about 2.3: 1, about 2.4: 1, or about 2.5: 1.

[0059] In some examples, the binder composition can also include one or more diluents. Illustrative diluents can be or include, but are not limited to, water, one or more alcohols, or a mixture thereof. Illustrative alcohols can be or include, but are not limited to, methanol, ethanol, propanol, isopropanol, butanol, or any mixture thereof. If the binder composition includes a diluent, the binder composition can include about 20 wt%, about 23 wt%, about 25 wt%, about 27 wt%, about 30 wt%, or about 33 wt% to about 37 wt%, about 40 wt%, about 43 wt%, about 45 wt%, about 47 wt%, or about 50 wt% of the diluent, based on a total weight of the binder composition. In some examples, the diluent can be or include water and at least a portion of the diluent can be generated or otherwise produced during the synthesis of the binder composition. In some examples, the diluent can be or include water and at least a portion of the diluent can be added to the binder composition to reduce the solids content thereof. [0060] In some examples, the binder composition can have a solids content of about 50 wt%, about 55 wt% or about 60 wt% to about 70 wt%, about 75 wt%, or about 80 wt%. For example, the binder composition can have a solids content of about 60 wt% to about 70 wt%, about 60 wt% to about 65 wt%, about 65 wt% to about 70 wt%, or about 63 wt% to about 67 wt%. In other examples, the binder composition can have a solids content of at least 60wt%, at least 62 wt%, at least 64 wt%, at least 66 wt%, or at least 68 wt% to about 70 wt%, about 72 wt%, about 74 wt%, about 76 wt%, about 78 wt%, or about 80 wt%. In other examples, the binder composition can have a solids content of about 55 wt% to about 70 wt%, about 60 wt% to about 65 wt%, about 62 wt% to about 67 wt%, about 58 wt% to about 63 wt%, or about 67 wt% to about 70 wt%.

[0061] In some examples, the binder composition can have a pH of about 7, about 7.3, about 7.5, about 7.7, or about 8 to about 8.2, about 8.4, about 8.6, about 8.8, about 9, about 9.5, or about 10 at a temperature of about 25°C. In some examples, the binder composition can have a pH of about 7, about 7.3, about 7.5, about 7.7, or about 8 to about 8.2, about 8.4, about 8.6, about 8.8, about 9, about 9.5, or about 10 at a temperature of about 25°C and a solids content of about 60 wt% to about 65 wt%. In other examples, the binder composition can have a pH of about 7.6 to about 8.8, about 7.8 to about 8.6, or about 8 to about 8.4 at a temperature of about 25°C and a solids content of about 60 wt% to about 65 wt%. In other examples, the binder composition can have a pH of about 7.6 to about 8.8, about 7.8 to about 8.6, or about 8 to about 8.4 at a temperature of about 25°C and a solids content of about 60 wt% to about 65 wt%, with the diluent being or including water.

[0062] In some examples, the binder composition can have a viscosity of about 100 cP, about 125 cP, about 150 cP, about 175 cP, or about 200 cP to about 300 cP, about 350 cP, about 400 cP, about 450 cP, about 500 cP, or about 750 cP at a temperature of about 25°C. In some examples, the binder composition can have a viscosity of about 100 cP, about 125 cP, about 150 cP, about 175 cP, or about 200 cP to about 300 cP, about 350 cP, about 400 cP, about 450 cP, about 500 cP, or about 750 cP at a temperature of about 25°C and a solids content of about 60 wt% to about 65 wt%. In some examples, the binder composition can have a viscosity of about 100 cP, about 125 cP, about 150 cP, about 175 cP, or about 200 cP to about 300 cP, about 350 cP, about 400 cP, about 450 cP, about 500 cP, or about 750 cP at a temperature of about 25°C and a solids content of about 60 wt% to about 65 wt%, with the diluent being or including water. [0063] The viscosity of the binder compositions discussed and described herein can be determined using a Brookfiled viscometer at a temperature of about 25°C. For example, a Brookfield viscometer, Model DV-II+, with a small sample adapter (e.g, a 10 mL adapter) with, for example, a number 31 spindle, can be used. The small sample adapter can allow the sample to be cooled or heated by the chamber jacket to maintain the temperature of the sample surrounding the spindle at a temperature of about 25°C. The appropriate spindle, such as a number 31 spindle, can be used to maximize torque.

[0064] In some examples, the binder composition can be applied to a plurality of substrates to produce a mixture or“resinated furnish”. In some examples, the plurality of substrates can be or include fibers. In some examples, the fibers, before or after applying the binder composition thereto, can be formed into mats or other products. As used herein, the terms "fiber", "fibers", "fibrous", "fiberglass", "fiber glass", "fiber web", and "glass fibers" refer to materials that have an elongated morphology exhibiting an aspect ratio (length to thickness or cross-sectional length) of greater than or equal to about 10, about 100, about 500, about 1,000, about 5,000, about 10,000 or greater.

[0065] The fibers or fiber webs can be or include natural fibers, synthetic fibers, inorganic fibers, or any mixture thereof. Inorganic fibers can be or include, but are not limited to, glass fibers, mineral fibers, ceramic fibers, carbon fibers, graphite fibers, metal fibers, metal coated glass fibers, organic coated glass fibers, or any mixture thereof. Illustrative glass fibers can be or include, but are not limited to, A-type glass fibers, C-type glass fibers, E-type glass fibers, S-type glass fibers, ECR-type glass fibers, WUCS glass fibers, wool glass fibers, or any mixture thereof. In some examples, the fibers can be glass fibers that are wet use chopped strand ("WIJCS") glass fibers. The WUCS glass fibers can be formed by conventional processes known in the art. The WUCS glass fibers can have a moisture content of about 5%, about 8%, or about 10% to about 20%, about 25%, or about 30%.

[0066] Synthetic fibers can be or include, but are not limited to, acrylic fibers, aromatic polyamide fibers, polyester fibers, aramid fibers, polyolefin fibers, or any mixture thereof. Natural fibers can be or include, but are not limited to, plant fibers extracted from any part of a plant, including, but not limited to, the stem, seeds, leaves, roots, or phloem. [0067] Prior to using the fibers to make a composite or fiberglass product, the fibers can be allowed to age for a period of time. For example, the fibers can be aged for a period of a few hours to several weeks before being used to make a fiberglass product. For fiberglass mat products, the fibers can typically be aged for about 3 days to about 30 days. Ageing the fibers can include simply storing the fibers at room temperature for the desired amount of time prior to making a fiberglass product therewith.

[0068] Fiberglass mats can be manufactured in a wet-laid or dry-laid process. In a wet-laid process, chopped bundles of fibers, having suitable length and diameter, can be introduced to an aqueous dispersant medium to produce an aqueous fiber slurry, known in the art as "white water." The fibers in the fiber slurry or white water can have a diameter of about 0.5 pm to about 500 pm and a length of about 5 mm to about 50 mm, for example. The fibers can be sized or unsized and wet or dry, as long as the fibers can be suitably dispersed within the fiber slurry or white water. The fiber slurry or white water can be agitated to produce a uniform dispersion of fibers having a suitable consistency. In some examples, the white water or the fiber slurry can include about 0.01 wt%, about 0.03 wt%, about 0.05 wt%, about 0.1 wt%, about 0.5 wt%, or about 1 wt% to about 2 wt%, about 3 wt%, about 5 wt%, about 7 wt%, about 10 wt%, about 12 wt%, about 15 wt%, about 18 wt%, about 20 wt%, about 25 wt%, or about 30 wt% of the fibers based on the weight of the fiber slurry or white water.

[0069] In some examples, a dispersing agent can be present in the fiber slurry or white water in an amount of about 10 ppm to about 8,000 ppm, about 100 ppm to about 5,000 ppm, or about 200 ppm to about 1,000 ppm. In some examples, one or more visocisty modifiers can be introduced to the fiber slurry. The introduction of one or more viscosity modifiers can reduce a settling time of the fibers and/or can improve the dispersion of the fibers in the aqueous solution. The amount of the viscosity modifier used can be effective to provide the viscosity needed to suspend the fibers in the fiber slurry or white water as needed to form the wet laid fiber product. The optional viscosity modifier can be introduced in an amount sufficient to provide a viscosity of about 1 cP, about 1.5 cP, or about 2 cP to about 8 cP, about 12 cP, or about 15 cP.

[0070] The fiber slurry, diluted or undiluted, can be introduced to a mat-forming machine that can include a mat forming screen, e.g, a wire screen or sheet of fabric, which can form a fiber product and can allow excess water to drain therefrom, thereby forming a wet or damp fiber mat. In some examples, the fibers can be collected on the screen in the form of a wet fiber mat and excess water can be removed by gravity and/or by vacuum assist. The removal of excess water via vacuum assist can include one or a series of vacuums. The fiber mat can be in the form of a non-woven fiber mat.

[0071] In some examples, the binder composition can be applied onto at least a portion of the dewatered wet fiber mat. Application of the binder composition can be accomplished via any suitable process, such as by soaking the mat in an excess of the binder composition, a falling film or curtain coater, or dipping. The amount of the binder composition that can be applied to the dewatered fiber mat can be about 5%, about 10%, or about 15% to about 25%, about 30%, about 35%, about 40%, or about 45%, based on a combined solids weight of the plurality of fibers and the binder composition. Excess strengthening resin can be removed, for example via a vacuum.

[0072] The binder composition, once applied to the fibers, can be at least partially cured to produce a composite or fiberglass product. For example, the fibers contacted with the binder composition can be heated to effect drying and at least partial curing of the binder composition. The duration and/or temperature the fibers can be contacted with the binder composition affect the rate of processability and/or handleability of the fibrous product and/or the degree of curing and property development of the binder composition. In some examples, the resinated furnish can be heated to a temperature of about l00°C, about l35°C, about l50°C, or about l70°C to about 200°C, about 250°C, or about 300°C. The curing time can be about 1 second to about 15 minutes. In some examples, the curing temperature can be a temperature of about l35°C to about 300°C for a time of about 1, about 2 seconds, about 5 seconds, about 10 seconds, or about 20 seconds to about 30 seconds, about 45 seconds, about 60 seconds, about 75 seconds, about 90 seconds, or about 120 seconds. In other examples, the curing temperature can be about l25°C to about 205°C for a time of about 1 second, about 2 seconds, about 3 seconds, about 5 seconds, or about 10 seconds to about 60 seconds, about 75 seconds, or about 90 seconds.

[0073] On heating, at least a portion of the diluent present in the resinated furnish can evaporate and the binder composition can be at least partially cured. These processes can take place in succession or simultaneously. Curing in the present context can be understood as meaning the chemical alteration of the binder composition, for example, crosslinking through the formation of bonds, including, but not limited to ionic bonds, covalent bonds, hydrogen bonds, between the various constituents of the binder composition.

[0074] Alternatively or in addition to heating the resinated furnish, catalytic curing can be used to at least partially cure the binder composition. In one example, the catalytic curing of the strengthening resin can include the addition of one or more acid catalysts. Illustrative acid catalysts can be or include, but are not limited to, one or more ammonium salts. Illustrative ammonium salts can be or include, but are not limited to, ammonium sulfate, ammonium chloride, or a mixture thereof.

[0075] In some examples, the drying and curing of the binder composition in the resinated furnish can be conducted in two or more distinct steps. For example, the resinated furnish can be first heated to a temperature and for a time sufficient to substantially dry but not substantially cure the binder composition and then heated for a second time at a higher temperature and/or for a longer period of time to effect curing of the binder composition. Such a preliminary procedure, referred to as "B-staging"— can be used to provide a treated product, for example, in roll form, which may at a later stage be fully cured, with or without forming or molding into a particular configuration, concurrent with the curing process.

[0076] The fiberglass product can be formed as a relatively thin product of about 0.25 mm (about 10 mils) to a relatively thick product of about 25.4 mm (about 1,000 mils). Depending on formation conditions, the density of the product can also be varied from a relatively fluffy low density product to a higher density. The fiberglass product can have a density of about 6 lbs/ft³ to about 10 lbs/ft³, or greater.

[0077] In some examples, a fiberglass product produced with the binder composition can have an average dry tensile strength of about 90 lbs/3 inches, about 95 lbs/3 inches, about 100 lbs/3 inches, about 105 lbs/3 inches, about 110 lbs/3 inches, about 115 lbs/3 inches, or about 120 lbs/3 inches to about 125 lbs/3 inches, about 130 lbs/3 inches, about 135 lbs/3 inches, about 140 lbs/3 inches, about 145 lbs/3 inches, or about 150 lbs/3 inches. The average dry tensile strength can be the average value taken from 2 or more samples. The average dry tensile strength can be measured according to ASTM D2l05-0l(20l4), with the average value being the average value of two or more samples. [0078] In some examples, a fiberglass product produced with the binder composition can have an average hot-wet (HW) tensile strength of about 60 lbs/3 inches, about 63 lbs/3 inches, about 65 lbs/3 inches, about 67 lbs/3 inches, about 70 lbs/3 inches, about 73 lbs/3 inches, or about 75 lbs/3 inches to about 80 lbs/3 inches, about 83 lbs/3 inches, about 85 lbs/3 inches, about 97 lbs/3 inches, about 90 lbs/3 inches, or about 95 lbs/3 inches. The average dry tensile strength can be the average vale taken from 2 or more samples. The average dry tensile strength can be measured according to ASTM D2l05-0l(20l4), with the average value being the average value of two or more samples.

[0079] In some examples, a fiberglass product produced with the binder composition can have an average tear strength of about 500 gF, about 520 gF, about 540 gF, about 550 gF, or about 560 gF to about 580 gF, about 600 gF, about 615 gF, about 630 gF, about 640 gF, or about 650 gF. The average tear strength can be measured according to TAPPI T 414, with the average value being the average value of two or more samples.

[0080] In some examples, the fiberglass product can be used by itself or incorporated into a variety of products. For example, fiberglass products can be used as or incorporated into insulation batts or rolls, composite flooring, roofing shingles, e.g . , asphalt shingles, siding, gypsum wall board, roving, microglass-based substrate for printed circuit boards, battery separators, filter stock, tape stock, carpet backing, and as reinforcement scrim in cementitious and non-cementitious coatings for masonry.

Examples

[0081] In order to provide a better understanding of the foregoing discussion, the following non limiting examples are offered. Although the examples can be directed to specific embodiments, they are not to be viewed as limiting the invention in any specific respect. All parts, proportions, and percentages are by weight unless otherwise indicated.

[0082] Three inventive binder compositions (Ex. 1, Ex. 2, and Ex. 3) were prepared. In Ex. 1, about 690.4 g of a 50% aqueous formaldehyde solution was introduced to a reaction vessel. To the reaction vessel, about 8 g of diethylenetriamine (DETA) was added to the aqueous formaldehyde solution to produce a first mixture and the first mixture was allowed to exotherm. Once the exotherm stopped, about 16 g of epichlorohydrin was added to the first mixture to produce a second mixture that was stirred for about 5 minutes. The second mixture was heated to a temperature of about 60°C and about 345.1 g of urea was added to produce a third mixture. The third mixture was heated to a temperature of about 95°C for about 20 minutes and then cooled to a temperature of about 87°C and the third mixture was reacted until a viscosity of about 300 cP was reached to produce the binder composition. Once the viscosity was reached, the reaction mixture was distilled to a solids content of about 60 wt% to about 65 wt%.

[0083] In Ex. 2, about 690.4 g of a 50% aqueous formaldehyde solution was introduced into a reaction vessel. To the reaction vessel, about 8 g of diethylenetriamine (DETA) was added to the aqueous formaldehyde solution to produce a first mixture and the first mixture was allowed to exotherm. Once the exotherm stopped, about 8 g of epichlorohydrin was added to the first mixture to produce a second mixture that was stirred for about 5 minutes. The second mixture was heated to a temperature of about 60°C and about 345.1 g of urea was added to produce a third mixture. The third mixture was heated to a temperature of about 95°C for about 20 minutes and then cooled to a temperature of about 87°C and the third mixture was reacted until a viscosity of about 250 cP was reached to produce the binder composition. Once the viscosity was reached, the reaction mixture was distilled to a solids content of about 60 wt% to about 65 wt%.

[0084] In Ex. 3, about 670.85 g of a 50% aqueous formaldehyde solution was introduced to a reaction vessel. To the reaction vessel, about 8 g of diethylenetriamine (DETA) was added to the aqueous formaldehyde solution to produce a first mixture and the first mixture was allowed to exotherm. Once the exotherm stopped, about 8 g of epichlorohydrin was added to the first mixture to produce a second mixture that was stirred for about 5 minutes. The second mixture was heated to a temperature of about 60°C and about 362.6 g of urea was added to produce a third mixture. The third mixture was heated to a temperature of about 95°C for about 20 minutes and then cooled to a temperature of about 87°C and the third mixture was reacted until a viscosity of about 250 cP was reached to produce the binder composition. Once the viscosity was reached, the reaction mixture was distilled to a solids content of about 60 wt% to about 65 wt%.

[0085] The binder compositions produced in Examples 1-3 had a pH of about 8 to about 8.4, a viscosity of about 150 cP to about 350 cP, a water dilutability of about 10: 1 of water to binder composition and the binder composition stayed in solution for at least 10 minutes.

[0086] Two comparative binder compositions (Cl and C2) were also used to produce fiberglass matts for comparative purposes. The Cl binder composition was a urea-formaldehyde (ETF) resin modified with 2 wt%, on a solids basis, of styrene maleic anhydride (SMA) and commercially sold under the name GP 245G93, available from Georgia-Pacific Chemicals LLC. The C2 binder composition was a urea-formaldehyde (570G73, available from Georgia-Pacific Chemicals LLC) that had about 5 wt% of RHOPLEX® GL-618 latex added thereto.

[0087] A handsheet study was performed with the Ex. 1, Cl, and C2 binder compositions. A Rohm and Haas model 4297 mixer was used to blend the mixtures. Dilutions were made to about 13 wt% solids with PAA white water, an aqueous solution of polyacrylamide. The plurality of glass fibers was composed of a 50/50 mixture of glass fibers having a length of about 1.25 inches and a length of about 1.375 inches and a moisture content of about 11.9 wt%. The handsheets were cured at a temperature of about 205°C for about 75 seconds.

[0088] As shown in Table 1, the binder composition of Ex. 1 had substantially the same average dry tensile strength as Cl and C2, but a statistically greater average tear strength.

[0089] Additional handsheets were made with the binder composition of Ex. 1, but the handsheets were cured at different temperatures for about 75 seconds.

[0090] As shown in Table 2, the binder composition of Ex. 1, under the processing conditions used to produce the handsheets had an optimal curing temperature of about l85°C to about l95°C. As also shown in Table 2 the %HW retention increased significantly at the cure temperature of about l95°C as compared to l85°C (94.1% vs. 79.6%). As such, the binder composition of Ex. 1 can be overcurred, while still retaining a desired dry tensile strength.

[0091] A series of binder compositions (Exs. 4-11) that had different initial and final aldehyde to amide molar ratios were prepared. The binder compositions of Ex. 4-11 were made according to the following procedure. The aldehyde (50 wt% aqueous formaldehyde solution or formaldehyde and UFC) was introduced to a reaction vessel. The UFC included about 60 wt% formaldehyde, about 25 wt% of urea, and about 15 wt% water. The polyamine (DETA) was added to the reaction vessel and the mixture was allowed to exotherm. Once the exotherm stopped, the epihalohydrin (epichlorohydrin) was added to the mixture and stirred for about 5 minutes. The reaction mixture was heated to a temperature of about 60°C and the amide (urea) was added to the mixture. The reaction mixture was heated to a temperature of about 95°C for about 20 minutes. The temperature of the reaction mixture was decreased to about 87°C and the reaction was allowed to continue until a binder composition that had a viscosity of about 300 cP was produced. Once viscosity was reached, the binder composition was distilled to desired solids. Additional amide (urea) was then added to the binder composition to produce a binder composition having a desired final aldehyde to amide (F :ET) molar ratio.

[0092] Handsheets were made that followed the same procedure used in Ex. 1, but the curing temperature was about l85°C and the curing time was about 75 seconds.

[0093] As shown in Table 4, the binder compositions were cured at 185 °C, which was a lower temperature than the control binders were cured. The binder compositions also exhibited consistent dry tensile properties. It can be seen that examples 5 and 10 exhibited higher dry tensile properties when mole ratios are varied.

[0094] The average dry tensile strength and the average HW tensile strength were measured according to ASTM D2l05-0l(20l4). The average dry tensile strength and the average HW tensile strength values were the average of 8 measurements. The tear strength was measured according to TAPPI T 414. The average tear strength values were the average of 12 measurements. The percent loss of ignition ("% LOI") was determined by weighing samples before and after 30 minutes at 650°C and calculating the change in weight percent. The % LOI was the average of 2 measurements. The percent hot-wet retention ("% HW") was the amount of dry tensile strength retained after immersing the sample in an 80°C water bath for 10 minutes. The %HW values were the average of 8 measurements.

[0095] Embodiments of the present disclosure further relate to any one or more of the following paragraphs:

[0096] 1. A binder composition for making a composite product, comprising: a first oligomer comprising a polyalcohol-monoether group covalently bonded thereto, the first oligomer having a chemical structure of:

first oligomer , wherein A and F are independently CH₂, O, or NH; B, C, D, and E are independently CH₂ or O; I, J, K, L, and M are independently CH₃ or H; X and Z are independently OH, NH₂, or NH; Y is O or NH; n, o, p, q, r, s, t, and u are independently an integer of 0 to 6; at least one of n, u, and t is an integer of 1 to 6; and the first oligomer is selected from the group consisting of: a urea-aldehyde oligomer; a melamine-aldehyde oligomer; a phenol-aldehyde oligomer; a phenol-urea-aldehyde oligomer; a melamine-urea-aldehyde oligomer; a biuret-aldehyde oligomer; an adipamide-aldehyde oligomer; a 2-cyano-guanidine-aldehyde oligomer; a thiourea-aldehyde oligomer; a cyanurate-aldehyde oligomer; a bis-phenol alcohol-aldehyde oligomer; a 4-te/V-butyl phenol -aldehyde oligomer; and a 2,4-di-tert-butylphenol-aldehyde oligomer, or a second oligomer comprising a polyalcohol- poly ether group covalently bonded thereto, the second oligomer having a chemical structure of:

second oligomer wherein A’ and F’ are independently CH₂, O, or NH; B’, C’, D’, and E’ are independently CEE or O; G, J’, K’, L’, and M’ are independently CH₃ or H; X’ and Z’ are independently OH, NH₂, or NH; Y’ is O or NH; n’, o’, p’, q’, r’, s’, t’, and u’ are independently an integer of 0 to 6; at least one of n’, u’, and t’ is an integer of 1 to 6; and the second oligomer is selected from the group consisting of: a urea- aldehyde oligomer; a melamine-aldehyde oligomer; a phenol-aldehyde oligomer; a phenol-urea- aldehyde oligomer; a melamine-urea-aldehyde oligomer; a biuret-aldehyde oligomer; an adipamide-aldehyde oligomer; a 2-cyano-guanidine-aldehyde oligomer; a thiourea-aldehyde oligomer; a cyanurate-aldehyde oligomer; a bis-phenol alcohol-aldehyde oligomer; a 4-tert- butylphenol-aldehyde oligomer; and a 2,4-di-tert-butylphenol-aldehyde oligomer.

[0097] 2. A process for making a binder composition, comprising: reacting a first mixture comprising a polyamine compound, a polyol compound, or a polyamine/polyol compound with an aldehyde compound to produce a first intermediate; combining an epihalohydrin compound with the first intermediate to produce a second mixture comprising the first intermediate and the epihalohydrin compound; reacting the second mixture comprising the first intermediate and the epihalohydrin compound to produce a second intermediate; combining an amide compound, a phenolic compound, or a mixture of an amide compound and a phenolic compound with the second intermediate to produce a third mixture comprising the second intermediate and the amide compound, the phenolic compound, or the mixture of the amide compound and the phenolic compound; and reacting the third mixture comprising the second intermediate and the amide compound, the phenolic compound, or the mixture of the amide compound and the phenolic compound to produce a first oligomer comprising a polyalcohol-monoether group covalently bonded thereto, a second oligomer comprising a polyalcohol-polyether group covalently bonded, or a mixture thereof, wherein: the first oligomer comprising the polyalcohol-monoether group covalently bonded thereto has a chemical structure of:

first oligomer , wherein A and F are independently CFh, O, or NH; B, C, D, and E are independently CEE or O; I, J, K, L, and M are independently C¾ or H; X and Z are independently OH, NH₂, or NH; Y is O or NH; n, o, p, q, r, s, t, and u are independently an integer of 0 to 6; at least one of n, u, and t is an integer of 1 to 6; and the first oligomer is selected from the group consisting of: a urea-aldehyde oligomer; a melamine-aldehyde oligomer; a phenol-aldehyde oligomer; a phenol-urea-aldehyde oligomer; a melamine-urea-aldehyde oligomer; a biuret-aldehyde oligomer; an adipamide-aldehyde oligomer; a 2-cyano-guanidine-aldehyde oligomer; a thiourea-aldehyde oligomer; a cyanurate-aldehyde oligomer; a bis-phenol alcohol-aldehyde oligomer; a 4-te/V-butyl phenol -aldehyde oligomer; and a 2,4-di-tert-butylphenol-aldehyde oligomer, and the second oligomer comprising the polyalcohol- poly ether group covalently bonded thereto has a chemical structure of:

second oligomer wherein A’ and F’ are independently CH₂, O, or NH; B’, C’, D’, and E’ are independently CH₂ or O; G, J’, K’, L and M’ are independently CH₃ or H; X’ and Z’ are independently OH, NH₂, or NH; Y’ is O or NH; n’, o’, p’, q’, r’, s’, f , and u’ are independently an integer of 0 to 6; at least one of n’, u’, and t’ is an integer of 1 to 6; and the second oligomer is selected from the group consisting of: a urea- aldehyde oligomer; a melamine-aldehyde oligomer; a phenol-aldehyde oligomer; a phenol-urea- aldehyde oligomer; a melamine-urea-aldehyde oligomer; a biuret-aldehyde oligomer; an adipamide-aldehyde oligomer; a 2-cyano-guanidine-aldehyde oligomer; a thiourea-aldehyde oligomer; a cyanurate-aldehyde oligomer; a bis-phenol alcohol-aldehyde oligomer; a 4-tert- butylphenol-aldehyde oligomer; and a 2,4-di-tert-butylphenol-aldehyde oligomer.

[0098] 3. A process for making a composite product, comprising: contacting a plurality of substrates with a binder composition comprising a first oligomer comprising a polyalcohol- monoether group covalently bonded thereto, a second oligomer comprising a polyalcohol- polyether group covalently bonded, or a mixture thereof to produce a resinated furnish, wherein: the first oligomer comprising the polyalcohol-monoether group covalently bonded thereto has a chemical structure of:

first oligomer , wherein A and F are independently CH₂, O, or NH; B, C, D, and E are independently CH₂ or O; I, J, K, L, and M are independently CH₃ or H; X and Z are independently OH, NH₂, or NH; Y is O or NH; n, o, p, q, r, s, t, and u are independently an integer of 0 to 6; at least one of n, u, and t is an integer of 1 to 6; and the first oligomer is selected from the group consisting of: a phenol-aldehyde oligomer; a urea-aldehyde oligomer; a melamine-aldehyde oligomer; a phenol-urea-aldehyde oligomer; a melamine-urea-aldehyde oligomer; a biuret-aldehyde oligomer; an adipamide-aldehyde oligomer; a 2-cyano-guanidine-aldehyde oligomer; a thiourea-aldehyde oligomer; a cyanurate-aldehyde oligomer; a bis-phenol alcohol-aldehyde oligomer; a 4-te/V-butyl phenol -aldehyde oligomer; and a 2,4-di-tert-butylphenol-aldehyde oligomer, and the second oligomer comprising the polyalcohol- polyether group covalently bonded thereto has a chemical structure of:

second oligomer wherein A’ and F’ are independently CH₂, O, or NH; B’, C’, D’, and E’ are independently CEE or O; G, J’, K’, L and M’ are independently CH₃ or H; X’ and Z’ are independently OH, NH₂, or NH; Y’ is O or NH; n’, o’, p’, q’, r’, s’, t’, and u’ are independently an integer of 0 to 6; at least one of n’, u’, and t’ is an integer of 1 to 6; and the second oligomer is selected from the group consisting of: a phenol- aldehyde oligomer; a urea-aldehyde oligomer; a melamine-aldehyde oligomer; a phenol-urea- aldehyde oligomer; a melamine-urea-aldehyde oligomer; a biuret-aldehyde oligomer; an adipamide-aldehyde oligomer; a 2-cyano-guanidine-aldehyde oligomer; a thiourea-aldehyde oligomer; a cyanurate-aldehyde oligomer; a bis-phenol alcohol-aldehyde oligomer; a 4-tert- butylphenol-aldehyde oligomer; and a 2,4-di-tert-butylphenol-aldehyde oligomer; and at least partially curing the binder composition in the resinated furnish to produce a composite product.

[0099] 4. The binder composition or process according to any one of paragraphs 1 to 3, wherein the binder composition comprises the first oligomer.

[00100] 5. The binder composition or process according to paragraph 4, wherein the first oligomer comprises the urea-aldehyde oligomer.

[00101] 6. The binder composition or process according to paragraph 5, wherein the urea-aldehyde oligomer has an aldehyde to urea molar ratio of about 1.75 : 1 to about 2.25 : 1.

[00102] 7. The binder composition or process according to paragraph 5 or 6, wherein the urea- aldehyde oligomer has a weight average molecular weight of about 200 to about 400.

[00103] 8. The binder composition or process according to paragraph 4, wherein the first oligomer comprises the melamine-aldehyde oligomer.

[00104] 9. The binder composition or process according to paragraph 4, wherein the first oligomer comprises the phenol-aldehyde oligomer.

[00105] 10. The binder composition or process according to any one of paragraphs 1 to 9, wherein the binder composition comprises the second oligomer.

[00106] 11. The binder composition or process according to paragraph 10, wherein the second oligomer comprises the urea-aldehyde oligomer.

[00107] 12. The binder composition or process according to paragraph 11, wherein the urea- aldehyde oligomer has an aldehyde to urea molar ratio of about 1.75: 1 to about 2.25: 1.

[00108] 13. The binder composition or process according to paragraph 11 or 12, wherein the urea- aldehyde oligomer has a weight average molecular weight of about 200 to about 400.

[00109] 14. The binder composition or process according to any one of paragraphs 1 to 13, wherein the binder composition comprises the first oligomer comprising the polyalcohol-monoether group covalently bonded thereto, and wherein A is NH; B and G are independently CH₂ or NH; C, D, E, and F are independently CH₂ or O; I, J, K, L, and M are independently CH₃ or H; X, Y, and Z are independently NH or O; n, o, p, q, r, s, t, and u are independently an integer of 0 or 1 ; at least one of n, u, and t is 1; and the first oligomer comprises the urea-aldehyde oligomer, the melamine- aldehyde oligomer, or the phenol-aldehyde oligomer.

[00110] 15. The binder composition or process according to paragraph 14, wherein the first oligomer comprises the urea-aldehyde oligomer.

[00111] 16. The binder composition or process according to any one of paragraphs 1 to 14, wherein the binder composition comprises the second oligomer comprising the polyalcohol-polyether group covalently bonded thereto, and wherein A’ is NH; B’ and G’ are independently CH₂ or NH; C’, D’, E’, and F’ are independently CH₂ or O; G, F, K’, L’, and M’ are independently CH₃ or H; X’, Y’, and Z’ are independently NH or O; n’, o’, p’, q’, r’, s’, t’, and u’ are independently an integer of 0 or 1; at least one of n’, u’, and t’ is 1; and the second oligomer comprises the urea- aldehyde oligomer, the melamine-aldehyde oligomer, or the phenol-aldehyde oligomer.

[00112] 17. The binder composition or process according to any one of paragraphs 1 to 16, wherein the binder composition further comprises water.

[00113] 18. The binder composition or process according to paragraph 17, wherein the binder composition comprises about 30 wt% to about 45 wt% of the water and about 55 wt% to about 70 wt% of a combined amount of any first oligomer and any second oligomer, wherein all weight percent values are based on a combined weight of the water, any first oligomer, and any second oligomer.

[00114] 19. The binder composition or process according to paragraph 17, wherein the binder composition comprises about 35 wt% to about 40 wt% of the water and about 60 wt% to about 65 wt% of a combined amount of any first oligomer and any second oligomer, wherein all weight percent values are based on a combined weight of the water, any first oligomer, and any second oligomer.

[00115] 20. The binder composition or process according to any one of paragraphs 17 to 19, wherein the binder composition has a viscosity of about 120 cps to about 400 cps at a temperature of about 25°C.

[00116] 21. The binder composition or process according to any one of paragraphs 17 to 20, wherein the binder composition has a pH of about 7.5 to about 9 at a temperature of about 25°C. [00117] 22. The binder composition according to any one of paragraphs 17 to 21, wherein the binder composition has a viscosity of about 150 cps to about 350 cps at a temperature of about 25°C.

[00118] 23. The binder composition or process according to any one of paragraphs 17 to 22, wherein the binder composition has a pH of about 8 to about 8.5 at a temperature of about 25°C.

[00119] 24. The process according to any one of paragraphs 3 to 23, wherein the binder composition in the resinated furnish is at least partially cured by heating the mixture to a temperature of about l25°C to about 300°C for a time period of about 2 seconds to about 2 minutes.

[00120] 25. The process according to any one of paragraphs 3 to 24, wherein the plurality of substrates comprises glass fibers, mineral fibers, ceramic fibers, synthetic fibers, or any mixture thereof.

[00121] 26. The process according to any one of paragraphs 3 to 25, wherein the composite product has an average dry tensile strength of at least 100 lbs/3 inches, as measured according to ASTM D2l05-0l(20l4).

[00122] 27. The process according to any one of paragraphs 3 to 26, wherein the composite product has an average hot-wet tensile strength of at least 65 lbs/3 inches, as measured according to ASTM D2l05-0l(20l4).

[00123] 28. The process according to any one of paragraphs 3 to 27, wherein the composite product has an average tear strength of at least 520 gF, as measured according to TAPPI T 414.

[00124] 29. The process according to any one of paragraphs 3 to 28, wherein the composite product comprises about 10 wt% to about 25 wt% of the at least partially cured binder composition, based on a dry weight of the plurality of substrates.

[00125] 30. The process according to any one of paragraphs 2 or 4 to 29, wherein the first mixture comprises the polyamine compound, and wherein the polyamine compound comprises diethylenetriamine (DETA), bis(hexamethylene)triamine, hexamethylenediamine, tetram ethyl enetetramine, tris(2-aminoethyle)amine, ethylene diamine, polyether amines, or any mixture thereof.

[00126] 31. The process according to any one of paragraphs 2 or 4 to 30, wherein the first mixture comprises the polyol compound, and wherein the polyol compound comprises diethylene glycol, polyvinyl alcohol, polyethylene glycol, pentaerythritol, sorbitol, triglycerol, or any mixture thereof.

[00127] 32. The process according to any one of paragraphs 2 or 4 to 31, wherein the first mixture comprises the polyamine/polyol compound, and wherein the polyamine/polyol compound comprises diethanolamine, triethanolamine, N-(2-hydroxyethyl)ethylenediamine, 2-(2- aminoethoxy)ethanol, or any mixture thereof.

[00128] 33. The process according to any one of paragraphs 2 or 4 to 32, wherein the epihalohydrin compound comprises epichlorohydrin, epibromohydrin, epiiodohydrin, or any mixture thereof.

[00129] 34. The process according to any one of paragraphs 2 or 4 to 33, wherein the amide compound is combined with the second intermediate to produce the third mixture.

[00130] 35. The process according to paragraph 34, wherein the amide compound comprises urea, melamine, or a mixture thereof.

[00131] 36. The process according to any one of paragraphs 2 or 4 to 35, wherein the phenolic compound is combined with the second intermediate to produce the third mixture.

[00132] 37. The process according to paragraph 35, wherein the phenolic compound comprises phenol.

[00133] 38. The process according to any one of paragraphs 2 or 4 to 37, wherein the aldehyde compound comprises formaldehyde.

[00134] 39. A polyalcohol-monoether having a chemical formula of:

, wherein A and F are independently CFh, O, or NH; B, C, D, and E are independently CEE or O; I, J, K, L, and M are independently C¾ or H; X and Z are independently OH, NH₂, or NH; Y is O or NH; n, o, p, q, r, s, t, and u are independently an integer of 0 to 6, at least one of n, u, and t is an integer of 1 to 6; and R is CL, Br, or I.

[00135] 40. A polyalcohol-polyether having a chemical formula of:

, wherein A and F are independently CH₂, O, or NH; B, C, D, and E are independently CEE or O; I, J, K, L, and M are independently C¾ or H; X and Z are independently OH, NH₂, or NH; Y is O or NH; n, o, p, q, r, s, t, and u are independently an integer of 0 to 6; at least one of n, u, and t is an integer of 1 to 6; and R is Cl, Br, or I.

[00136] 41. The polyalcohol-monoether or the polyalcohol-polyether according to paragraphs 39 or 40, wherein A is NH; B and G are independently CH₂ or NH; C, D, E, and F are independently CH₂ or O; I, J, K, L, and M are independently C¾ or H; X, Y, and Z are independently NH or O; n, o, p, q, r, s, t, and u are independently an integer of 0 or 1; at least one of n, u, and t is 1, and R is Cl.

[00137] Certain embodiments and features have been described using a set of numerical upper limits and a set of numerical lower limits. It should be appreciated that ranges including the combination of any two values, e.g ., the combination of any lower value with any upper value, the combination of any two lower values, and/or the combination of any two upper values are contemplated unless otherwise indicated. Certain lower limits, upper limits and ranges appear in one or more claims below. All numerical values are "about" or "approximately" the indicated value, and take into account experimental error and variations that would be expected by a person having ordinary skill in the art.

[00138] Various terms have been defined above. To the extent a term used in a claim is not defined above, it should be given the broadest definition persons in the pertinent art have given that term as reflected in at least one printed publication or issued patent. Furthermore, all patents, test procedures, and other documents cited in this application are fully incorporated by reference to the extent such disclosure is not inconsistent with this application and for all jurisdictions in which such incorporation is permitted.

[00139] While the foregoing is directed to embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.

Claims

Claims: What is claimed is:

1. A binder composition for making a composite product, comprising:

a first oligomer comprising a polyalcohol-monoether group covalently bonded thereto, the first oligomer having a chemical structure of:

first oligomer

wherein A and F are independently CH₂, O, or NH; B, C, D, and E are independently CEE or O; I, J, K, L, and M are independently C¾ or H; X and Z are independently OH, NH₂, or NH; Y is O or NH; n, o, p, q, r, s, t, and u are independently an integer of 0 to 6; at least one of n, u, and t is an integer of 1 to 6; and the first oligomer is selected from the group consisting of: a urea-aldehyde oligomer; a melamine-aldehyde oligomer; a phenol-aldehyde oligomer; a phenol-urea-aldehyde oligomer; a melamine -urea-aldehyde oligomer; a biuret-aldehyde oligomer; an adipamide-aldehyde oligomer; a 2-cyano-guanidine-aldehyde oligomer; a thiourea-aldehyde oligomer; a cyanurate- aldehyde oligomer; a bis-phenol alcohol-aldehyde oligomer; a 4-/tW-butylphenol -aldehyde oligomer; and a 2,4-di-tert-butylphenol-aldehyde oligomer, or

a second oligomer comprising a polyalcohol-polyether group covalently bonded thereto, the second oligomer having a chemical structure of:

second oligomer wherein A’ and F are independently CH₂, O, or NH; B’, C’, D’, and E’ are independently CEE or O; G, J’, K’, L’, and M’ are independently CH₃ or H; X’ and Z’ are independently OH, NH₂, or NH; Y’ is O or NH; n’, o’, p’, q’, r’, s’, t’, and u’ are independently an integer of 0 to 6; at least one of n’, u’, and t’ is an integer of 1 to 6; and the second oligomer is selected from the group consisting of: a urea-aldehyde oligomer; a melamine-aldehyde oligomer; a phenol-aldehyde oligomer; a phenol-urea-aldehyde oligomer; a melamine-urea-aldehyde oligomer; a biuret-aldehyde oligomer; an adipamide-aldehyde oligomer; a 2-cyano-guanidine-aldehyde oligomer; a thiourea- aldehyde oligomer; a cyanurate-aldehyde oligomer; a bis-phenol alcohol-aldehyde oligomer; a 4- /f/Abutylphenol -aldehyde oligomer; and a 2,4-di-tert-butylphenol-aldehyde oligomer.

2. The binder composition of claim 1, wherein the binder composition comprises the first oligomer, wherein the first oligomer comprises the urea-aldehyde oligomer, and wherein the urea- aldehyde oligomer has an aldehyde to urea molar ratio of about 1.75: 1 to about 2.25: 1.

3. The binder composition of claim 1, wherein the binder composition comprises the first oligomer, wherein the first oligomer comprises the urea-aldehyde oligomer, and wherein the urea- aldehyde oligomer has a weight average molecular weight of about 200 to about 400.

4. The binder composition of claim 1, wherein the binder composition comprises the second oligomer, wherein the second oligomer comprises the urea-aldehyde oligomer, and wherein the urea-aldehyde oligomer has an aldehyde to urea molar ratio of about 1.75: 1 to about 2.25: 1.

5. The binder composition of claim 1, wherein the binder composition comprises the second oligomer, wherein the second oligomer comprises the urea-aldehyde oligomer, and wherein the urea-aldehyde oligomer has a weight average molecular weight of about 200 to about 400.

6. The binder composition of claim 1, wherein the binder composition comprises the first oligomer comprising the polyalcohol-monoether group covalently bonded thereto, and wherein A is NH; B and G are independently CH₂ or NH; C, D, E, and F are independently CH₂ or O; I, J, K, L, and M are independently CH₃ or H; X, Y, and Z are independently NH or O; n, o, p, q, r, s, t, and u are independently an integer of 0 or 1, at least one of n, u, and t is 1; and the first oligomer comprises the urea-aldehyde oligomer.

7. The binder composition of claim 1, wherein the binder composition comprises the second oligomer comprising the polyalcohol-polyether group covalently bonded thereto, and wherein A’ is NH; B’ and G’ are independently CH₂ or NH; C D’, E’, and F are independently CH₂ or O; G, G, K’, L’, and M’ are independently CH₃ or H; X’, Y’, and Z’ are independently NH or O; n’, o’, p’, q’, r’, s’, t’, and u’ are independently an integer of 0 or 1; at least one of n’, u’, and t’ is 1; and the second oligomer comprises the urea-aldehyde oligomer.

8. The binder composition of claim 1, wherein the binder composition further comprises water.

9. The binder composition of claim 8, wherein the binder composition comprises about 30 wt% to about 45 wt% of the water and about 55 wt% to about 70 wt% of a combined amount of any first oligomer and any second oligomer, wherein all weight percent values are based on a combined weight of the water, any first oligomer, and any second oligomer.

10. The binder composition of claim 8, wherein the binder composition has a viscosity of about 120 cps to about 400 cps at a temperature of about 25°C.

11. The binder composition of claim 8, wherein the binder composition has a pH of about 7.5 to about 9 at a temperature of about 25°C.

12. The binder composition of claim 8, wherein:

the binder composition comprises about 35 wt% to about 40 wt% of the water and about 60 wt% to about 65 wt% of a combined amount of any first oligomer and any second oligomer, wherein all weight percent values are based on a combined weight of the water, any first oligomer, and any second oligomer,

the binder composition has a viscosity of about 150 cps to about 350 cps at a temperature of about 25°C, and the binder composition has a pH of about 8 to about 8.5 at a temperature of about 25°C.

13. A process for making a binder composition, comprising:

reacting a first mixture comprising a poly amine compound, a polyol compound, or a polyamine/polyol compound with an aldehyde compound to produce a first intermediate;

combining an epihalohydrin compound with the first intermediate to produce a second mixture comprising the first intermediate and the epihalohydrin compound;

reacting the second mixture comprising the first intermediate and the epihalohydrin compound to produce a second intermediate;

combining an amide compound, a phenolic compound, or a mixture of an amide compound and a phenolic compound with the second intermediate to produce a third mixture comprising the second intermediate and the amide compound, the phenolic compound, or the mixture of the amide compound and the phenolic compound; and

reacting the third mixture comprising the second intermediate and the amide compound, the phenolic compound, or the mixture of the amide compound and the phenolic compound to produce a first oligomer comprising a polyalcohol-monoether group covalently bonded thereto, a second oligomer comprising a polyalcohol-polyether group covalently bonded, or a mixture thereof, wherein:

the first oligomer comprising the polyalcohol-monoether group covalently bonded thereto has a chemical structure of:

first oligomer

wherein A and F are independently CH₂, O, or NH; B, C, D, and E are independently CEE or O; I, J, K, L, and M are independently C¾ or H; X and Z are independently OH, NH₂, or NH; Y is O or NH; n, o, p, q, r, s, t, and u are independently an integer of 0 to 6; at least one of n, u, and t is an integer of 1 to 6; and the first oligomer is selected from the group consisting of: a urea-aldehyde oligomer; a melamine-aldehyde oligomer; a phenol-aldehyde oligomer; a phenol-urea-aldehyde oligomer; a melamine -urea-aldehyde oligomer; a biuret-aldehyde oligomer; an adipamide-aldehyde oligomer; a 2-cyano-guanidine-aldehyde oligomer; a thiourea-aldehyde oligomer; a cyanurate- aldehyde oligomer; a bis-phenol alcohol-aldehyde oligomer; a 4-/tv7-butylphenol -aldehyde oligomer; and a 2,4-di-tert-butylphenol-aldehyde oligomer, and

the second oligomer comprising the polyalcohol-polyether group covalently bonded thereto has a chemical structure of:

second oligomer

wherein A’ and F’ are independently CFh, O, or NH; B’, C’, D’, and E’ are independently CFb or O; G, J’, K’, L’, and M’ are independently CEE or H; X’ and Z’ are independently OH, NH₂, or NH; Y’ is O or NH; n’, o’, p’, q’, r’, s’, t’, and u’ are independently an integer of 0 to 6; at least one of n’, u’, and t’ is an integer of 1 to 6; and the second oligomer is selected from the group consisting of: a urea-aldehyde oligomer; a melamine-aldehyde oligomer; a phenol-aldehyde oligomer; a phenol-urea-aldehyde oligomer; a melamine-urea-aldehyde oligomer; a biuret-aldehyde oligomer; an adipamide-aldehyde oligomer; a 2-cyano-guanidine-aldehyde oligomer; a thiourea- aldehyde oligomer; a cyanurate-aldehyde oligomer; a bis-phenol alcohol-aldehyde oligomer; a 4- /tv7-butylphenol -aldehyde oligomer; and a 2,4-di-tert-butylphenol-aldehyde oligomer.

14. A process for making a composite product, comprising:

contacting a plurality of substrates with a binder composition comprising a first oligomer comprising a polyalcohol-monoether group covalently bonded thereto, a second oligomer comprising a polyalcohol-polyether group covalently bonded thereto, or a mixture thereof to produce a resinated furnish, wherein:

the first oligomer comprising the polyalcohol-monoether group covalently bonded thereto has a chemical structure of:

first oligomer

wherein A and F are independently CH₂, O, or NH; B, C, D, and E are independently CH₂ or O; I, J, K, L, and M are independently CH₃ or H; X and Z are independently OH, NH₂, or NH; Y is O or NH; n, o, p, q, r, s, t, and u are independently an integer of 0 to 6; at least one of n, u, and t is an integer of 1 to 6; and the first oligomer is selected from the group consisting of: a urea- aldehyde oligomer; a melamine-aldehyde oligomer; a phenol-aldehyde oligomer; a phenol-urea- aldehyde oligomer; a melamine -urea-aldehyde oligomer; a biuret-aldehyde oligomer; an adipamide- aldehyde oligomer; a 2-cyano-guanidine-aldehyde oligomer; a thiourea-aldehyde oligomer; a cyanurate-aldehyde oligomer; a bis-phenol alcohol-aldehyde oligomer; a 4-/er/-butylphenol- aldehyde oligomer; and a 2,4-di-tert-butylphenol-aldehyde oligomer, and

the second oligomer comprising the polyalcohol-polyether group covalently bonded thereto has a chemical structure of:

k second oligomer

wherein A’ and F’ are independently CH₂, O, or NH; B’, C’, D’, and E’ are independently CFb or O; G, E, K’, L’, and M’ are independently CEE or H; X’ and Z’ are independently OH, NH₂, or NH; Y’ is O or NH; n’, o’, p’, q’, r’, s’, t’, and u’ are independently an integer of 0 to 6; at least one of n’, u’, and t’ is an integer of 1 to 6; and the second oligomer is selected from the group consisting of: a urea-aldehyde oligomer; a melamine-aldehyde oligomer; a phenol-aldehyde oligomer; a phenol-urea-aldehyde oligomer; a melamine-urea-aldehyde oligomer; a biuret-aldehyde oligomer; an adipamide-aldehyde oligomer; a 2-cyano-guanidine-aldehyde oligomer; a thiourea- aldehyde oligomer; a cyanurate-aldehyde oligomer; a bis-phenol alcohol-aldehyde oligomer; a 4- /f/Abutylphenol -aldehyde oligomer; and a 2,4-di-tert-butylphenol-aldehyde oligomer; and

at least partially curing the binder composition in the resinated furnish to produce a composite product.

15. The process of claim 14, wherein the binder composition in the resinated furnish is at least partially cured by heating the mixture to a temperature of about l25°C to about 300°C for a time period of about 2 seconds to about 2 minutes.

16. The process of claim 14, wherein the plurality of substrates comprises glass fibers, mineral fibers, ceramic fibers, synthetic fibers, or any mixture thereof.

17. The process of claim 14, wherein:

the composite product has an average dry tensile strength of at least 100 lbs/3 inches, as measured according to ASTM D2l05-0l(20l4),

the composite product has an average hot-wet tensile strength of at least 65 lbs/3 inches, as measured according to ASTM D2l05-0l(20l4), and

the composite product has an average tear strength of at least 520 gF, as measured according to TAPPI T 414.

18. The process of claim 14, wherein the composite product comprises about 10 wt% to about 25 wt% of the at least partially cured binder composition, based on a dry weight of the plurality of substrates.

19. The process of claim 14, wherein the first mixture comprises the polyamine compound, wherein the polyamine compound comprises diethylenetriamine (DETA), bis(hexamethylene)triamine, hexamethylenediamine, tetramethylenetetramine, tris(2- aminoethyle)amine, ethylene diamine, polyether amines, or any mixture thereof, wherein the epihalohydrin compound comprises epichlorohydrin, wherein the amide compound is combined with the second intermediate to produce the third mixture, and wherein . the amide compound comprises urea, melamine, or a mixture thereof.

20. The process of claim 14, wherein the first mixture comprises the polyol compound, wherein the polyol compound comprises diethylene glycol, polyvinyl alcohol, polyethylene glycol, pentaerythritol, sorbitol, triglycerol, or any mixture thereof, wherein the epihalohydrin compound comprises epichlorohydrin, wherein the amide compound is combined with the second intermediate to produce the third mixture, and wherein the amide compound comprises urea, melamine, or a mixture thereof.