Alkylated phenolic resin composition and application

Abstract

Embodiments of the present disclosure generally relate to phenolic resin compositions, methods of making the same, and uses thereof. In one embodiment, a resin composition is provided. The present invention relates to a resin composition comprising a wax emulsion and a polymer composition, the polymer composition comprising an alkylphenol-phenol-aldehyde polymer, the alkylphenol-phenol-aldehyde polymer comprising: an alkylphenol monomer unit; and a phenol compound comonomer unit. In another embodiment, an article of manufacture is provided that includes a lignocellulosic substrate and a resin composition that includes an alkylphenol-phenol-aldehyde polymer, a polyol, and a wax emulsion.

Description

[0001] Cross-references to related applications

[0002] This application claims the benefit and priority of U.S. Provisional Application Serial No. 63 / 538,635, filed September 15, 2023, which is incorporated herein by reference in its entirety. Technical Field

[0003] The embodiments disclosed herein generally relate to phenolic resin compositions, methods for preparing them, and their uses. Background Technology

[0004] Phenolic resins, such as phenol-aldehyde resins, are widely used as binders and adhesives in structural lignocellulosic composites such as oriented strand board (OSB), particleboard, composite boards, and plywood. Phenolic resins are typically water-based, requiring the loss of water for curing, and lack water resistance. Therefore, conventional phenolic resins perform poorly in the production of lignocellulosic composites manufactured under steam preheating or high humidity conditions. For example, exposure to steam (forced steam air) dilutes the phenolic resin, leading to excessive penetration, washing out, or both, resulting in poor bonding between the resin and the wood substrate. High humidity and steam slow down the curing process of the phenolic resin, thus requiring increased curing cycle time for the board to cure, negatively impacting productivity and yield. Dilution, excessive penetration, and washing out also weaken the physical properties of the composite. For example, lignocellulosic composites made from conventional phenolic resins suffer from high water absorption and thickness swelling. High water absorption and thickness expansion can lead to poor dimensional stability in composite materials, resulting in joint protrusions, sheet warping, and unevenness. Poor mechanical stability in composites made with conventional phenolic resins can also affect structural integrity and reduce load-bearing capacity.

[0005] There is a demand for new phenolic resin compositions. Summary of the Invention

[0006] Overview

[0007] The embodiments disclosed herein generally relate to phenolic resin compositions, methods for preparing them, and their uses. Unlike conventional phenolic resins, the embodiments described herein can be used with a steam preheater and in a continuous steam process without sacrificing linear velocity or final board properties. Furthermore, the phenolic resin compositions described herein can cure rapidly, thus without sacrificing manufacturing time. Moreover, compared to conventional phenolic resins, the resin compositions of this disclosure are able to produce lignocellulose composite products with excellent water absorption and thickness swelling test results, demonstrating their superior mechanical properties. Additionally, the embodiments described herein can be used in moisture-proof applications without sacrificing the water properties of the final board.

[0008] In one embodiment, a resin composition is provided. The resin composition comprises a wax emulsion and a polymer composition comprising an alkylphenol-phenol-aldehyde polymer, the alkylphenol-phenol-aldehyde polymer comprising: the wax emulsion; and the polymer composition comprising the alkylphenol-phenol-aldehyde polymer. The alkylphenol-phenol-aldehyde polymer comprises alkylphenol monomer units and phenolic compound comonomer units, the alkylphenol monomer units being represented by formula (I):

[0009]

[0010] Where R is an unsubstituted hydrocarbon group having 1-40 carbon atoms or a substituted hydrocarbon group having 1-40 carbon atoms.

[0011] In another embodiment, a resin composition is provided. The resin composition comprises a wax emulsion and a polymer composition, the polymer composition comprising a condensation product of a reaction mixture, the reaction mixture comprising an alkylphenol compound, a phenol compound, an aldehyde, a base, a polyol, and a solvent.

[0012] In another embodiment, a curable resin composition is provided. The curable resin composition comprises a wax emulsion. The curable resin composition further comprises a reaction product of a phenolic compound; formaldehyde; and an alkylphenol having 1-40 carbon atoms in the alkyl group of the alkylphenol, wherein the molar ratio of the formaldehyde to the total amount of the phenol and the alkylphenol is about 2:1 to about 2.6:1.

[0013] In another embodiment, an article comprising a lignocellulose material and the composition described herein is provided.

[0014] In another embodiment, an article of manufacture is provided. The article of manufacture comprises a lignocellulose matrix and a resin composition comprising an alkylphenol-phenol-aldehyde polymer, a polyol, and a wax emulsion.

[0015] In another embodiment, a resin composition is provided. The resin composition comprises a wax emulsion; a phenolic resin; and a polymer composition comprising an alkylphenol-phenolic polymer.

[0016] In another embodiment, an article of manufacture is provided. The article of manufacture comprises a lignocellulose matrix; and a resin composition comprising: an alkylphenol-phenol-aldehyde polymer; a phenolic resin; and a wax emulsion.

[0017] In another embodiment, a method for forming a resin composition is provided. The method includes heating a reaction mixture to form a polymer composition, the reaction mixture comprising two or more phenolic compounds, an aldehyde, a base, a polyol, and a solvent, wherein the first phenolic compound of the two or more phenolic compounds comprises an alkylphenol having the following formula:

[0018]

[0019] R contains 1-40 carbon atoms, and the aldehyde is selected from formaldehyde, oligooxyformaldehyde, and combinations thereof. The method further includes introducing a wax emulsion together with the polymer composition to form a resin composition. Attached Figure Description

[0020] To gain a more detailed understanding of the features described above in this disclosure, a more specific description of the disclosure, which has been briefly outlined above, can be obtained by referring to embodiments (some of which are shown in the accompanying drawings). However, it should be noted that the drawings illustrate only exemplary embodiments and should not be considered as limiting their scope, allowing for other equally effective embodiments.

[0021] Figure 1 The image shows a superimposed gel permeation chromatography (GPC) chromatogram of high molecular weight alkylphenol-phenol-aldehyde polymer compositions, low molecular weight alkylphenol-phenol-aldehyde polymer compositions and their blends.

[0022] Figure 2 It is a bar chart showing the components of high molecular weight alkylphenol-phenol-aldehyde polymer compositions, low molecular weight alkylphenol-phenol-aldehyde polymer compositions and their blends. Detailed Implementation

[0023] Detailed instructions

[0024] Embodiments of this disclosure generally relate to phenolic resin compositions, methods of preparing the same, and uses thereof. The inventors have discovered phenolic resin compositions capable of overcoming many obstacles encountered with conventional phenolic resins during the manufacture of lignocellulosic composites. Briefly, and in some embodiments, the phenolic resin composition may comprise an alkylphenol-phenol-aldehyde polymer, a wax emulsion, and optionally one or more additives such as rheology modifiers.

[0025] As mentioned above, conventional phenolic resins perform poorly in the production of lignocellulosic composites manufactured under steam preheating or high humidity conditions. Lignocellulosic composites such as OSB are typically produced via continuous presses that use steam preheaters to heat the pads and initiate the curing process in order to increase line speed and maximize production yield. Although the steam has a low moisture content (dew point), it affects the curing of the adhesive used to manufacture the boards. Lignocellulosic composite manufacturers operating continuous press steam preheater processes typically rely on polymeric methylene diphenyl diisocyanate (pMDI) as the adhesive. During steam application, the hydrophobicity of pMDI helps prevent the adhesive from washing out, and the moisture present during this steam application helps pMDI cure more quickly as an isocyanate. In contrast, exposing conventional phenolic resin adhesives to steam dilutes the resin, leading to excessive resin penetration into the lignocellulosic matrix, washing out, or both, resulting in poor bonding between the resin and the lignocellulosic matrix.

[0026] To enhance the performance of phenolic resins, for example, the inventors have discovered that partial substitution of phenol in phenolic resins results in alkylphenol-phenol-aldehyde resins with improved hydrophobic properties, improved surface tension for better surface coverage (resin distribution), and improved wetting properties. In some instances, it has been found that alkylphenol-phenol-aldehyde resins with reduced amounts of smaller molecular species (e.g., hydroxymethylphenol) and increased amounts of oligomers, medium polymers, macropolymers, and very macropolymers can exhibit better performance. Here, the aldehyde to phenol / alkylphenol ratio and / or the amount of catalyst (e.g., sodium hydroxide) can be controlled to achieve, for example, the desired type of bonding, polydispersity, and polymer molecular weight distribution between monomers (e.g., formaldehyde, phenol, and alkylphenol) to balance reactivity and curing speed.

[0027] The inventors have also discovered that phenolic resin compositions containing wax emulsions (e.g., sodium lignosulfonate porous paraffin) can improve water properties without affecting the bonding and durability of the finished lignocellulose composite material (e.g., composite board or sheet).

[0028] The inventors have also discovered that one or more optional additives in the phenolic resin composition, such as rheology modifiers, surfactants, or both, can provide beneficial properties. Rheology modifiers (e.g., polyols, such as glycols and / or glycerols, etc.) can partially replace water in the resin composition solution. The rheology modifier can be added to the polymer precursor mixture during the reaction to form an alkylphenol-phenol-aldehyde polymer. Additionally or alternatively, the rheology modifier can be added to the alkylphenol-phenol-aldehyde polymer and the wax emulsion. The rheology modifier can help solubilize the polymer solution to promote an increase in molecular weight. This substitution can, for example, increase the solids content of the resin composition, which can improve heat transfer during the manufacture of lignocellulose composites, improve resin flow, and improve resin penetration when applied to a substrate. Surfactants can contribute to resin distribution and penetration control on lignocellulose substrates.

[0029] In some embodiments, different amounts of catalyst (e.g., sodium hydroxide) are used to form alkylphenol-phenol-aldehyde polymers with different molecular weight distributions.

[0030] Compared to conventional resin compositions, the resin compositions described herein are fast-curing, high-molecular-weight resin compositions. Furthermore, lignocellulose composites manufactured using the resin compositions described herein exhibit improved mechanical properties compared to conventional techniques.

[0031] The headings are used for convenience only and do not limit the scope of this disclosure. The aspects described herein may be combined with other aspects. As used herein, a “composition” may comprise a component (one or more) of the composition, a reaction product (one or more) of two or more components of the composition, and / or a balance of remaining starting components (one or more). The compositions of this disclosure can be prepared by any suitable mixing process.

[0032] Resin Composition

[0033] The resin composition disclosed herein may comprise an alkylphenol-phenol-aldehyde polymer composition and a wax emulsion. The resin composition may further comprise one or more additional additives. These one or more additional additives may comprise a rheology modifier, a surfactant, or a combination thereof. The rheology modifier may be derived from a rheology modifier used during the synthesis of the alkylphenol-phenol-aldehyde polymer composition. Additionally or alternatively, a rheology modifier may be added to the alkylphenol-phenol-aldehyde polymer composition and the wax emulsion.

[0034] As further described below, the resin compositions of this disclosure can be used with lignocellulosic substrates to form articles such as oriented strand board, particleboard, fiberboard, medium density fiberboard, building panels, composite panels and plywood, although other applications are also considered.

[0035] Alkylphenol-phenol-aldehyde polymer composition

[0036] Alkylphenol-phenol-aldehyde polymer compositions can be formed by reacting a mixture comprising two or more phenolic compounds, an aldehyde, and a catalyst. The mixture may further comprise one or more optional components such as a solvent, a rheology modifier, or a combination thereof, as well as other optional components. The rheology modifier can be used to aid in the solvation of the polymer solution to promote an increase in molecular weight.

[0037] The two or more phenolic compounds comprise alkylphenol compounds and phenol compounds. The phenol compound may comprise phenol, resorcinol, or a combination thereof. The alkylphenol compound promotes improved water properties, such as water absorption and thickness swelling, in the compositions described herein and articles produced using such compositions. Any suitable alkylphenol compound may be used. A suitable alkylphenol may be represented by formula (I):

[0038] .

[0039] In formula (I), R is an unsubstituted hydrocarbon group, a substituted hydrocarbon group, or a functional group containing at least one element from groups 13-17 of the periodic table. In formula (I), x represents the number of R groups attached to the aromatic ring, and can be an integer of 1-4, for example 1-3, for example 1, 2, 3, or 4.

[0040] In formula (I), at least one R group is an unsubstituted hydrocarbon group or a substituted hydrocarbon group. When there is more than one R group, the R groups may be the same or different.

[0041] The R group in formula (I) has any suitable number of carbon atoms, for example, 1-100 carbon atoms, 1-50 carbon atoms, 1-40 carbon atoms, 2-30 carbon atoms, 3-20 carbon atoms, or 6-15 carbon atoms. The number of carbon atoms in the R group of formula (I) can be about 15, at least about 10, less than about 20, greater than about 12, or about 10 to about 20. The R group of formula (I) can be unsubstituted or substituted, linear or branched, saturated or unsaturated, cyclic or acyclic. Regarding saturation, the R group of formula (I) can be fully saturated, partially unsaturated, or completely unsaturated.

[0042] In formula (I), R can be an unsubstituted hydrocarbon group. An "unsubstituted hydrocarbon group" means a group consisting only of hydrogen and carbon atoms. Illustrative but non-limiting examples of unsubstituted hydrocarbon groups include alkyl groups having 1-40 carbon atoms, such as 1-20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl, pentyl, hexyl, heptyl, octyl, ethyl-2-hexyl, isooctyl, nonyl, n-decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, eicosyl or isomers thereof; alicyclic groups having 3-20 carbon atoms such as cyclopentyl or cyclohexyl; aromatic groups having 6-20 carbon atoms such as phenyl or naphthyl; or any combination thereof.

[0043] In formula (I), R can be a substituted hydrocarbon group. A "substituted hydrocarbon group" refers to an unsubstituted hydrocarbon group in which at least one hydrogen atom is replaced by at least one heteroatom or heteroatom-containing group, which is, for example, one or more elements from groups 13-17 of the periodic table, such as halogens (F, Cl, Br, or I), O, N, Se, Te, P, As, Sb, S, B, Si, Ge, Sn, Pb, etc., for example, C(O)R. C(C)NR 2. C(O)OR NR 2. OR 、SeR TeR PR 2. AsR 2. SbR 2. SR SO x (where x = 2 or 3), BR 2. SiR 3. GeR 3. SnR 3. PbR 3rd grade, of which R It is independently hydrogen or an unsubstituted hydrocarbon group, or at least one heteroatom of which has been inserted into the unsubstituted hydrocarbon group.

[0044] When at least one R group is an unsubstituted or substituted hydrocarbon group, the other R group (when x > 1) can be a functional group containing at least one element from Groups 13-17 of the periodic table. When the R group is a functional group containing at least one element from Groups 13-17, the R group can be a halogen (F, Cl, Br, or I), O, N, Se, Te, P, As, Sb, S, B, Si, Ge, Sn, Pb, etc., for example, C(O)R. C(C)NR 2. C(O)OR NR 2. OR 、SeR TeR PR 2. AsR 2. SbR 2. SR SO x (where x = 2 or 3), BR 2. SiR 3. GeR 3. SnR 3. PbR 3rd grade, of which R It is independently hydrogen or an unsubstituted hydrocarbon group, or at least one heteroatom of which has been inserted into the unsubstituted hydrocarbon group.

[0045] As used herein, references to R groups, alkyl groups, substituted alkyl groups, hydrocarbon groups, or substituted hydrocarbon groups (e.g., butyl) without specifying a particular isomer clearly disclose all isomers (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl). For example, a reference to an R group having four carbon atoms clearly discloses all its isomers. When a compound is described herein without specifying a particular isomer, enantiomer, or diastereomer, for example, in the form of a chemical formula or chemical name, the description is intended to include every isomer and enantiomer of the described compound (alone or in any combination).

[0046] More than one alkylphenol compound may be used. The alkylphenol of formula (I) may include cardanol, cresol, xylenol, ethylphenol, alkylresorcinol, its isomers, or combinations thereof. Suitable isomers for this alkylphenol compound include ortho, meta, and para isomers, such as ortho, meta, and para-cresols. For the purposes of this disclosure, alkylresorcinol is a dihydroxybenzene having one or two alkyl chains present on a ring. The one or two alkyl chains present on the ring of the alkylresorcinol may have 1-3 carbon atoms, although a higher number of carbon atoms is also considered.

[0047] An illustrative but non-limiting example of an alkylphenol is cashew phenol. In at least one embodiment, the R group of formula (I) is C. 15 H 30-n , where n is 0, 2, 4 or 6, and cashew phenol has formula (II):

[0048]

[0049] In equation (II), the dashed line indicates the presence or absence of unsaturation. As an example, triunsaturated cashew phenol (R=C 15 H 24 ; CAS number 37330-39-5) is shown in the following structure:

[0050]

[0051] As another example, monounsaturated cashew phenol (R=C 15 H 28 The CAS number (8007-24-7) is shown in the following structure:

[0052]

[0053] The double bonds (one or more) in cashew phenol can be cis, trans, or a combination thereof.

[0054] One or more phenolic compounds may be used in the polymer compositions described herein. Furthermore, one or more alkylphenols, such as one or more cashew phenols, may be used in the compositions described herein. For example, the compositions described herein may comprise a mixture of two or more of the following substances: cashew phenols having formula (II): triunsaturated cashew phenol (R=C 15 H 24 (As shown in the structure above), diunsaturated cashew phenol (R=C 15 H 26 ), monounsaturated cashew phenol (R=C 15 H 28 ) and saturated cashew phenols (R=C 15 H 30 (in any suitable proportion).

[0055] The alkylphenols used can be in the form of distillates, such as cashew nut distillate (CND), for example, cashew nut distillate under the trademark name 1500-1 of Palmer International Inc.

[0056] This aldehyde can be any suitable aldehyde, such as formaldehyde. Besides formaldehyde, oligooxyformaldehyde ((CH2O)) is another example. nFormalin (an aqueous solution of formaldehyde) can be used as a source of formaldehyde. Additionally or alternatively, formalin (an aqueous solution of formaldehyde) can be used as a source of formaldehyde. Alkyl aldehydes can be used, additionally or alternatively. Suitable alkyl aldehydes include those having 1-20 carbon atoms, for example 1-12 carbon atoms, or 3-15 carbon atoms, for example 5-12 carbon atoms, though other alkyl aldehydes are also considered. The number of carbon atoms in the alkyl aldehyde can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms, or a range thereof. Each of the above numbers may be preceded by the phrases “about,” “at least about,” “less than about,” or “greater than about,” and any of the above numbers may be used alone to describe an open range or in combination to describe a closed range. Illustrative but non-limiting examples of alkyl aldehydes include 3,5,5-trimethylhexanal, nonanal, 2-ethylhexanal, or combinations thereof. The polymer compositions disclosed herein may be in the form of formaldehyde-free polymer compositions. Alternatively, the polymer compositions described herein may be in the form of formaldehyde-containing polymer compositions.

[0057] Other aldehydes and ketones were also considered. These aldehydes may include formaldehyde, paraformaldehyde, alkyl aldehydes, or combinations thereof.

[0058] When the aldehyde is formaldehyde, the alkylphenol-phenol-aldehyde polymer composition is an alkylphenol-phenol-formaldehyde polymer (APFP) composition.

[0059] The amount of each phenolic compound, the amount of aldehyde, their molar ratio, or their combination can determine the molecular structure and physical properties of the polymer composition.

[0060] For the purposes of this disclosure, the weight percentage (wt%) of each component in the polymer compositions described herein is based on a solids weight percentage (% solids weight). The total weight % of the polymer compositions described herein does not exceed 100% by weight.

[0061] The total amount (by weight%) of the phenolic compounds (alkylphenols and phenols) in the polymer composition may be from about 0.1% by weight to about 40% by weight, for example from about 0.5% by weight to about 40% by weight, for example from about 1% by weight to about 35% by weight, for example from about 10% by weight to about 30% by weight, for example from about 15% by weight to about 25% by weight, based on the total weight percentage of the polymer composition. Other amounts may be considered. Any of the above figures may be used alone to describe an open range or in combination to describe a closed range. The total amount (wt%) of the at least phenolic compound in the polymer composition, based on the total weight of the polymer composition, may be 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, or 40, or a range thereof, though higher or lower amounts may also be considered. Each of the above figures may be preceded by the phrases “about,” “at least about,” “less than about,” or “greater than about,” and any of the above figures may be used alone to describe an open range or in combination to describe a closed range.

[0062] The total weight percentage of the alkylphenol compound may be greater than 0 wt%, about 15 wt% or less, or combinations thereof, for example, greater than 0 wt% to about 12 wt%, for example, about 0.1 wt% to about 12 wt%, for example, about 0.9 wt% to about 10 wt%, for example, about 1 wt% to about 10 wt%, for example, about 2 wt% to about 8 wt%, for example, about 4 wt% to about 6 wt%, based on the total weight percentage of two or more phenolic compounds, where the total weight percentage of two or more phenolic compounds does not exceed 100 wt%. Other amounts are also considered. Any of the above figures may be used alone to describe an open range or in combination to describe a closed range.

[0063] The total weight percentage of the phenolic compound can be about 85% by weight or more, less than 100% by weight, or a combination thereof, such as about 85% by weight to less than 100% by weight, such as about 88% by weight to less than 100% by weight, such as about 88% by weight to about 99.9% by weight, such as about 90% by weight to about 99.1% by weight, such as about 90% by weight to about 99% by weight, such as about 92% by weight to about 98% by weight, such as about 94% by weight to about 96% by weight, although other amounts are also considered. Any of the above figures can be used alone to describe an open range or in combination to describe a closed range.

[0064] The total amount of aldehyde in the polymer composition can be from about 0.1% by weight to about 35% by weight, for example from about 0.5% by weight to about 35% by weight, for example from about 1% by weight to about 25% by weight, for example from about 2% by weight to about 10% by weight, for example from about 3% by weight to about 5% by weight, based on the total weight of the polymer composition, although other amounts are also considered. Any of the above figures can be used alone to describe an open range or in combination to describe a closed range. The total amount (by weight%) of the aldehyde in the polymer composition, based on the total weight of the polymer composition, can be 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34 or 35, or a range thereof, although higher or lower amounts are also considered. Each of the above numbers may be preceded by the terms “about,” “at least about,” “less than about,” or “greater than about,” and any of the above numbers may be used alone to describe an open range or in combination to describe a closed range.

[0065] The molar ratio of the total amount of aldehydes to phenolic compounds (aldehyde / (phenolic compound + alkylphenol compound)) can be from about 2 to about 2.7, for example from about 2.1 to about 2.6, for example from about 2.2 to about 2.5, for example from about 2.3 to about 2.4, although other amounts are also taken into account. Any of the above figures can be used alone to describe an open range or in combination to describe a closed range.

[0066] Suitable polymer compositions described herein may contain catalysts such as bases or acids, such that the polymer composition may be in the form of resole resins or novolac resins. Resole resins are formed when prepared using a base, and novolac resins are formed when prepared using an acid. The base or acid acts as a catalyst for the reaction between the at least one phenolic compound and the at least one aldehyde. Illustrative but non-limiting examples of suitable bases include potassium hydroxide (KOH), sodium hydroxide (NaOH), lithium hydroxide (LiOH), barium hydroxide (Ba(OH)2), calcium hydroxide (Ca(OH)2), ammonium hydroxide (NH4OH), organic amines, sodium carbonate, potassium carbonate, or combinations thereof. Illustrative but non-limiting examples of suitable acids include inorganic and organic acids, such as hydrochloric acid (HCl), sulfuric acid (H2SO4), nitric acid (HNO3), phosphoric acid (H3PO4), sulfonic acid, sulfonamide acid, haloacetic acid, or combinations thereof. Other bases and acids are also considered.

[0067] The total amount of catalyst (e.g., base) in the polymer composition may be from about 0.1 wt% to about 15 wt%, for example from about 0.5 wt% to about 10 wt%, for example from about 1 wt% to about 9 wt%, for example from about 2.5 wt% to about 8 wt%, for example from about 3 wt% to about 5 wt%, based on the total weight % of the polymer composition. The total amount (wt%) of the at least one base (or acid, if used) in the polymer composition, based on the total weight % of the polymer composition, may be 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15, or a range thereof, although higher or lower amounts are also considered. Each of the above figures may be preceded by the wording “about,” “at least about,” “less than about,” or “greater than about,” and any of the above figures may be used alone to describe an open range or in combination to describe a closed range.

[0068] In addition to the phenolic compound, the aldehyde, and the catalyst (base or acid), the polymer composition described herein may further comprise at least one rheology modifier, such as a polyol. The polyol may contain two or more hydroxyl groups, such as diols and triols. Illustrative but non-limiting examples of suitable polyols may include glycerol, crude glycerol, refined glycerol, ethylene glycol, diethylene glycol, propylene glycol, propane-1,2,3-triol, glycerol, 1,2,3-trihydroxypropane, 1,2,3-propanetriol, or combinations thereof. Other suitable polyols include polyether polyols. Crude glycerol comprises an unpurified composition that is commonly used in industry and commercially available. Other components in crude glycerol include methanol, water, and various organic compounds based on precursor materials, etc. However, the specifications of crude glycerol, apart from its glycerol content, vary considerably.

[0069] Crude glycerol is distinguished from 97+% industrial grade and 99+% refined grade. Refined glycerol can be further classified as Kosher, USP (United States Pharmacopeia), or USP Kosher based on its source and processing. One example of crude glycerol is 82% to 85% glycerol, which is the most common because most biodiesel plants do not upgrade to more than 82% to 85%. Another example of crude glycerol is 92% to 95% glycerol. This 92% to 95% crude glycerol is much less common because relatively few biodiesel plants produce or upgrade to 92% to 95% crude glycerol levels. The polymer compositions described herein may contain crude glycerol, such as 82% to 85% glycerol or 92% to 95% glycerol, alone or in combination.

[0070] In some instances, crude glycerol having 82% to 85% glycerol may comprise a mixture of glycerol such as glycerol CAS No. 56-81-5, sodium chloride CAS # 7647-14-15, sodium sulfate 7757-82-6, water CAS No. 7732-18-5, and MONG (non-glycerol organic matter). In at least one instance, crude glycerol having 92% to 95% glycerol may comprise a mixture of glycerol, 1,2,3-propanetriol, and fatty acid methyl esters, such as glycerol such as glycerol CAS No. 56-81-5, water CAS No. 7732-18-5, potassium sulfate CAS No. 7778-80-5, fatty acid esters CAS No. 68937-84-8, and methanol CAS No. 7732-18-5. Other crude glycerols have also been considered.

[0071] The total amount of the polyol in the polymer composition may be less than about 25% by weight, for example from about 0.1% by weight to about 25% by weight, for example from about 0.5% by weight to about 20% by weight, for example from about 1% by weight to about 15% by weight, for example from about 1% by weight to about 12% by weight, for example from about 2% by weight to about 10% by weight, for example from about 4% by weight to about 6% by weight, based on the total weight of the polymer composition. The total amount (by weight) of the rheology modifier (e.g., polyol) based on the total weight of the polymer composition may be 0, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 or 25, or a range thereof, although higher or lower amounts are also considered. Each of the above numbers may be preceded by the terms “about,” “at least about,” “less than about,” or “greater than about,” and any of the above numbers may be used alone to describe an open range or in combination to describe a closed range.

[0072] The polymer composition may optionally contain urea. The total amount of urea in the polymer composition may be about 30% by weight or less, for example, about 0.1% by weight to about 30% by weight, for example, about 0.1% by weight to about 25% by weight, for example, about 1% by weight to about 20%, for example, about 5% by weight to about 15% by weight, for example, about 5% by weight to about 10% by weight, or about 10% by weight to about 15% by weight, based on the total weight of the polymer composition. The amount (by weight) of urea in the polymer composition, based on the total weight of the polymer composition, may be 0, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30, or a range thereof, although higher or lower amounts are also considered. Each of the above numbers may be preceded by the terms “about,” “at least about,” “less than about,” or “greater than about,” and any of the above numbers may be used alone to describe an open range or in combination to describe a closed range.

[0073] The polymer composition may further comprise solvents such as water, organic solvents, or both. Non-limiting examples of organic solvents include n-butanol, toluene, xylene, or mixtures thereof. The total amount of solvent (water, organic solvent, or both) in the polymer composition is based on a weight percentage of the total polymer composition and ranges from about 1% to about 99% by weight, for example from about 10% to about 90% by weight, for example from about 30% to about 70% by weight, for example from about 40% to about 60% by weight, for example from about 45% to about 58% by weight, although other amounts are also considered. Any of the above figures may be used alone to describe an open range or in combination to describe a closed range.

[0074] When the polymer composition contains a solvent such as water, one or more components of the polymer composition may be present in the form of one or more ions. For example, one or more anions such as Cl or one or more cations such as Na may be present in the composition.

[0075] Additional components of the polymer compositions described herein may include surfactants, defoamers, or combinations thereof.

[0076] The extent to which polymerization can be performed to form alkylphenol-phenol-aldehyde prepolymers and polymers allows for the formation of various condensation products such as hydroxymethylphenols, oligomers, medium-sized polymers, large polymers, and very large polymers. Number-average molecular weight (Mn), weight-average molecular weight (Mw), and z-average molecular weight (Mz) are determined by gel permeation chromatography (GPC) relative to a series of internal standards (sodium polystyrene sulfonate) of varying molecular weights, used to generate calibration curves to fit the molecular weights of the alkylphenol-phenol-aldehyde polymers. Molecular weight moments (distribution averages) are calculated using a UV detector. These distribution weight values ​​are categorized as Mn, Mw, and Mz. Mn is the number of molecules per unit mass (average chain length), which is sensitive to low molecular weight species. Mw is the weight-average molecular weight in the sample, and Mz is the average molecular weight, primarily sensitive to larger molecules.

[0077] The alkyl-phenol-formaldehyde polymer may have an Mn value in the range of about 200 g / mol to about 800 g / mol, an Mw value in the range of about 20,000 g / mol to about 40,000 g / mol, an Mz value in the range of about 200,000 g / mol to about 300,000 g / mol, or a combination thereof.

[0078] Alkylphenol-phenol-aldehyde condensation products can be formed from the polymer compositions described herein. For each class (low molecular weight, oligomer, medium and large / very large polymers), the percentage of the polymer composition was calculated from the elution retention time and detector response (mV) chromatograms obtained by a UV detector.

[0079] The polymer composition may have one or more of the following properties or characteristics:

[0080] (a) A first component comprising hydroxymethylated phenol and phenol, a second component comprising oligomers, a third component comprising medium-sized polymers, and a fourth component comprising macropolymers and very macropolymers, or combinations thereof. The total percentage of the types present in the polymer composition is based on the percentage of very macropolymers, macropolymers, medium-sized polymers, oligomers, hydroxymethylated phenols, and phenols, and does not exceed 100%.

[0081] (b) The percentage of the first component containing hydroxymethylated phenol and phenol is from about 0% to about 10%, for example from about 2% to about 8%, for example from about 4% to about 6%, though other values ​​are also considered. Any of the above figures may be used alone to describe an open range or in combination to describe a closed range.

[0082] (c) The percentage of the second component containing oligomers is from about 4% to about 20%, for example from about 8% to about 16%, for example from about 10% to about 14%, based on the total percentage of the species present in the polymer composition, though other values ​​are also considered. Any of the above figures may be used alone to describe an open range or in combination to describe a closed range.

[0083] (d) The percentage of the third component comprising a medium-sized polymer is from about 5% to about 20%, for example from about 8% to about 16%, for example from about 10% to about 15%, based on the total percentage of the species present in the polymer composition, though other values ​​are also considered. Any of the above figures may be used alone to describe an open range or in combination to describe a closed range.

[0084] (e) The percentage of the fourth component comprising macropolymers and very macropolymers is approximately 50% to approximately 90%, for example, approximately 55% to approximately 85%, for example, approximately 60% to approximately 80%, for example, approximately 65% ​​to approximately 75%, though other values ​​are also considered. Any of the above figures may be used alone to describe an open range or in combination to describe a closed range.

[0085] The composition of each species (component 1, component 2, component 3, and component 4) was calculated based on the UV detector response (mV) and elution time (minutes). Large and very large polymers eluted from approximately 20 minutes to approximately 27.5 minutes, medium-sized polymers from approximately 27.5 minutes to approximately 31.9 minutes, oligomers from approximately 31.9 minutes to approximately 36.5 minutes, hydroxymethylated phenols from approximately 36.8 minutes to approximately 42 minutes, and phenols from approximately 44.8 minutes. The percentage composition of these species was calculated as the ratio of the UV response trace (mV) of each species within the aforementioned elution time range to the total UV response trace (mV) of all species eluted from approximately 20 minutes to approximately 44.8 minutes.

[0086] (f) The total solids content in the polymer composition (in the percentage of non-volatile solids) can be any suitable amount, such as about 40 wt% to about 60 wt%, about 42 wt% to about 55 wt%, about 44 wt% to about 52 wt%, about 46 wt% to about 50 wt%, based on the total percentage of the polymer composition, although other amounts are also considered. Any of the above figures can be used alone to describe an open range or in combination to describe a closed range.

[0087] (g) The basicity (in pH) of the polymer composition may be about 7.5 or greater, for example about 8.5 to about 13, or at least about 8, or less than about 14. The basicity (in pH) may be 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, or 14, or a range thereof. Each of the above figures may be preceded by the terms “about,” “at least about,” “less than about,” or “greater than about,” and any of the above figures may be used alone to describe an open range or in combination to describe a closed range.

[0088] The alkylphenol-phenol-aldehyde polymer composition can be characterized as comprising a high molecular weight component and a low molecular weight component. The high molecular weight component may comprise macropolymers, very macropolymers, or combinations thereof. The low molecular weight component may comprise phenol, hydroxymethylated phenols, oligomers, medium-sized polymers, or combinations thereof.

[0089] The alkylphenol-phenol-aldehyde polymer composition may contain a high molecular weight component in an amount of about 50% to about 90% by weight, for example about 55% to about 85% by weight, for example about 60% to about 80% by weight, for example about 65% to about 75% by weight, based on the total weight of the alkylphenol-phenol-aldehyde polymer, the total weight percentage of the alkylphenol-phenol-aldehyde polymer not exceeding 100% by weight. Any of the above figures may be used alone to describe an open range or in combination to describe a closed range.

[0090] The alkylphenol-phenol-aldehyde polymer may contain low molecular weight components in amounts from about 10% to about 50% by weight, for example from about 15% to about 45% by weight, for example from about 20% to about 40% by weight, for example from about 25% to about 35% by weight, based on the total weight percentage of the alkylphenol-phenol-aldehyde polymer. Any of the above figures may be used alone to describe an open range or in combination to describe a closed range.

[0091] One or more alkylphenol-phenol-aldehyde compositions may be used in conjunction with the embodiments described herein. For example, a first alkylphenol-phenol-aldehyde composition and a second alkylphenol-phenol-aldehyde composition may be combined in any suitable amount. The first alkylphenol-phenol-aldehyde composition may be characterized as containing a higher amount of a low molecular weight component than the second alkylphenol-phenol-aldehyde composition, and the second alkylphenol-phenol-aldehyde composition may be characterized as containing a higher amount of a high molecular weight component.

[0092] The resin compositions described herein may comprise a ratio of high molecular weight alkylphenol-phenol-aldehyde to low molecular weight alkylphenol-phenol-aldehyde of about 7:3 to about 9:1, for example about 7.5:2.5 to about 8.5:1.5, for example about 8:2. Any of the above figures may be used alone to describe an open range or in combination to describe a closed range. As further described below, the resin compositions described herein further comprise a wax emulsion.

[0093] Table 1 provides the data obtained from carbon-13 nuclear magnetic resonance (NMR) 13 Non-limiting examples of the percentage of structural identity of alkylphenol-phenol-aldehyde polymer compositions obtained by C10 NMR analysis. Table 2 provides a description of structural identity with typical chemical shifts.

[0094] Table 1: Percentage of Structural Identity

[0095]

[0096] Table 2: Structural Identity Description

[0097]

[0098] This alkylphenol-phenol-aldehyde polymer composition can be prepared by any suitable method. For example, the alkylphenol-phenol-aldehyde polymer composition can be formed by a condensation reaction of the two or more phenolic compounds and the aldehyde. The reaction mixture may contain the amounts described herein for the polymer composition.

[0099] The two or more phenolic compounds and the aldehyde react in the presence of at least one base or at least one acid (e.g., one or more of the bases and acids described above) to form a reaction mixture comprising an alkylphenol-phenol-aldehyde polymer product. When a base catalyst is used, a methylphenolic resin can be formed, and when an acid catalyst is used, a phenolic varnish resin can be formed. Water is also produced during the condensation reaction. At least a portion of the water produced can be removed during, after, or both during and after the formation of the alkylphenol-phenol-aldehyde polymer composition by distillation, azeotropic distillation, vacuum distillation, and other suitable methods.

[0100] To form the alkylphenol-phenol-aldehyde polymer composition, the phenolic compound and the aldehyde can be used in the weight percentages described above. Alternatively, the alkylphenol-phenol-aldehyde polymer composition can be formed using a molar ratio of the aldehyde to the total amount of the phenolic compound, which is from about 1:1 to about 4.5:1, for example from about 1.5:1 to about 3.5:1, for example from about 1.5:1 to about 2.8:1, for example from about 2:1 to about 2.5, although higher or lower molar ratios have also been considered.

[0101] Water can be used as a solvent in the condensation reaction. An organic solvent can be used in the condensation reaction, and this organic solvent can form an azeotrope with water. For example, n-butanol, toluene, xylene, and mixtures thereof can be used. The solvent and the reactant mixture can be heated at a temperature of about 90°C to about 200°C, for example, about 100°C to about 160°C, although higher or lower temperatures are also considered. The solvent can also be removed during or after the condensation reaction. Additionally or alternatively, the solvent (e.g., those that do not release protons under condensation conditions) can be retained in the product after the condensation reaction.

[0102] After the formation of this alkylphenol-phenol-aldehyde polymer composition, the acid or base catalyst can be neutralized. The polymer composition can be used directly or after neutralization of the acid or base catalyst.

[0103] The alkylphenol-phenol-aldehyde polymer composition comprises alkylphenol monomer units (corresponding to the first monomer after polymerization), phenolic compound monomer units (corresponding to the second monomer after polymerization), and aldehyde compound comonomer units. In these and other embodiments, the alkylphenol-phenol-aldehyde polymer may have one or more of the following properties:

[0104] (a) The amount of alkylphenol monomer units in the alkylphenol-phenol-aldehyde polymer may be greater than 0 wt% to about 15 wt%, for example greater than 0 wt% to about 12 wt%, for example about 0.1 wt% to about 12 wt%, for example about 0.9 wt% to about 10 wt%, for example about 1 wt% to about 10 wt%, for example about 2 wt% to about 8 wt%, for example about 4 wt% to about 6 wt%, based on the total weight of the alkylphenol monomer units and phenolic compound monomer units, the total weight of the alkylphenol monomer units and phenolic compound monomer units shall not exceed 100 wt%. Other amounts are also considered. Any of the above figures may be used alone to describe an open range or in combination to describe a closed range.

[0105] (b) The amount of phenolic monomer units in the alkylphenol-phenolic-aldehyde polymer may be from about 85% by weight to less than 100% by weight, for example from about 88% by weight to less than 100% by weight, for example from about 88% by weight to about 99.9% by weight, for example from about 90% by weight to about 99.1% by weight, for example from about 90% by weight to about 99% by weight, for example from about 92% by weight to about 98% by weight, for example from about 94% by weight to about 96% by weight, based on the total weight percentage of the alkylphenol monomer units and the phenolic monomer units, although other amounts are also taken into account. Any of the above figures may be used alone to describe an open range or in combination to describe a closed range.

[0106] In addition to the alkylphenol-phenol-aldehyde polymer and the wax emulsion, the resin compositions described herein may optionally contain a phenolic resin. Any suitable phenolic resin can be used, such as commercially available phenolic resins. The phenolic resin may contain a phenol-aldehyde polymer. Therefore, and in some embodiments, a resin composition is provided comprising the wax emulsion, the alkylphenol-phenol-aldehyde polymer, and the phenolic resin described herein.

[0107] wax emulsion

[0108] In addition to the alkylphenol-phenol-aldehyde polymer composition, the resin composition further comprises a wax emulsion. As used herein, the term "wax emulsion" refers to an aqueous emulsion of one or more waxes that have been emulsified. The wax emulsion may contain waxes such as petroleum-based waxes, coal-derived waxes, synthetic waxes, bio-based waxes, or combinations thereof. The wax is emulsified using various chemical measures, including saponification, nonionic emulsifiers, lignin sulfonate dispersants, or combinations thereof, to form the wax emulsion.

[0109] Petroleum-based waxes may comprise paraffin wax, oil, or combinations thereof, such as slack wax. The petroleum-based wax may have an average carbon chain length of about 29-39 carbon atoms. The petroleum-based wax may have a melting point of about 38°C to about 70°C. The petroleum-based wax may have a minimum flash point of 218°C or higher, for example, about 218°C to about 271°C. The oil content of the petroleum-based wax may be, for example, less than about 20% by weight, for example, from about 10% to less than 20% by weight. The petroleum-based wax may have an average chain length of about 29-39 carbon atoms. Examples of petroleum-based waxes may include slack wax, scaly wax, fully refined wax, or combinations thereof.

[0110] Coal-derived waxes refer to those waxes derived from lignite or brown coal. Coal-derived waxes may have an acid value of about 5 mg KOH / g to about 35 mg KOH / g, a saponification value of about 80 mg KOH / g to about 105 mg KOH / g, a melting point greater than about 82.2 °C, or combinations thereof. Montan wax is an illustrative but not limiting example of coal-derived waxes.

[0111] Bio-based waxes refer to a class of waxes derived from plant and / or animal fats and oils, such as non-hydrogenated, partially hydrogenated, and / or fully hydrogenated fats and oils. Examples of these types of waxes may include carnauba wax, soy wax, carnauba wax, candelilla wax, tallow wax, beeswax, lanolin, or combinations thereof.

[0112] Synthetic waxes refer to polyethylene (PE) waxes, Fischer-Tropsch (FT) waxes, or α-olefin (AO) waxes derived from the polymerization of ethylene.

[0113] As described above, the wax is emulsified to form a wax emulsion. This wax emulsion can be a composition. The wax emulsion can be emulsified using saponification. Saponification can be achieved by combining the wax with a strongly basic material (e.g., an alkali metal hydroxide or other hydroxide). Examples of such hydroxides include sodium hydroxide, potassium hydroxide, ammonium hydroxide, or combinations thereof. The amount of strongly basic material used to saponify the wax can be calculated based on the saponification value of the wax. For example, the saponification value divided by 1000 equals the number of grams of potassium hydroxide added per gram of wax.

[0114] This wax emulsion can be prepared using surfactants as nonionic emulsifiers. Surfactants (or nonionic emulsifiers) may include sorbitol monostearate, sorbitol isostearate, sorbitol laurate, sorbitol oleate, sorbitol palmitate, sorbitol sesquioleate, sorbitol monoisostearate ethoxylate, sorbitol monolaurate ethoxylate, sorbitol monooleate ethoxylate, sorbitol monopalmitate ethoxylate, sorbitol monostearate ethoxylate, sorbitol tetraoleate ethoxylate, sorbitol tetrastearate ethoxylate, sorbitol tristearate ethoxylate, sorbitol hexastearate ethoxylate, or combinations thereof. The nonionic emulsifier can be used in amounts from about 1.0% by weight to about 15.0% by weight, based on the total weight of the wax emulsion, which does not exceed 100% by weight.

[0115] Alternatively or additionally, the wax emulsion may be prepared using an ionic dispersant. The ionic dispersant may include polynaphthalene sulfonic acid, lignin sulfonate, sodium lignin sulfonate, calcium polynaphthalene sulfonate, or combinations thereof. The ionic dispersant may be used in an amount from about 0.1% by weight to about 20.0% by weight, based on the total weight of the emulsion.

[0116] In at least one embodiment, the wax emulsion comprises lignin sulfonate paraffin, such as sodium lignin sulfonate paraffin.

[0117] Wax emulsions can be prepared as follows: Water and water-soluble components are combined and then heated to a temperature between approximately 185°F (85°C) and approximately 205°F (96.1°C). A wax compound is incorporated and heated to a temperature between approximately 185°F (85°C) and approximately 205°F (96.1°C). The aqueous and wax mixtures are then combined. The resulting mixture is then placed in a homogenizer to achieve a distribution range of micelle diameters. This micelle diameter distribution can range from approximately 0.3 micrometers to approximately 1.5 micrometers, for example from approximately 0.4 micrometers to approximately 1 micrometer. This degree of homogenization can be obtained, for example, by using a dual-orifice homogenizer operating at approximately 3,000 psig to approximately 8,000 psig.

[0118] The wax emulsions useful in this article may possess a variety of properties. The emulsion is stable for at least one week, for example, at least one month, and for example, at least six months. The formed wax emulsion may have a pH of less than 12.5, for example, from about 8.0 to about 12.4. The wax emulsion may have a viscosity of from about 10 cps to about 50 cps, for example, from about 5 cps to about 20 cps. The average solid content of the wax emulsion may be from about 40% by weight to about 60% by weight.

[0119] The alkylphenol-phenol-aldehyde polymer composition can be combined with the wax emulsion using any suitable technique to form a resin composition. For example, the wax emulsion can be introduced together with the alkylphenol-phenol-aldehyde polymer composition under normal stirring conditions to form a resin composition as a blend or mixture.

[0120] The resin composition comprises an alkylphenol-phenol-aldehyde polymer composition, a wax emulsion, and one or more optional components. For the purposes of this disclosure, the weight % of each component in the resin composition described herein is based on a solids weight basis percentage (% solids weight basis). The total weight % of the resin composition described herein does not exceed 100% by weight.

[0121] The amount of alkylphenol-phenol-aldehyde polymer composition that may be contained in the resin composition may be from about 70% by weight to less than 100% by weight, for example, from about 70% by weight to about 99% by weight, from about 75% by weight to about 95% by weight, from about 80% by weight to about 90% by weight, from about 85% by weight to about 99% by weight, from about 85% by weight to about 95% by weight, or from about 85% by weight to about 90% by weight, although other amounts are also considered. Any of the above figures may be used alone to describe an open range or in combination to describe a closed range.

[0122] The amount of wax emulsion that may be contained in the resin composition may be greater than 0 wt% to about 30 wt%, for example, about 1 wt% to about 30 wt%, about 5 wt% to about 15 wt%, greater than 0 wt% to about 13 wt%, about 2 wt% to about 12 wt%, about 4 wt% to about 10 wt%, or about 6 wt% to about 8 wt%, although other amounts are also considered. Any of the above figures may be used alone to describe an open range or in combination to describe a closed range.

[0123] The resin compositions described herein can be one-component systems (1K systems) because polymerization does not occur before the application of a stimulant (e.g., heat). 1K systems already contain all the necessary components and are storage-stable. The resin compositions described herein are also considered suitable as storable components of 2K systems or other multi-component systems.

[0124] The resin composition described herein may be a curable resin composition. This curable resin composition may be a 1K system.

[0125] The aforementioned stoichiometric range of the components used to form the alkylphenol-phenol-aldehyde polymer allows for the formation of various types of polymer distributions and polydispersities to achieve desired molecular weight profiles, linkages, and functionalities. The hydrocarbon chain of the alkylphenol enhances water properties due to its hydrophobicity. The hydrocarbon chain of the alkylphenol also prevents the phenol-formaldehyde polymer from being washed out during steam application. The presence of the alkylphenol has also been observed to reduce surface tension, which allows for good resin distribution and polymer coverage of the substrate surface area.

[0126] In addition to the use of alkylphenols, this wax emulsion further enhances the water properties of the resin composition. Water in the resin solution slows down the curing rate due to the high energy and long time required to evaporate moisture during the very short press cycle time in application. To overcome the curing process and improve heat transfer, and in some embodiments, some of the water can be replaced with rheology modifiers (e.g., polyols such as glycerol, diethylene glycol, or ethylene glycol). These rheology modifiers can act as solvates the polymer solution in the same way as water during synthesis, while still achieving the desired molecular weight distribution. Rheology modifiers can also improve polymer flow and penetration into the substrate (e.g., lignocellulose substrate) for better bonding.

[0127] Uses and Products

[0128] Embodiments of this disclosure also relate to the use of the resin compositions described herein. The resin compositions described herein can be used as adhesives, binders, sealants, or coatings, and for other uses in a variety of applications, such as cellulose, lignocellulose, and wood products, including structural cellulose, lignocellulose, and wood products, materials, or composites. Such products, materials, and composites include, but are not limited to, oriented strand board (OSB), particleboard, fiberboard, medium-density fiberboard, building boards, composite boards, and plywood, although other applications are also considered. The resin compositions can be used in building construction or any suitable manufacture in which cellulose, lignocellulose, or wood products are used. The resin compositions are generally used in the production of composites, adhesives, insulating materials, molded products, bonding agents, laminates, and other articles and manufactured goods. Therefore, and in some embodiments, the articles comprise the resin compositions described herein; and cellulose or wood products, materials, or composites.

[0129] The following embodiments are provided to provide those skilled in the art with a complete disclosure and illustration of how to implement and use embodiments of this disclosure, and are not intended to limit the scope of embodiments of this disclosure. Efforts have been made to ensure the accuracy of the figures used, but some experimental errors and biases should be taken into account.

[0130] Example

[0131] Embodiments for preparing various alkylphenol-phenol-aldehyde polymers and mixing them with wax emulsions to form the resin compositions described herein. OSB pads formed and cured using the example resin compositions and commercial resins were evaluated. The inventors have discovered that cashew nut distillate can provide finished OSB pads with water resistance, moisture resistance, reduced surface tension, valuable wetting properties, and flexibility.

[0132] Evaluation of OSB samples

[0133] Internal bond strength was evaluated using the following procedure. After the OSB board was fabricated, a 2-inch x 2-inch sample specimen was cut from the OSB board and glued to both sides of the stainless steel block. The specimen was then pulled apart using a tensile testing instrument to measure the tensile bond strength. Internal bond strength was measured in pounds per square inch (psi).

[0134] Water absorption and thickness expansion were determined using the following procedure: Cut a 6-inch x 6-inch sample from the OSB plate. Measure the initial weight of the sample. Also measure the initial thickness on all four sides, 1 inch from the edge of the plate, using a micrometer. Place the sample in a temperature-controlled bath at 21°C for 24 hours, with the surface of the plate submerged 1 inch below the surface. After 24 hours, remove the sample and drain. Measure the final weight. Also measure the final thickness on all four sides, 1 inch from the edge of the plate, using a micrometer. Calculate the percentage water absorption (%WA) and percentage thickness expansion (%TS) using the following equations:

[0135] %WA = ((Final weight - Initial weight) / (Initial weight)) × 100

[0136] %TS = ((final thickness - initial thickness) / (initial thickness)) × 100

[0137] Durability (maximum momentum failure load) was determined using the following procedure: A 4.5-inch × 14-inch sample was cut from an OSB plate. The sample was immersed in a bath at 65°C and -15 mmHg for 30 minutes, followed by immersion at atmospheric pressure for 30 minutes. The sample was dried at 82°C until all moisture had evaporated. The maximum momentum failure load was measured. This test simulates the extreme humidity and moisture exposure of the OSB. Durability (maximum momentum failure load) was measured in pounds-force-inches (lbf·in).

[0138] Example 1: Alkylphenol-phenol-aldehyde polymer

[0139] Scheme 1 illustrates the addition reaction of the example. Typically, the reaction involves forming a mixture comprising phenol (A), cashew nut distillate (B), formaldehyde (C), and sodium hydroxide (NaOH), and heating the resulting mixture. Urea and / or polyols may also be present in the mixture. Cashew nut distillate (B) is monounsaturated cashew nut phenol (CAS No. 8007-24-7, 3-pentadeca-8-enylphenol), available from Palmer International (1500-1), as shown in Scheme 1.

[0140] Option 1

[0141]

[0142] Triunsaturated cashew phenol (CAS No. 37330-39-5) can also be used as shown in Scheme 1.

[0143]

[0144] Various reactions occur when the mixture is heated, such as hydroxymethylation (Scheme 2), pre-condensation reactions forming oligomers (Scheme 3), and condensation reactions forming large and very large polymer linkages (Scheme 4). Unless otherwise specified to the contrary or the context clearly indicates otherwise, references to the term "polymer" include references to "oligomer".

[0145] Scheme 2 illustrates the selected hydroxymethylation reaction to form the hydroxymethylation products of the examples. The reaction of phenol (A), cashew nut distillate (B), and formaldehyde (C) forms hydroxymethylated adducts (sodium monomethylolphenol and sodium monomethylolalkylphenol) (D) and (E). These hydroxymethylated products react with formaldehyde to form adducts (F) and (G) (sodium dimethylolphenol and sodium dimethylolalkylphenol, which also react with formaldehyde to form adducts (H) and (I) (sodium trimethylolphenol and sodium trimethylolalkylphenol). These adducts (D)-(I) contain hydroxymethylated phenol, which may constitute at least a portion of the compositions described herein. Although Scheme 2 shows the R group as a triunsaturated R group or a monounsaturated R group, diunsaturated R groups are also considered, as described herein.

[0146] Option 2

[0147]

[0148] Scheme 3 illustrates an illustrative but non-limiting example of an oligomer represented by formula (1-A)-(1-F) formed by a pre-condensation reaction on a mixture comprising, for example, one or more adducts (D)-(I). These oligomers represented by formula (1-A)-(1-F) (dimers, trimers, and tetramers), as well as other oligomers, may constitute at least a portion of the compositions described herein. In Scheme 3, R is the group shown in Scheme 2.

[0149] Option 3

[0150]

[0151] Scheme 4 illustrates illustrative but non-limiting examples of large and very large polymers represented by formula (2-A) formed by condensation reactions. These large and very large polymers represented by formula (2-A), as well as other large and very large polymers, may constitute at least a portion of the compositions described herein. In Scheme 4, R is the group shown in Scheme 2, and n is an integer from 1 to 20.

[0152] Option 4

[0153]

[0154] Example 2: Resin Composition of the Example

[0155] Table 3 shows a comparison of the surface tension of the alkylphenol-phenol-formaldehyde polymer composition used as an embodiment of this disclosure with that of a commercial phenol-formaldehyde polymer.

[0156] Table 3

[0157]

[0158] In summary, Table 3 shows that the presence of alkylphenols in phenol-formaldehyde polymers reduces surface tension, which allows for good resin distribution and surface area coverage of the polymer on substrates such as lignocellulose substrates.

[0159] The compositions of various examples are formed from a mixture of an alkylphenol-phenol-aldehyde polymer composition and a wax emulsion. The alkylphenol-phenol-aldehyde polymer is an alkylphenol-phenol-formaldehyde polymer (APFP) composition. These compositions are evaluated relative to a commercial phenol-formaldehyde resin (ME1021RC).

[0160] The example compositions are shown in Tables 4A and 4B and comprise APFP prepared with the listed components and a 10% lignin sulfonate wax emulsion. Example 1-1 comprises APFP prepared with about 1% cashew nut distillate (CND) and 0% glycerol. Example 1-2 comprises APFP prepared with about 10% CND and in the presence of about 8% glycerol. Example 1-3 comprises APFP prepared with about 1% CND and about 3.5% glycerol. Example 1-4 comprises high molecular weight APFP prepared without glycerol and with about 1% (CND). Example 1-5 comprises low molecular weight APFP prepared without glycerol and with about 4.8% (CND). When high CND levels are used as in Examples 1-5, the production of high molecular weight APFP can be limited due to the steric hindrance of the long hydrocarbon chains of alkylphenols. Example 1-6 comprises a blend of 70% (wt) high molecular weight APFP and 30% (wt) low molecular weight APFP. Solid content calculated according to ASTM D4426-01.

[0161] Table 4A

[0162]

[0163] Table 4B

[0164]

[0165] First, APFPs of various examples were prepared using the components shown in Tables 4A and 4B. Then, about 10% by weight of a lignin sulfonate wax emulsion was slowly added under normal stirring to ensure adequate dispersion in the APFPs. Regarding Examples 1-6, high molecular weight and low molecular weight APFPs were blended, and then a lignin sulfonate wax emulsion was slowly added under normal stirring to ensure adequate dispersion in the blend.

[0166] Table 5 shows the Mn, Mw, and Mz data for the selected APFPs in Examples 1-4, 1-5, and 1-6.

[0167] Table 5

[0168]

[0169] Figure 1A superposition of GPC chromatograms for the 70 / 30 blend (black), the high molecular weight APFP composition (blue), and the low molecular weight APFP composition (red) is shown. GPC chromatograms were collected using a UV detector. The chromatograms are presented in five sections: section (A) represents very large / large polymers, such as polymers represented by formula (2-A); section (B) represents medium-sized polymers; section (C) represents oligomers (dimers, trimers, and tetramers), such as oligomers represented by formulas (IA), (IC), and (IE); section (D) represents hydroxymethylated phenols, such as phenols represented by formulas (D), (E), (G), and (I); and section (E) represents phenol.

[0170] Figure 2 This is a bar chart showing the composition (in percent) of the components in the 70 / 30 blend, the high molecular weight APFP composition, and the low molecular weight APFP composition. Percentages are calculated based on elution retention time. As shown, the high molecular weight APFP composition contains approximately 87.3% very large polymer (VLP) / large polymer (LP), approximately 6.1% medium polymer, approximately 5.5% oligomer, and approximately 1.1% hydroxymethylated phenol and phenol. The low molecular weight APFP composition contains approximately 59.6% VLP and LP, approximately 17.2% medium polymer, approximately 18.5% oligomer, and approximately 4.9% hydroxymethylated phenol and phenol. The 70 / 30 blend has a composition between the two and contains approximately 76% VLP and LP, approximately 10.3% medium polymer, approximately 11.1% oligomer, and approximately 2.7% hydroxymethylated phenol and phenol.

[0171] Example 3: Manufacturing conditions for the example board

[0172] In a mixer, a lignocellulose substrate (poplar), a premixed resin / lignosulfonate wax emulsion, and wax are blended for top and bottom surface application. In a mixer, the lignocellulose substrate (poplar), polymethylene diphenyl diisocyanate (pMDI), and wax are blended for core application. After blending, a 24-inch x 24-inch oriented strand board (OSB) mat is formed, consisting of 30% top and bottom surfaces and 40% core on each side. This formed 24-inch x 24-inch mat is placed under a steam preheater press at a dew point of 92–95°C for 10 seconds, then transferred to the main press for final curing. Table 6 shows the selected parameters for OSB adhesive and wax application to the lignocellulose substrate, as well as the OSB pressing parameters.

[0173] Table 6

[0174]

[0175] Example 4: Applied Research

[0176] Several plate studies were completed. Selected results are shown in Tables 7A and 7B. Two polymers (Examples 1-3 and Examples 1-6) were evaluated relative to pMDI as a control. A commercial phenol-formaldehyde resin (ME1021RC) was used as a comparative example (C.Ex.). Examples 1-3 were low-alkalinity, low-CND, and moderately condensed molecular weight polymers synthesized with a rheology modifier (glycerol). Examples 1-6 were blends of 70% high-alkalinity, low-CND, and highly condensed molecular weight polymers with 30% high-alkalinity, high-CND, and moderately condensed molecular weight polymers. OSB pads were prepared as described above. In Tables 7A and 7B, “SP%” refers to the rate of application of adhesive or wax on a wood substrate. The percentage of water absorption (%WA), percentage of thickness swelling (%TS), internal bond strength, and durability (maximum momentum failure load) were determined as described above. Group 1 shows a comparative example of 100% pMDI and conventional commercial phenolic resin. Group 2 shows a comparative example of 100% pMDI and a low-basic, low-CND, and moderately condensed molecular weight polymer synthesized with a rheology modifier (glycerol). Group 3 shows a comparative example of blends of 100% pMDI and 70% high-basic, low-CND, and highly condensed molecular weight polymers versus 30% high-basic, high-CND, and moderately condensed molecular weight polymers. Groups 4-6 are repeat studies of Group 3 to validate the results.

[0177] Table 7A

[0178]

[0179] Table 7B

[0180]

[0181] In Group 1, conventional commercial phenolic resins were significantly inferior to pMDI in all properties. In Group 2, improved performance was observed in alkylphenol-phenol-aldehyde resin emulsions with lignin sulfonate waxes compared to conventional commercial phenolic resins. In Group 3, alkylphenol-phenol-aldehyde resin emulsions with lignin sulfonate waxes achieved properties comparable to pMDI in terms of internal bond strength, 24-hour thickness expansion (%), and durability. Groups 4-6 were repeat studies of Group 3 to validate the results.

[0182] Groups 3-6 consist of two blended resin systems, each composed of 70% very high-development molecular weight polymers and 30% medium-development polymers with a very diverse molecular weight distribution. These blended resin systems achieve rapid curing through the highly condensed polymer major component and reactivity through the medium-condensed polymer minor component. Alkylphenol levels are also increased by blending the two resin systems without affecting the degree of condensation, resulting in hydrophobicity and improved water properties. Group 2 lacks the diversity in polymer molecular weight distribution.

[0183] Example 5: Air and Moisture Barrier OSB

[0184] Air and moisture barrier oriented strand board (OSB) can be used in conjunction with an integrated water-resistant paper overlay for wall and roof applications. For these applications, the water properties of the final product (e.g., 24-hour water absorption rate and thickness expansion) are relevant.

[0185] The various example compositions are formed from a mixture of an alkylphenol-phenol-aldehyde polymer composition and a wax emulsion. The alkylphenol-phenol-aldehyde polymer is an APFP composition. These example compositions are evaluated relative to commercial phenol-formaldehyde resins. Table 8 shows the example compositions and controls made from commercial phenolic polymers. In Table 8, Example 8-1 contains Example APFP, Example 8-2 contains a commercial phenolic polymer, and Example 8-3 contains a 50 / 50 blend of the APFP polymer (Example 8-1) and the commercial phenolic polymer (Example 8-2). Example 8-4 is a control (wax-free) containing a commercial phenolic polymer. Solid content is calculated according to ASTM D4426-01.

[0186] Table 8

[0187]

[0188] First, the APFP of Examples and the comparative phenolic polymer were prepared using the components shown in Table 8. The APFP of Examples, the comparative phenolic polymer, and their 50 / 50 blends were each mixed with approximately 7% by weight of a lignin sulfonate wax emulsion, added slowly under normal stirring to ensure adequate dispersion in the polymer. No wax emulsion was added to Examples 8-4.

[0189] Table 9 shows the Mn, Mw, and Mz data for the selected APFPs in Examples 8-1, 8-2, 8-3, and 8-4.

[0190] Table 9

[0191]

[0192] In a mixer, a lignocellulose matrix (Southern Yellow Pine), a premixed resin / lignosulfonate wax emulsion, and wax were blended for top and bottom surface application. In a mixer, the lignocellulose matrix, polymeric methylene diphenyl diisocyanate (pMDI), and wax were blended for core application. After blending, a 24-inch x 24-inch oriented strand board (OSB) mat was formed, consisting of 32.5% top and bottom surfaces and 35% core on each side. This formed 24-inch x 24-inch mat was placed under a press at 226°C to achieve a target thickness of 0.4375 inches and pressed for 60 seconds to cure. Table 10 shows the selected parameters for OSB adhesive and wax application to the lignocellulose matrix, as well as the OSB pressing parameters.

[0193] Table 10

[0194]

[0195] Several board studies were completed. Selected results are shown in Table 11. Examples 8-3 comprise 50 / 50 blends of APFP polymer (Example 8-1) and a commercial phenolic polymer (Example 8-2). APFP (Example 8-3) was evaluated relative to pMDI as a control. Example 8-4 is a control (wax-free) comprising a commercial phenolic polymer. OSB pads were prepared as described above. In Table 11, “SP%” refers to the rate of adhesive or wax application on the wood substrate. The percentage of water absorption (%WA) and percentage of thickness swelling (%TS) were determined as described above.

[0196] Table 11

[0197]

[0198] OSB prepared using the resins of Examples 8-3 was determined to have similar properties to pMDI in terms of water absorption % and 24-hour thickness swelling %; however, the thickness swelling % was improved relative to pMDI. OSB prepared using the resins of Examples 8-3 was determined to be significantly superior to the conventional phenolic polymer resins of Examples 8-4 in both water absorption % and 24-hour thickness swelling %. Overall, the data indicate that resin compositions comprising phenolic resin, APFP polymer, and wax emulsion can be used in moisture barrier applications without compromising the water properties of the final board.

[0199] Embodiments of this disclosure generally relate to phenolic resin compositions, methods of preparing them, and their uses. As described herein, the alkylphenol-phenol-aldehyde polymers of the compositions disclosed may be designed to have specific molecular weight profiles for use in continuous steam application processes. In some embodiments, this may mean reducing the majority of smaller molecular weights to hydroxymethylated phenols and increasing oligomers and medium-sized polymers as well as large and very large polymers with moderate development. Also as described herein, wax emulsions may be blended with the polymers to improve water properties without affecting the bonding and durability of the finished board. Furthermore, rheology modifiers may be incorporated to partially replace formulation water to increase solids for better heat transfer during board manufacturing and also to improve resin flow and penetration when applied to a substrate.

[0200] Combinations of monomer substitution, molecular weight distribution, and chemical additives can be used to overcome the effects of steam on the curing of phenolic resins without sacrificing production time or final board performance. Replacing a portion of phenol with alkylphenols can help achieve the desired molecular weight distribution. The alkyl chains provided by alkylphenols are inherently hydrophobic and contribute hydrophobicity and flexibility to the finished resin. The molecular weight distribution of the polymer can be controlled by the order of reactant addition and condensation methods, resulting in fewer low molecular weight varieties, which may be detrimental to the resin's performance under steam preheating conditions. The addition of wax emulsions is used to further improve moisture resistance. The use of specific surfactants helps control the distribution and penetration of the resin onto wood substrates.

[0201] The resin compositions described herein can have high solids content, high alkalinity, high molecular weight, or combinations thereof. Such properties allow for faster curing speeds than conventional phenolic resins. Furthermore, lignocellulose composites manufactured using the resin compositions described herein exhibit improved mechanical properties compared to conventional techniques. In addition, this resin composition can produce lignocellulose composite products with excellent water absorption and thickness swelling test results, making these composite products more water-resistant and durable than conventional composite products.

[0202] Implementation Plan List

[0203] This disclosure provides for the following and other aspects, each of which may be considered to optionally include any alternative implementation:

[0204] Clause 1. A resin composition comprising:

[0205] Wax emulsions; and

[0206] A polymer composition comprising an alkylphenol-phenol-aldehyde polymer, the alkylphenol-phenol-aldehyde polymer comprising:

[0207] An alkylphenol monomer unit, represented by formula (I):

[0208]

[0209] Wherein R is an unsubstituted hydrocarbon group having 1-40 carbon atoms or a substituted hydrocarbon group having 1-40 carbon atoms; and

[0210] Phenolic compound comonomer unit.

[0211] Clause 2. The resin composition of Clause 1, wherein: the alkylphenol monomer unit comprises cashew phenol, cresol, xylenol, ethylphenol, alkylresorcinol, isomers thereof, or combinations thereof; and the phenolic compound comonomer unit comprises phenol, resorcinol, or combinations thereof.

[0212] Clause 3. The resin composition of Clause 1 or Clause 2, wherein the wax emulsion comprises: petroleum-based wax, coal-derived wax, synthetic wax, bio-based wax or a combination thereof; and an emulsifier comprising alkali metal hydroxides, surfactants, ionic dispersants or a combination thereof.

[0213] Clause 4. The resin composition of any one of Clauses 1-3, wherein the wax emulsion comprises lignin sulfonate porous paraffin.

[0214] Clause 5. A resin composition of any one of Clauses 1-4, wherein: R in formula (I) is meta-positioned relative to a hydroxyl (-OH) group; and R in formula (I) is C 15 H 30-n And n is 0, 2, 4 or 6.

[0215] Clause 6. A resin composition of any one of Clauses 1-5, wherein the alkylphenol-phenol-aldehyde polymer comprises: a high molecular weight component and a low molecular weight component; a high molecular weight component of about 50% to about 90% based on the total percentage of very large polymers, large polymers, medium polymers, oligomers, hydroxymethylated phenols and phenols present in the alkylphenol-phenol-aldehyde polymer, the total percentage not exceeding 100%; and a low molecular weight component of about 1% to about 20% based on the total percentage.

[0216] Clause 7. The resin composition of any one of Clauses 1-6, wherein the alkylphenol-phenol-aldehyde polymer has: a number-average molecular weight (Mn) of about 200 g / mol to about 800 g / mol; a weight-average molecular weight (Mw) of about 20,000 g / mol to about 40,000 g / mol; and a z-average molecular weight (Mz) of about 200,000 g / mol to about 300,000 g / mol.

[0217] Clause 8. A resin composition of any one of Clauses 1-7, wherein the alkylphenol-phenol-aldehyde polymer comprises: an alkylphenol monomer unit of greater than 0% to about 12% by weight based on the total weight% of the alkylphenol monomer unit and the phenolic compound comonomer unit, wherein the total weight% of the alkylphenol monomer unit and the phenolic compound comonomer unit does not exceed 100% by weight; and a phenolic monomer unit of about 88% to less than 100% by weight based on the total weight% of the alkylphenol monomer unit and the phenolic compound comonomer unit.

[0218] Clause 9. The resin composition of any one of Clauses 1-8 further comprises a rheology modifier, a surfactant, or a combination thereof.

[0219] Clause 10. The resin composition of Clause 9, wherein the rheology modifier comprises a polyol.

[0220] Clause 11. The resin composition of Clause 10, wherein the polyol comprises glycerol, crude glycerol, refined glycerol, ethylene glycol, diethylene glycol, propylene glycol, propane-1,2,3-triol, glycerol, 1,2,3-trihydroxypropane, 1,2,3-propanetriol, or a combination thereof.

[0221] Clause 12. The resin composition of Clause 10 or Clause 11, wherein the polyol comprises glycerol.

[0222] Clause 13. The resin composition of any one of Clauses 1-12 further comprises water.

[0223] Clause 14. A resin composition of any one of Clauses 1-13, wherein the resin composition comprises: about 70% by weight or more of the alkylphenol-phenol-aldehyde polymer based on the total weight % of the resin composition, the total weight % of the resin composition not exceeding 100% by weight; and the wax emulsion of greater than 0% by weight to about 30% by weight based on the total weight % of the resin composition.

[0224] Clause 15. A resin composition of any one of Clauses 1-14, wherein the resin composition comprises: a wax emulsion of greater than 0% by weight to about 13% by weight based on the total weight% of the resin composition.

[0225] Clause 16. A resin composition comprising:

[0226] Wax emulsions; and

[0227] A polymer composition comprising a condensation product of a reaction mixture comprising: an alkylphenol compound; a phenolic compound; an aldehyde; a base; a polyol; and a solvent.

[0228] Clause 17. The resin composition of Clause 16, wherein the resin composition comprises a wax emulsion of greater than 0% by weight to about 13% by weight based on the total weight of the resin composition.

[0229] Clause 18. The resin composition of Clause 16 or Clause 17, wherein the polymer composition comprises: from about 10% to about 25% by weight of the alkylphenol compound plus the phenol compound, based on the total weight% of the polymer composition, wherein the total weight% of the polymer composition does not exceed 100% by weight; from about 5% to about 10% by weight of the aldehyde, based on the total weight% of the polymer composition; from about 2.5% to about 8% by weight of the base, based on the total weight% of the polymer composition; from more than 0% to about 12% by weight of the polyol, based on the total weight% of the polymer composition; and from about 45% to about 58% by weight of the solvent, based on the total weight% of the polymer composition.

[0230] Clause 19. A resin composition of any one of Clauses 17-19, wherein the alkylphenol-phenol-aldehyde polymer comprises: more than 0% to about 12% by weight of the alkylphenol compound based on the total weight percentage of the alkylphenol compound and the phenol compound, wherein the total weight percentage of the alkylphenol compound and the phenol compound does not exceed 100% by weight; about 88% to less than 100% by weight of the phenol compound based on the total weight percentage of the alkylphenol compound and the phenol compound; the molar ratio of the aldehyde to the total amount of the alkylphenol compound plus the phenol compound is about 2:1 to about 2.6:1; or a combination thereof.

[0231] Clause 20. A curable resin composition comprising:

[0232] The wax emulsions described herein; and

[0233] The reaction products of the following substances are: phenolic compounds; formaldehyde; and alkylphenols having 1-40 carbon atoms in the alkyl group of the alkylphenol, wherein the molar ratio of the formaldehyde to the total amount of the phenol and the alkylphenol is about 2:1 to about 2.6:1.

[0234] Clause 21. The curable resin composition of claim 16, wherein: the alkylphenol comprises cashew phenol, cresol, xylenol, ethylphenol, alkylresorcinol, isomers thereof, or combinations thereof; and the phenolic compound comprises phenol, resorcinol, or combinations thereof.

[0235] Clause 22. Manufactured articles, comprising:

[0236] Lignocellulose substrate; and

[0237] A resin composition comprising:

[0238] The alkylphenol-phenol-aldehyde polymer described herein;

[0239] The polyols described in this article; and

[0240] The wax emulsion described in this article.

[0241] Clause 23. A resin composition comprising:

[0242] The lignin sulfonate wax emulsion described in this article;

[0243] The phenolic resin described herein; and

[0244] Polymer compositions comprising the alkylphenol-phenol-aldehyde polymers described herein.

[0245] Clause 24. Manufactured articles, including:

[0246] The lignocellulose substrates described herein; and

[0247] A resin composition comprising:

[0248] The alkylphenol-phenol-aldehyde polymer described herein;

[0249] The phenolic resin described herein; and

[0250] The wax emulsion described in this article.

[0251] As can be seen from the foregoing general description and specific aspects, while the forms of the described aspects have been illustrated and described, various modifications may be made without departing from the spirit and scope of this disclosure. Therefore, this disclosure is not intended to be limited thereto. Similarly, the term "comprising" is considered synonymous with the term "including." Likewise, whenever the transitional phrase "comprising" is used before a composition, element, or group of elements, it should be understood that we also consider it to be the same composition or group of elements for which the transitional phrases "consistently composed of," "composed of," "selected from," or "is" are used before stating the composition, element, or groups of elements, and vice versa; for example, the terms "comprising," "consistently composed of," or "composed of" also include the product of a combination of elements listed after the term.

[0252] For the purposes of this disclosure, and unless otherwise specified, all numerical values ​​in this detailed description and the claims herein are values ​​indicated by the words “about” or “approximately”, and take into account experimental errors and biases as would be expected by those skilled in the art. For the sake of brevity, only certain ranges are explicitly disclosed herein. However, any lower limit may be combined with any upper limit to describe a range not explicitly stated, and any lower limit may be combined with any other lower limit to describe a range not explicitly stated, just as any upper limit may be combined with any other upper limit to describe a range not explicitly stated. Furthermore, a range includes each point or individual value between its endpoints, even if not explicitly stated. Thus, each point or individual value may be used as its own lower or upper limit combined with any other point or individual value or any other lower or upper limit to describe a range not explicitly stated.

[0253] As used herein, the indefinite articles “a” or “an” mean “at least one…” unless otherwise specified or the context clearly indicates otherwise. For example, an aspect containing “polymer composition” includes an aspect containing one, two or more polymer compositions, unless otherwise specified or the context clearly indicates that it contains only one polymer composition.

[0254] Although the foregoing addresses aspects of this disclosure, other and further aspects of this disclosure may be devised without departing from its essential scope, which is defined by the appended claims.

Claims

1. A resin composition comprising: Wax emulsions; and A polymer composition comprising an alkylphenol-phenol-aldehyde polymer, the alkylphenol-phenol-aldehyde polymer comprising: An alkylphenol monomer unit, represented by formula (I): Wherein R is an unsubstituted hydrocarbon group having 1-40 carbon atoms or a substituted hydrocarbon group having 1-40 carbon atoms; and Phenolic compound comonomer unit.

2. The resin composition of claim 1, wherein: The alkylphenol monomer unit includes cashew phenol, cresol, xylenol, ethylphenol, alkylresorcinol, its isomers, or combinations thereof; and The phenolic compound comonomer unit includes phenol, resorcinol, or a combination thereof.

3. The resin composition of any one of claims 1 or 2, wherein the wax emulsion comprises: Petroleum-based waxes, coal-derived waxes, synthetic waxes, bio-based waxes, or combinations thereof; and Emulsifiers, including alkali metal hydroxides, surfactants, ionic dispersants, or combinations thereof.

4. The resin composition of any one of claims 1-3, wherein the wax emulsion comprises lignin sulfonate porous paraffin.

5. The resin composition according to any one of claims 1-4, wherein: In formula (I), R is meta-positioned relative to the hydroxyl (-OH) group; and In equation (I), R is C 15 H 30-n , where n is 0, 2, 4 or 6.

6. The resin composition of any one of claims 1-5, wherein the alkylphenol-phenol-aldehyde polymer comprises: High molecular weight components and low molecular weight components; Based on the total percentage of high molecular weight components in the alkylphenol-phenol-aldehyde polymer, which is approximately 50% to approximately 90% of very large polymers, large polymers, medium polymers, oligomers, hydroxymethylated phenols, and phenols, and this total percentage does not exceed 100%; and Based on this total percentage, approximately 1% to approximately 20% of the low molecular weight components.

7. The resin composition of any one of claims 1-6, wherein the alkylphenol-phenol-aldehyde polymer comprises: The number-average molecular weight (Mn) is approximately 200 g / mol to approximately 800 g / mol; The weight-average molecular weight (Mw) is approximately 20,000 g / mol to approximately 40,000 g / mol; and The z-average molecular weight is approximately 200,000 g / mol to approximately 300,000 g / mol.

8. The resin composition of any one of claims 1-7, wherein the alkylphenol-phenol-aldehyde polymer comprises: Based on the total weight percentage of the alkylphenol monomer unit and the phenolic compound comonomer unit, the alkylphenol monomer unit comprises greater than 0% to about 12% by weight, and the total weight percentage of the alkylphenol monomer unit and the phenolic compound comonomer unit does not exceed 100% by weight; and The phenol monomer unit comprises approximately 88% to less than 100% by weight of the total weight of the alkylphenol monomer unit and the phenolic compound comonomer unit.

9. The resin composition of any one of claims 1-8, further comprising a rheology modifier, a surfactant, or a combination thereof.

10. The resin composition of claim 9, wherein the rheology modifier comprises a polyol.

11. The resin composition of claim 10, wherein the polyol comprises glycerol, crude glycerol, refined glycerol, ethylene glycol, diethylene glycol, propylene glycol, propane-1,2,3-triol, glycerol, 1,2,3-trihydroxypropane, 1,2,3-propanetriol, or a combination thereof.

12. The resin composition of claim 10, wherein the polyol comprises glycerol.

13. The resin composition of any one of claims 1-12, further comprising water.

14. The resin composition of any one of claims 1-13, wherein the resin composition comprises: Based on the total weight percentage of the resin composition, approximately 70% by weight or more of the alkylphenol-phenol-aldehyde polymer, wherein the total weight percentage of the resin composition does not exceed 100% by weight; and The wax emulsion comprises more than 0% by weight to about 30% by weight based on the total weight of the resin composition.

15. The resin composition of any one of claims 1-14, wherein the resin composition comprises: The wax emulsion comprises more than 0% by weight to about 13% by weight based on the total weight of the resin composition.

16. A curable resin composition comprising: Wax emulsions; and The reaction products of the following substances: Phenolic compounds; Formaldehyde; and Alkylphenol, wherein the alkyl group of the alkylphenol has 1-40 carbon atoms. in: The molar ratio of formaldehyde to the total amount of phenol and alkylphenol is about 2:1 to about 2.6:

1.

17. The curable resin composition of claim 16, wherein: The alkylphenols include cashew phenol, cresol, xylenol, ethylphenol, alkylresorcinol, their isomers, or combinations thereof; and The phenolic compounds include phenol, resorcinol, or combinations thereof.

18. Manufactured articles, including: Lignocellulose substrate; and A resin composition comprising: Alkylphenol-phenol-aldehyde polymers; Polyols; and Wax emulsion.

19. A resin composition comprising: Lignosulfonate wax emulsion; Phenolic resin; and Polymer compositions comprising alkylphenol-phenol-aldehyde polymers.

20. Manufactured articles, including: Lignocellulose substrate; and A resin composition comprising: Alkylphenol-phenol-aldehyde polymers; Phenolic resin; and Wax emulsion.

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