Process for forming epoxy resin composition and separation process

Abstract

Embodiments of the present disclosure generally relate to processes for forming epoxy resin compositions and processes for separating substrates from complex mixtures. In one embodiment, a process for preparing an epoxy resin composition is provided and includes: reacting a mixture comprising a substrate, an epihalohydrin, and a catalyst to form a first composition comprising a halohydrin reaction product; introducing an alkaline agent with the first composition to form a second composition comprising an epoxy resin product; introducing a liquid epoxy resin together with the second composition to form a resin mixture; and removing unreacted epihalohydrin from the resin mixture to form the epoxy resin composition. In another embodiment, a process for separating a substrate from a substrate source is provided and includes introducing an epihalohydrin with the substrate source comprising the substrate, the substrate comprising at least one hydroxyl group, and separating the epihalohydrin and the substrate from the substrate source.

Description

[0001] Cross-related related applications

[0002] This application claims priority to U.S. non-provisional patent application No. 18 / 130,876, filed on April 4, 2023, and U.S. non-provisional patent application No. 18 / 130,883, filed on April 4, 2023, each of which is incorporated herein by reference in its entirety. Technical Field

[0003] Embodiments of the present disclosure generally relate to processes for forming epoxy resin compositions and processes for separating substrates from complex mixtures. Background Art

[0004] The synthesis of epoxy resins, such as liquid epoxy resin (LER) compositions and solid epoxy resin (SER) compositions, involves a two-step reaction to convert a hydroxyl-containing substrate (e.g., a phenolic substrate) or an amine-containing substrate into a product mixture comprising a glycidylation product using, for example, epichlorohydrin (ECH). The product mixture is discharged from a reactor and transferred to a separate reactor for post-processing. The product mixture is subjected to a post-processing process to remove salts formed during glycidylation, remove excess ECH, and convert the halohydrin reaction product into the desired glycidylation product. Problems arise when conventional post-processing processes are applied to non-conventional substrates, such as alcohols of biological origin (e.g., phenols), alcohols present in epoxy resin recycle streams, and alcohols present in phenolic resin recycle streams. For example, when glycidylation is performed on non-conventional substrates, the resulting product mixture is, for example, insoluble in the solvent used for the post-processing process. Furthermore, the product mixture is too viscous to be discharged or removed from the glycidylation reactor and transferred to a reactor for post-processing. Even if the product mixture is not transferred to a different reactor, the halohydrin reaction product present in the product mixture cannot be converted to the desired glycidyl ether because the halohydrin reaction product is insoluble in the solvent used for the conversion.

[0005] Furthermore, non-conventional substrates are often derived from unpurified waste streams or are crude raw materials. For example, bio-derived alcohols can be derived from lignin waste streams, and alcohols present in epoxy or phenolic resins can be derived from recycled epoxy and phenolic resins, respectively. In each case, the hydroxyl-containing substrate to be converted into the desired glycidyl ether is present in a complex composition. Conventionally, waste streams are purified by some form of fractionation or depolymerization before glycidylation is attempted. The solvents utilized in the fractionation and depolymerization are not carried over into the downstream glycidylation process, but are instead recycled or discarded. Such additional steps, in addition to the solvent, increase process complexity and cost, making the use of waste streams for glycidylation commercially unattractive.

[0006] Therefore, there is a need for new and improved processes for forming epoxy resin compositions. There is also a need for new and improved processes for separating substrates from raw materials and recycle streams. Summary of the Invention

[0007] Embodiments of the present disclosure generally relate to processes for forming epoxy resin compositions. Unlike conventional techniques, the embodiments described herein can be used to form epoxy resin compositions from, for example, bio-based substrates (bio-derived alcohols), alcohols present in resin recycle streams (such as epoxy resin waste streams and phenolic resin waste streams), or combinations thereof.

[0008] Embodiments of the present disclosure also relate to processes for separating substrates (such as substrates used for glycidylation reactions) from complex mixtures (such as feedstocks, waste streams, or recycle streams, as well as other complex mixtures). Unlike conventional techniques for separating glycidylation substrates (alcohols) from complex mixtures, the embodiments described herein can reduce resin production costs by, for example, using epihalohydrins as extraction solvents.

[0009] In one embodiment, a process for forming an epoxy resin composition is provided. The process includes reacting a mixture comprising a substrate containing at least one hydroxyl group, an epihalohydrin, and a catalyst to form a first composition comprising a halohydrin reaction product. The process further includes introducing an alkaline agent together with the first composition to form a second composition comprising an epoxy resin product, a residual halohydrin reaction product, and a salt. The process further includes introducing a liquid epoxy resin together with the second composition to form a liquid resin mixture; and removing unreacted epihalohydrin from the liquid resin mixture to form an epoxy resin composition.

[0010] In another embodiment, a process for preparing a liquid epoxy resin composition is provided. The process includes reacting a mixture comprising a bio-derived alcohol, an epihalohydrin, and a catalyst to form a first composition comprising a halohydrin reaction product. The process further includes introducing an alkaline reagent together with the first composition to form a second composition comprising a glycidylation product, a residual halohydrin reaction product, and a salt; introducing a liquid epoxy resin together with the second composition to form a liquid resin mixture; and removing unreacted epihalohydrin from the liquid resin mixture. The process further includes separating the salt from the liquid resin mixture. After separating the salt from the liquid resin mixture, the process further includes forming a liquid epoxy resin composition by the following steps: converting at least a portion of the residual halohydrin reaction product in the liquid resin mixture into an epoxy resin; and performing liquid-liquid separation on the liquid resin mixture; or a combination thereof.

[0011] In another embodiment, a process for converting a substrate into a liquid epoxy resin composition is provided. The process includes reacting a mixture comprising a substrate, an epihalohydrin, and a catalyst to form a first composition comprising a halohydrin reaction product and a salt, the substrate comprising a bio-derived alcohol, an alcohol present in a resin waste stream, an alcohol present in a resin recycle stream, or a combination thereof. The process further includes introducing an alkaline reagent with the first composition to form a second composition comprising a glycidylation product, a residual halohydrin reaction product, and a salt; and introducing a liquid epoxy resin with the second composition to form a liquid resin mixture having a viscosity of about 15 Pa·s or less at 25°C. The process further includes removing unreacted epihalohydrin from the liquid resin mixture; and separating the salt from the liquid resin mixture to form the liquid epoxy resin composition.

[0012] In another embodiment, a process is provided that includes introducing an epihalohydrin along with a substrate source comprising a substrate, the substrate comprising at least one hydroxyl group; and separating the epihalohydrin and the substrate from the substrate source.

[0013] In another embodiment, a process is provided that includes introducing an acid solution and an epihalohydrin along with a substrate source comprising a substrate, the substrate comprising at least one hydroxyl group; and separating the epihalohydrin and the substrate from the substrate source.

[0014] In another embodiment, a process for preparing an epoxy resin composition is provided. The process includes introducing a first epihalohydrin along with a substrate source, the substrate source comprising a substrate comprising at least one hydroxyl group; separating at least a portion of the first epihalohydrin and the substrate from the substrate source; and converting the substrate into the epoxy resin composition. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] In order that the above-mentioned features of the present disclosure may be understood in detail, a more particular description of the present disclosure may be given by reference to embodiments, as briefly summarized above, some of which are illustrated in the accompanying drawings. It should be noted, however, that the drawings illustrate only exemplary embodiments and are not to be considered limiting of its scope, which may admit to other equally effective embodiments.

[0016] Figure 1 A flow chart illustrating a conventional process for forming an epoxy resin composition is shown.

[0017] Figure 2 A flow chart illustrating a process for forming an epoxy resin composition according to at least one embodiment of the present disclosure.

[0018] Figure 3 is a flow chart showing selected operations of a process for forming an epoxy resin composition according to at least one embodiment of the present disclosure.

[0019] Figure 4 A flow chart illustrating selected operations of a process for separating a substrate from a substrate source in accordance with at least one embodiment of the present disclosure.

[0020] Figure 5 A flow chart illustrating selected operations of a process for separating a substrate from a substrate source in accordance with at least one embodiment of the present disclosure.

[0021] The drawings included herein illustrate various embodiments of the disclosure. It is contemplated that elements and features of one embodiment may be beneficially incorporated in other embodiments without further recitation. DETAILED DESCRIPTION

[0022] Embodiments of the present disclosure generally relate to processes for forming epoxy resin compositions. Embodiments of the present disclosure also relate to processes for separating substrates from complex mixtures.

[0023] Unlike conventional techniques, embodiments described herein can be used to form epoxy resin compositions from, for example, bio-based substrates (alcohols of biological origin), and alcohols present in resin recycle streams (such as epoxy resin waste streams and phenolic resin waste streams), or combinations thereof. Such alcohols can include phenols and aliphatic alcohols and other. In addition, embodiments described herein can be used together with existing production facilities without the need to transform such production facilities. The embodiments of the present disclosure can achieve simple and effective glycidylation of non-conventional substrates with excellent post-processing efficiency. In addition, embodiments described herein can reduce the production cost of bio-based resin compositions and avoid reactor shutdown due to cleaning.

[0024] Embodiments of the present disclosure also relate to processes for separating substrates (such as substrates for glycidylation reactions) from complex mixtures (such as feedstock, waste streams or recycle streams, and other complex mixtures). Unlike conventional techniques for separating glycidylation substrates (alcohols) from complex mixtures, the embodiments described herein can reduce resin production costs by, for example, using epihalohydrins as solvents.

[0025] Headings are used for convenience only and do not limit the scope of the disclosure.The embodiments described herein can be combined with other embodiments.

[0026] As used herein, a "composition" can include a component of the composition, the reaction product of two or more components of the composition, a balance of remaining starting components, or a combination thereof. The compositions of the present disclosure can be prepared by any suitable mixing process.

[0027] As described above, conventional processes for forming epoxy resin compositions from non-conventional substrates, such as alcohols of biosource (e.g., biosourced polyphenols) or alcohols present in a recycle stream containing epoxy or phenolic resins, fail or are inefficient. Such failure and inefficiency may be due to the high viscosity and insolubility of the product mixture formed from glycidylation. For example, conventional processing after removal of salts, excess ECH, and glycidylation byproducts is performed using methyl isobutyl ketone (MIBK), toluene, xylene, methylene chloride, hexane, or methylethyl ketone (MEK). When the glycidylation reaction is performed on non-conventional substrates, such as alcohols, phenols, polyols, and polyphenols of biosource or present in a recycle stream, these solvents are unable to dissolve the product mixture of the glycidylation reaction.

[0028] As used herein, a substrate comprising at least one alcohol (biologically derived alcohol, alcohol present in a waste stream, alcohol present in a recycle stream, and others) is a reactant of a reaction.

[0029] As used herein, "phenolic substrate" and "polyphenol" are used interchangeably such that a description of one includes a description of the other. For example, a description of a polyphenol includes both "polyphenol" and "phenolic substrate."

[0030] Biosourced alcohols and alcohols present in recycle streams are compounds that have at least one hydroxyl group (-OH) present in the compound. The at least one hydroxyl group can be present as a phenolic hydroxyl group, a hydroxyl group attached to a non-aromatic carbon (such as an alkyl hydroxyl group), or a combination thereof. Biosourced alcohols and alcohols present in recycle streams can include polyols (compounds containing more than one alcohol), polyphenols (compounds containing more than one phenol), combinations thereof, and others.

[0031] Figure 1A flow chart illustrating a conventional process for forming an epoxy resin composition is provided. Conventional process 100 includes a reaction subprocess 105 and a post-process 115 occurring in separate units. Reaction subprocess 105 and post-process 115 may occur in the same unit. Reaction subprocess 105 is a glycidylation reaction. Reaction subprocess 105 is coupled to post-process 115 as indicated by line 110. Reaction subprocess 105 includes reacting a substrate (such as bisphenol) with an epihalohydrin in the presence of a catalyst to form a product mixture including a glycidylation product. Reaction subprocess 105 includes a coupling reaction of epihalohydrin and bisphenol to form a halohydrin reaction product (intermediate substance). Reaction subprocess 105 also includes a closed loop reaction of the halohydrin reaction product to form a glycidylation product. Sometimes, a small portion of the halohydrin reaction product remains in the product mixture including the glycidylation product. This residual halohydrin reaction product may be converted into a glycidylation product during post-process 115. Once the reaction is considered complete in the reaction sub-process 105, the epihalohydrin is removed and the product mixture is transferred to a post-process 115 via line 110. The post-process 115 comprises removing salt and brine by phase separation using an organic solvent such as methyl isobutylketone (MIBK), toluene, xylene, methylene chloride, hexane or methyl ethyl ketone (MEK) and other solvents. The organic phase with the reaction product and the intermediate substance (e.g., the halohydrin reaction product) then undergoes another closed loop reaction, wherein the intermediate substance can be converted into the desired glycidyl product. Salt and brine can be removed, and residual organic solvent and water can be removed to form an epoxy resin composition.

[0032] When non-conventional substrates (such as bio-derived alcohols, bio-derived phenols, alcohols present in a recycle stream containing epoxy or phenolic resins, phenols present in a recycle stream containing epoxy or phenolic resins, or combinations thereof) are used in conventional process 100, problems arise (as indicated by the "dashed X" along line 110). For example, when certain non-conventional substrates undergo a reaction sub-process, the product mixture exiting line 110 is insoluble in the organic solvent, too viscous to be used for further processing, or too viscous to be removed from the coupling unit and fed to a post-processing unit, among other problems. Overall, conventional process 100 is at least unsuitable for non-conventional substrates.

[0033] The present inventors have found that adding a liquid epoxy resin to the product mixture formed by glycidylation facilitates the post-processing process. Figure 2A flow chart illustrating a process 200 for forming an epoxy resin composition according to at least one embodiment of the present disclosure is provided. Unlike conventional processes for forming epoxy resin compositions, process 200 and embodiments of the process described herein are capable of using non-conventional substrates (such as bio-derived alcohols, bio-derived phenols, alcohols present in a recycle stream containing an epoxy or phenolic resin, phenols present in a recycle stream containing an epoxy or phenolic resin, or combinations thereof, among others). Conventional substrates (e.g., non-bio-derived phenols or non-bio-derived alcohols) can also be used with the processes described herein.

[0034] Process 200 includes reaction subprocess 205 and post-processing subprocess 215. In some embodiments, reaction subprocess 205 can be carried out in coupling unit or reactor, and post-processing subprocess 215 can be carried out in post-processing unit or reactor. Herein, line 210 represents that the product mixture formed in reaction subprocess 205 is fed to post-processing unit from coupling unit, wherein carries out post-processing subprocess 215. That is, coupling reaction subprocess 205 and post-processing subprocess 215 makes each unit or reactor be coupled. Or, line 210 can represent to carry out post-processing subprocess 215 and post-processing subprocess 215 can be carried out in the reactor identical with the reactor for reaction subprocess 205, or carry out on the spot or carry out continuously.

[0035] Reaction subprocess 205 includes coupling substrate (such as bisphenol, aliphatic alcohol or its combination) with epihalohydrin in the presence of catalyst to form halohydrin reaction product (or halohydrin intermediate). Reaction subprocess 205 also includes circulating the halohydrin reaction product into a product mixture including glycidyl products by using an alkaline reagent. In some embodiments, the catalyst and the alkaline reagent can be identical. In at least one embodiment, the catalyst and the alkaline reagent can be different. In some embodiments, alkaline reagents can be utilized to carry out coupling and dead looping, such as sodium hydroxide and other. The operation of reaction subprocess 205 and post-processing subprocess 215 can be similar to reaction subprocess 105 and post-processing subprocess 115.

[0036] However, different from conventional processes, before product self-reaction subprocess 205 is fed to post-process 215, liquid epoxy resin 207 is added to the product of reaction subprocess by line 208. Liquid epoxy resin (liquid epoxyresin, LER) can prevent the product gelation or solidification from glycidylation when removing residual epihalohydrin. LER is added to the product mixture and can help dissolve product mixture and reduce the viscosity of product mixture. LER is added to product mixture and can also help product mixture to be discharged from reactor and product mixture is transferred to a separate reactor for carrying out post-processing. In addition, LER is added to product mixture and can help remove salt and brine formed during dead cycle, remove by-product formed by reaction, remove unreacted epihalohydrin or its combination. In this way, embodiments as described herein can use non-conventional substrates to form epoxy resin composition.

[0037] Embodiments described herein are generally directed to the process forming epoxy resin composition. The process generally includes reacting a mixture of a substrate (such as an alcohol-containing substrate, such as bisphenol), an epihalohydrin and a catalyst under reaction conditions to form a mixture comprising a reaction product. The process may further include adding an alkaline reagent to the mixture to form a product mixture. The product mixture may include, for example, a glycidyl product (epoxy resin) and optionally one or more optional components (such as residual halohydrin reaction product, solvent, unreacted epihalohydrin, its combination and other components). Before (such as by removing excess epihalohydrin) terminating the reaction, liquid epoxy resin is added to the mixture. Liquid epoxy resin is introduced into the reaction product to, for example, prevent the reaction product from solidifying due to glycidyl reaction when removing epihalohydrin. When needed, the reaction can be stopped by, for example, removing epihalohydrin, to form epoxy resin composition. In some embodiments, the reaction product may then undergo post-processing, which may include purification operations (such as, epihalohydrin removal, solvent removal, salt removal), another glycidyl reaction and other operations to form purified epoxy resin composition.

[0038] As further described below, conventional processes for forming epoxy resin compositions cannot utilize different substrates for glycidylation reactions. For example, conventional processes cannot utilize bio-derived materials such as lignin to form epoxy resin compositions. One of the reasons for this problem is that the reaction product generated by the glycidylation reaction becomes gel-like or solidifies. As a gel or solid, the epoxy resin composition does not undergo the post-processing process typically performed in a separate reactor as a glycidylation reaction. Even if the generated reaction product is not transferred to a different reactor, the halohydrin reaction product present in the reaction product cannot be converted into the desired glycidyl ether in the post-processing stage because the halohydrin reaction product is in an insoluble mixture. When the conversion of the halohydrin reaction product is not performed in the post-processing stage but in the reaction stage, gelation and solidification remain a problem because a glycidyl product is formed. In addition, solidification and gelation are problems of washing and extracting using solvents, water, and combinations thereof.

[0039] Figure 3 is a flow chart showing selected operations of a process 300 for forming an epoxy resin composition. Figure 3 For non-limiting examples. Process 300 is included in the reaction of the mixture comprising substrate, epihalohydrin and catalyst under reaction conditions to form the first composition. The mixture can further include solvent and other components. The first composition formed by operation 305 can include halohydrin reaction product (further described below), epoxy resin (for example, required glycidyl product), its combination, and other components, such as the salt formed during the reaction.

[0040] Suitable substrates (compounds) for use in operation 305 may include bio-derived alcohols and alcohols present in the resin recycle stream. The substrate for use in operation 305 may be interchangeably referred to as a glycidyl substrate.

[0041] Suitable substrates can include at least one hydroxyl group (-OH) present in the substrate. At least one hydroxyl group can exist as a phenolic hydroxyl group, a hydroxyl group (such as an alkyl hydroxyl group or an aliphatic hydroxyl group) connected to a non-aromatic carbon, or a combination thereof. Alcohols of biological origin and alcohols present in the circulating stream can include polyols (compounds containing more than one alcohol), polyphenols (compounds containing more than one phenol, such as bisphenols, trisphenols, tetraphenols, etc., can be utilized), combinations thereof, and others. A substrate having an alcohol connected to an aromatic carbon and an alcohol (e.g., an alkyl hydroxyl group) connected to a non-aromatic carbon can be utilized. In addition, a substrate separated from a mixture by an embodiment described herein (e.g., process 400 or process 500 as described below) can be used as a substrate for process 300.

[0042] Although the embodiments described herein are discussed with reference to phenols, polyphenols, or phenolic moieties for simplicity, it will be understood that any suitable substrate comprising at least one hydroxyl group (—OH) may be used.

[0043] Suitable alcohols that can be used in the embodiments described herein (e.g., operation 305) can include conventional alcohols used for glycidylation (e.g., synthetic and non-biologically derived polyphenols) as well as non-conventional alcohols and non-conventional polyphenols. Non-conventional alcohols and polyphenols refer to alcohols and polyphenols that are not conventionally used to form epoxy resins, phenolic resins, and other resins, as well as alcohols and polyphenols that are not conventionally used in glycidylation reactions.

[0044] In some embodiments, biomass comprises alcohol, polyphenol, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, phenolic acid, Additionally or alternatively, biomass includes municipal solid waste, byproducts and waste from wood processing, byproducts and waste from papermaking or wood processing, byproducts and waste from agricultural and forestry activities, rotational crops, wood, wood chips, sawdust, straw, firewood, wood materials, paper, waste paper, yard waste, and the like. Thus, polyphenols present in such materials (biomass) can be used with the embodiments described herein.

[0045] Suitable alcohols may include alcohols (e.g., polyphenols and alkyl alcohols) present in industrial lignin, kraft lignin, and organosolv lignin. Industrial lignin refers to natural lignin or raw lignin derivatives obtained as a result of the delignification process of lignocellulosic biomass. Kraft lignin refers to industrial lignin obtained from kraft pulp by converting a biobased substrate (e.g., one of those described above, such as wood) into pulp through the kraft pulping process. Organosolv lignin refers to lignin obtained by the organosolv process, which is a pulping technology that uses an organic solvent to dissolve lignin and hemicellulose.

[0046] Non-conventional alcohols (e.g., polyols and alkyl alcohols) comprise, consist essentially of, or consist of alcohols present in recycle or waste streams comprising epoxy resins, phenolic resins, or combinations thereof, as well as other resins. Such waste and recycle streams can be those used or produced during resin processing or manufacturing.

[0047] In some embodiments, non-conventional alcohol can form a mixture of materials or a part of a complex mixture. This mixture or complex mixture is called a substrate source. As described below, and if necessary, such substrate sources can be processed to extract from the substrate source or otherwise separate the desired non-conventional alcohol (substrate) to be used for glycidylation. Below, with reference to, for example, process 400 and process 500, non-limiting examples of processes for separating the desired substrate from the substrate source are described.

[0048] In some embodiments, suitable polyphenols include mononuclear and polynuclear polyphenols, including those represented by Formula (Ia), Formula (Ib), Formula (Ic), Formula (Id), or combinations thereof:

[0049] (R)2-Ph-(A) n -Ph-(R)2(Ia);

[0050] P-Ph-[A-Ph] m -R(Ib);

[0051] R-Ph-A 1 -(Ph-R)2(Ic); or

[0052]

[0053] Wherein, for formula (Ia)-(Id):

[0054] Ph is a phenol group (an aromatic group having a hydroxyl functional group);

[0055] Each A group is independently an unsubstituted hydrocarbon group, a substituted hydrocarbon group, or a functional group comprising at least one element from Groups 13-17 of the Periodic Table of the Elements, and each A group is independently divalent, trivalent, or tetravalent;

[0056] Each A 1 The group is an unsubstituted hydrocarbon group, a substituted hydrocarbon group, or a functional group comprising at least one element from Groups 13 to 17 of the Periodic Table of Elements, and each A 1 The groups are independently divalent, trivalent, or tetravalent;

[0057] Each R group is independently hydrogen, an unsubstituted hydrocarbon group, a substituted hydrocarbon group, or a functional group comprising at least one element from Groups 13 to 17 of the Periodic Table of the Elements, and each R group within the same polyphenol may be the same or different;

[0058] m is 1 to 6, such as 1 to 3 or 1, 2, 3, 4, 5 or 6;

[0059] n is 0 or 1; and

[0060] p is 1 to 100, such as 1 to 20, such as 1 to 10, such as 1 to 5, such as 1, 2, 3, 4 or 5.

[0061] When group A, A 1 When the group or the R group is a functional group containing at least one element from Groups 13 to 17, the A group, A 1 The group or R group can be halogen (F, Cl, Br or I), O, N, Se, Te, P, As, Sb, S, B, Si, Ge, Sn, Pb and similar elements, such as C(O)R*, C(C)NR*2, C(O)OR*, NR*2, OR*, SeR*, TeR*, PR*2, AsR*2, SbR*2, SR*, SO x (wherein x = 2 or 3), BR*2, SiR*3, GeR*3, SnR*3, PbR*3 and the like, wherein R* is independently hydrogen or an unsubstituted hydrocarbon group, or wherein at least one heteroatom has been inserted into the unsubstituted hydrocarbon group.

[0062] A, A of formula (Ia)-(Id) 1 Each of A, R, and R can independently have any suitable number of carbon atoms, such as 1 to 20 carbon atoms, such as about 1 to about 12 carbon atoms, such as 1 to 10 carbon atoms, such as 1 to 5 carbon atoms, such as 1 to 4 carbon atoms. In some embodiments, A, A, R, and R in Formulas (Ia)-(Id) are 1 and the number of carbon atoms in R can independently be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20. Each of the aforementioned numbers may be preceded by the words "about," "at least about," "less than about," or "greater than about," and any of the aforementioned numbers can be used alone to describe an open range or in combination to describe a closed range. A, A of formula (Ia)-(Id) 1 Each of A and R can independently be linear or branched, saturated or unsaturated, cyclic or acyclic, aromatic or non-aromatic. 1 Each of R and R may independently be fully saturated, partially unsaturated, or fully unsaturated.

[0063] In some embodiments, A, A 1Each of R and R may be an unsubstituted hydrocarbon group. "Unsubstituted hydrocarbon group" refers to a group consisting solely of hydrogen and carbon atoms. Non-limiting examples of unsubstituted hydrocarbon groups include alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary and tertiary butyl, pentyl, hexyl, heptyl, octyl, ethyl-2-hexyl, isooctyl, nonyl, n-decyl, isodecyl, or isomers thereof; cycloaliphatic groups having 3 to 20 carbon atoms, such as cyclopentyl or cyclohexyl; aromatic groups having 6 to 20 carbon atoms, such as phenyl or naphthyl; or any combination thereof.

[0064] In some embodiments, A, A of Formula (Ia)-(Id) 1 and R may be a substituted hydrocarbyl group. "Substituted hydrocarbyl" refers to an unsubstituted hydrocarbyl group in which at least one hydrogen of the unsubstituted hydrocarbyl group has been replaced with at least one heteroatom or heteroatom-containing group, such as one or more elements from Groups 13-17 of the Periodic Table of the Elements, such as halogens (F, Cl, Br, or I), O, N, Se, Te, P, As, Sb, S, B, Si, Ge, Sn, Pb, and the like, such as C(O)R*, C(C)NR*2, C(O)OR*, NR*2, OR*, SeR*, TeR*, PR*2, AsR*2, SbR*2, SR*, SO x (wherein x = 2 or 3), BR*2, SiR*3, GeR*3, SnR*3, PbR*3 and the like, wherein R* is independently hydrogen or an unsubstituted hydrocarbon group, or wherein at least one heteroatom has been inserted into the unsubstituted hydrocarbon group.

[0065] In at least one embodiment, each A group of formula (Ia)-(Id) is independently a divalent hydrocarbon group having 1 to 12 carbon atoms, -O-, -S-, -SS-,

[0066] In some embodiments of Formulas (Ia)-(Id), each A is independently a divalent group, A 1 is a trivalent group or a combination thereof.

[0067] In some embodiments, each R group of Formulas (Ia)-(Id) is independently hydrogen, an unsubstituted hydrocarbyl group having 1 to 10 carbon atoms, a halogen (such as Cl or Br), a hydroxyl group (-OH), or a substituted hydrocarbyl group having 1 to 10 carbon atoms. For example, the substituted hydrocarbyl group may be -OR*, wherein the oxygen atom is attached to the ring and wherein R* may include 1 to 10 carbon atoms, such as 1 to 5 carbon atoms, such as 2 to 4 carbon atoms. As another example, the substituted hydrocarbyl group may be a hydrocarbon chain with OH or OR*, or the substituted hydrocarbyl group may be an aromatic unit with OH or OR*.

[0068] In some embodiments, the polyphenol is represented by formula (II):

[0069]

[0070] In formula (II), A 2 is a divalent group, a trivalent group or a tetravalent group, such as those described above for A in formulas (Ia) to (Id). In formula (II), R 1 、R 2 、R 3 and R 4 Each of can be an R group as described above for R in formulas (Ia)-(Id), such as hydrogen, an unsubstituted hydrocarbon group, a substituted hydrocarbon group, or a functional group comprising at least one element from Groups 13-17 of the Periodic Table of the Elements. 1 、R 2 、R 3 and R 4 Each of can be the same or different.

[0071] As shown in formula (II), R 1 and R 2 Each of R is independently located at the ortho, meta, or para position of the hydroxyl group on the aromatic ring. 3 、R 4 and each of the hydroxyl groups (-OH) is independently located on the aromatic ring A 2 In some embodiments, R in formula (II) 1 、R 2 、R 3 and R 4 Each of the R in formula (II) may be independently hydrogen, an unsubstituted hydrocarbon group having 1 to 20 carbon atoms (such as 1 to 12, such as 1 to 10, such as 2 to 6), or a substituted hydrocarbon group having 1 to 20 carbon atoms (such as 1 to 12, such as 1 to 10, such as 2 to 6). In at least one embodiment, R in formula (II) 1 、R 2 、R 3 and R 4 Each of the -OH group, an alkyl group with an -OH group, an -OR* group, an alkyl group with an -OR* group, an aromatic group with 6 to 20 carbon atoms (such as phenyl, naphthyl and others), or an aromatic group with 6 to 20 carbon atoms and an -OR* group. For the -OR* group, the oxygen atom is connected to the aromatic ring and R* may include 1 to 10 carbon atoms, such as 1 to 5 carbon atoms, such as 2 to 4 carbon atoms. For example, -OR* may be an alkoxy group, such as methoxy, ethoxy, propoxy, butoxy and isomers thereof.

[0072] In some embodiments, R in formula (II) 1 、R 2 、R 3 and R 4 Each of the R is independently a group that does not react with the reactant with the epoxide. For example, and in at least one embodiment, R in formula (II) 1 、R 2 、R 3 and R 4 Each of the groups is independently -(C1-C5)alkyl or -O(C1-C5)alkyl.

[0073] In at least one embodiment, the phenol of formula (I) is a bisphenol. In formula (II), and in some embodiments, R 1 or R 2 At least one of is located in the ortho position relative to the hydroxyl group on the aromatic ring. In some embodiments, R 3 or R 4 At least one of the A 2 In some embodiments, the hydroxyl group of the aromatic ring (on the right side of formula (II)) is located on the aromatic ring A 2 counterpoint.

[0074] Illustrative but non-limiting examples of the polyphenol of formula (II) include tetramethylbisphenol F (TMBPF; CAS No. 5384-21-4; also known as 4,4'-methylenebis(2,6-dimethylphenol)) (IIa); 4,4'-methylenebis(2,6-diethylphenol) (CAS No. 73576-37-1, (IIb)); 4,4'-methylenebis(2,6-diisopropylphenol) (CAS No. 24742-46-9, (IIc)); 4,4'-methylenebis(2,6-di-tert-butylphenol) (CAS No. 118-82-1, (IId)); 4,4'-methylenebis(2,6-dimethoxyphenol) (CAS No. 15640-40-1, (IIe)); bisphenol A (TMBPA; CAS No. 5613-46-7) (IIf); or combinations thereof:

[0075]

[0076] The polyphenols described above may be of biological origin (eg, derived from biomass, or from a process that converts biomass into products such as industrial lignin, kraft lignin, or organosolv lignin), or may be synthetic (ie, from a non-biological source).

[0077] As described above, the substrate used for glycidylation (e.g., operation 305) may include a component of a recycle stream (or derived from a recycle stream) that includes an epoxy resin, a phenolic resin, or a combination thereof. Illustrative but non-limiting examples of such substrates derived from a recycle stream include novolac resins, epoxy novolacs, phenolic oligomers from pyrolyzed composites based on bisphenol A-liquid epoxy resins, and phenolic oligomers from solvolyzed composites based on bisphenol A-liquid epoxy resins.

[0078] The substrate that can be used in the glycidylation reaction (eg, operation 305 ) can also include a resin represented by formula (III) or a derivative thereof:

[0079]

[0080] In formula (III), x can be 1 to 20, such as 1 to 10, such as 4 to 8. In some embodiments, x of formula (III) can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20. Each of the aforementioned numbers can be preceded by the words "about," "at least about," "less than about," or "greater than about," and any of the aforementioned numbers can be used alone to describe an open range or in combination to describe a closed range.

[0081] The resin represented by formula (III) is an example of a compound having a hydroxyl group present on a non-aromatic carbon (a base material having an alkyl hydroxyl group or an aliphatic hydroxyl group).

[0082] Suitable substrates for operation 305 can include any of the foregoing materials, combinations of the foregoing materials in any proportions.

[0083] Suitable epihalohydrins for use in operation 305 include those represented by formula (IV):

[0084]

[0085] In formula (IV), R 5 R of the epihalohydrin shown in formula (IV) is hydrogen, an unsubstituted hydrocarbon group or a substituted hydrocarbon group. 5 The group may include 1 to 20 carbon atoms, such as 1 to 10 carbon atoms, such as 1 to 4 carbon atoms. The X group in formula (IV) is a halogen, such as fluorine, chlorine, bromine or iodine, such as chlorine or bromine. In some embodiments, the epihalohydrin comprises epichlorohydrin (X in formula (IV) = Cl and R 5 =H; CAS No. 106-89-8), epibromohydrin (X in formula (IV) = Br and R 5 =H; CAS No. 3132-64-7) or a combination thereof.

[0086] During operation 305, a solvent can be used. The solvent for operation 305 is generally an organic solvent. The organic solvent for operation 305 can include alcohol, ketone, aromatic hydrocarbon and halogenated aliphatic compound, such as isopropyl alcohol, ethanol, methanol, methyl isobutyl ketone, methyl ethyl ketone, toluene, xylene, methylene dichloride, ethylene dichloride, its mixture and other. The combination of solvents can be used. In at least one embodiment, epihalohydrin can be used as solvent. For example, epichlorohydrin can be used as reactant and solvent.

[0087] As described above, a basic reagent, or a basic reagent and a catalyst, can be used to form a glycidylation product (a closed-loop epoxide product) from a substrate (such as a bisphenol, an aliphatic alcohol, or a combination thereof) and an epihalohydrin reactant.

[0088] The basic reagent can couple the substrate with the epihalohydrin to form a halohydrin reaction product (or halohydrin intermediate) and to cycle the halohydrin reaction product back into a glycidyl product. In another aspect, a catalyst is selected to at least perform the coupling.

[0089] For example, ammonium and phosphonium salts can couple but are not sufficiently basic to undergo a closed-loop reaction to form epoxides. In contrast, alkaline reagents such as sodium hydroxide can act as both a coupling catalyst and a closed-loop reagent.

[0090] Process 300 further includes introducing an alkaline agent into the first composition to form a second composition at operation 310. In some embodiments, operation 305 may be optional, for example, when the catalyst is also an alkaline agent. When the catalyst is also an alkaline agent, the alkaline agent may act as a catalyst both at the beginning of the reaction (primarily forming a first composition comprising a halohydrin reaction product) and later in the reaction (primarily forming a second composition comprising a closed-loop glycidylation product).

[0091] Operation 310 can be performed under the same or similar conditions as described for operation 305. The second composition can include a product mixture comprising, consisting essentially of, or consisting of the epoxy resin (the desired epoxy product), the residual halohydrin reaction product, combinations thereof, and other components (such as salts formed during the reaction).

[0092] Suitable catalysts that can be used in operation 305 may comprise, consist essentially of, or consist of alkali metal hydroxides, alkaline earth metal hydroxides, ammonium salts, phosphonium salts, sulfonium salts, lithium salts, or combinations thereof. Non-limiting examples of alkali metal hydroxides may include, but are not limited to, sodium hydroxide, potassium hydroxide, lithium hydroxide, or combinations thereof, and others. Illustrative but non-limiting examples of alkaline earth metal hydroxides include calcium hydroxide, magnesium hydroxide, combinations thereof, and others. Suitable ammonium salts include tetramethylammonium chloride, tetrabutylammonium chloride, tetrabutylammonium bromide, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, tetraethylammonium chloride, tetraethanolammonium chloride, tetraethanolammonium hydroxide, or combinations thereof, and others. Suitable phosphonium salts include ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium bicarbonate, benzyltriphenylphosphonium chloride, tetrabutylphosphonium chloride, and the like. Suitable sulfonium salts include thiourea catalysts, such as tetramethylthiourea and N,N'-diphenylthiourea. Mixtures of catalysts may be used with the embodiments herein. In at least one embodiment, the catalyst comprises, consists essentially of, or consists of sodium hydroxide, potassium hydroxide, calcium hydroxide, tetramethylammonium chloride (TMAC), tetrabutylammonium chloride (TBAC), tetrabutylammonium bromide (TBAB), or combinations thereof.

[0093] Suitable alkaline agents may include, but are not limited to, alkali metal hydroxides, alkaline earth metal hydroxides, or combinations thereof, such as sodium hydroxide (NaOH), potassium hydroxide (KOH), lithium hydroxide (LiOH), calcium hydroxide (Ca(OH)2), magnesium hydroxide (Mg(OH)2), or combinations thereof, such as NaOH, KOH, (Ca(OH)2), or combinations thereof. Mixtures of alkaline agents may be used with embodiments herein.

[0094] Epihalohydrin and substrate can be about 1:1 to about 50:1 by the molar ratio of the hydroxyl group (aromatic hydroxyl group, alkyl hydroxyl group) of epihalohydrin and substrate, such as about 1.1 to about 35:1, such as about 1.2:1 to about 20:1, such as about 1.5:1 to about 10:1 molar ratio provides, but also considers other amounts.Any aforementioned numeral can be used alone to describe open-ended scope or be used in combination to describe closed-ended scope.

[0095] In some embodiments, the epihalohydrin and the substrate may be provided in a mass ratio of excess (greater than 1:1) epihalohydrin to substrate.

[0096] The weight ratio of the solvent (e.g., toluene or epihalohydrin) to the substrate for operation 305 can be from about 1:1 to about 50:1, such as from about 2:1 to about 20:1, such as from about 5:1 to about 12:1, but other amounts are also contemplated. Any of the aforementioned numbers can be used alone to describe an open range or in combination to describe a closed range.

[0097] The amount of the catalyst for operation 305 can be any quantity that is suitable for the reaction between catalysis polyphenol and epihalohydrin.Catalyst and substrate can be about 0.01:1 to about 0.5:1 by the molar ratio of the hydroxyl group (for example, aromatic hydroxyl group, alkyl hydroxyl group) of catalyst and substrate, such as about 0.05:1 to about 0.2:1, such as about 0.1:1 to about 0.15:1 provide, although also consider other amounts.Any aforementioned numeral can be used alone to describe open range or be used in combination to describe closed range.

[0098] The amount of the alkaline reagent for the closed loop reaction in operation 310 is determined to a great extent by the amount of the epihalohydrin of the reaction. For example, when making polyphenol glycidyl with the hydroxyl (aromatic hydroxyl, alkyl hydroxyl) of more than two equivalents of excess epihalohydrin / substrate, the hydroxyl equivalent of molar excess catalyst / substrate is used, such as about 1.2: 1 to about 5: 1, such as about 1.5: 1 to about 3.5: 1, such as about 2: 1 to about 3: 1, but other amounts are also considered. Any of the aforementioned numerals can be used alone to describe an open range or used in combination to describe a closed range.

[0099] In some embodiments, each of the catalyst (in operation 305), the alkaline agent (in operation 310), or a combination thereof may be independently added to the substrate, epihalohydrin, and solvent in solid or solution form. When the catalyst or alkaline agent is used as a solution with the other reactants, the solution (catalyst or alkaline agent in solvent) may contain from about 15% to about 65% by weight of the catalyst or alkaline agent, such as from about 20% to about 55% by weight of the catalyst or alkaline agent, such as from about 30% to about 45% by weight of the catalyst or alkaline agent, but other amounts are also contemplated.

[0100] The reaction conditions of operation 310 can comprise feeding time (or injection time), feeding back time (or injection back time) and total reaction time.The feeding time is the period in which alkaline reagent is added to base material, epihalohydrin and solvent.The feeding time of operation 310 can be approximately 10 minutes to approximately 8 hours, such as approximately 40 minutes to approximately 6 hours, such as approximately 1 hour to approximately 2 hours, but also considers other periods.Any aforementioned numeral can be used separately to describe open range or be used in combination to describe closed range.

[0101] The time after feeding of operation 310 is the period from the time when all alkaline reagents are added during operation 310 to the time when operation 310 reactions are terminated. The end of reaction can be based on the time point at which a certain percentage conversion has occurred for substrate. For example, the time after feeding of operation 310 can be the time at which the feeding time ends and the halohydrin reaction product (or halohydrin intermediate material) has been approximately 90% or more converted into the time between the points of the dead cycle product, such as approximately 91% or more conversion, such as approximately 92% or more conversion, such as approximately 93% or more conversion, such as approximately 94% or more conversion, such as approximately 95% or more conversion, such as approximately 96% or more conversion, such as approximately 97% or more conversion, such as approximately 98% or more conversion, such as approximately 99% or more conversion, such as approximately 99.9% or more conversion, such as approximately 100% conversion, but other conversion amounts are also considered. Any of the aforementioned numerals can be used alone to describe an open range or used in combination to describe a closed range.

[0102] In some non-limiting examples, the post-feed time of operation 310 can be from about 20 minutes to about 5 hours, such as from about 1 hour to about 3 hours, such as from about 1.5 hours to about 2 hours, although other time periods are also contemplated. Any of the foregoing numbers can be used alone to describe an open-ended range or in combination to describe a closed range.

[0103] The total reaction time of operation 310 is the sum of the feeding time and the time after the feeding. The total reaction time of operation 310 can be from about 0.5 hours to about 13 hours, such as from about 0.5 hours to about 9 hours, such as from about 1 hour to about 6 hours, such as from about 2 hours to about 4.5 hours, although other time periods are also contemplated. Any of the aforementioned numbers can be used alone to describe an open range or in combination to describe a closed range.

[0104] The reaction time of operation 305 can be from about 0.5 hours to about 13 hours, such as from about 0.5 hours to about 9 hours, such as from about 1 hour to about 6 hours, such as from about 2 hours to about 4.5 hours, although other time periods are also contemplated. Any of the aforementioned numbers can be used alone to describe an open range or in combination to describe a closed range.

[0105] The reaction conditions of operation 305, operation 310, or both may include a reactor temperature of about 20°C to about 100°C, such as about 35°C to about 95°C, such as about 50°C to about 90°C, although other temperatures are contemplated. Any of the aforementioned numbers may be used alone to describe an open-ended range or in combination to describe a closed-ended range. The reactor temperature is the temperature monitored by a temperature probe.

[0106] The reaction conditions of operation 305, operation 310, or both may also include reactor pressure measured in absolute pressure units. The reactor pressure may be from about 100 mbara (about 10 kPa (absolute)) to about 1,500 mbara (about 150 kPa (absolute)), such as from about 150 mbara (about 15 kPa (absolute)) to about 1,000 mbara (about 100 kPa (absolute)), such as from about 200 mbara (about 20 kPa (absolute)) to about 400 mbara (about 40 kPa (absolute), although other pressures are contemplated. Any of the foregoing numbers may be used alone to describe an open-ended range or in combination to describe a closed range.

[0107] Operation 305, operation 310 or both reaction conditions can comprise stirring, mixing, agitation or its combination.For stirring, mixing or stirring device can comprise batch reaction vessel, semi-batch reaction vessel, continuous static mixer or other suitable device.Can use mechanical agitation or jet mixing.In some embodiments, water and epichlorohydrin can be as steam by for example during at least a portion of operation 305, distillation from reaction mixture and remove (for example, continuously or periodically).Distillation can be azeotropic distillation.Epihalohydrin can return or be circulated in reaction mixture.

[0108] The reaction conditions of operation 305, operation 310 or both may optionally include the use of non-reactive gases, such as nitrogen, argon or a combination thereof. For example, a mixture comprising substrate, epihalohydrin, solvent and catalyst may be used with these or other non-reactive gases to degas various components or otherwise remove oxygen from the mixture.

[0109] As described herein, the first composition formed from operation 305, the second composition from operation 310 or both can include glycidyl products (epoxy resins), such as products wherein the hydroxyl group of substrate has been converted into glycidyl ethers. Optionally, the first composition, the second composition or both can include one or more optional components. One or more optional components can include intermediate substances (for example, halohydrin reaction products), salts, brine, solvents, unreacted starting materials (epihalohydrin, substrate, catalyst or its mixture), combinations thereof, and other components. As non-limiting examples, and as shown in scheme 1, glycidyl ethers with formula (V-1), halohydrin reaction products (or halohydrin intermediate substances) with formula (V-2) or combinations thereof can be formed by the reaction of polyphenols (as example alcohol) and epihalohydrin.

[0110] Solution 1

[0111]

[0112] In formula (V-1) and formula (V-2), the wavy bond represents a connection with other parts of the polyphenol.

[0113] Process 300 further includes introducing a liquid epoxy resin (LER) together with the second composition to form a resin mixture when operating 315. The resin mixture formed when operating 315 can be a liquid resin mixture. As described above, the use of LER can prevent the second composition (e.g., the product of reaction sub-process 205) from gelling or solidifying when removing epihalohydrin. Adding LER helps to dissolve the second composition and reduce its viscosity. Adding LER to the product mixture can also help to discharge the second composition from the unit or reactor used for reaction sub-process 205, and transfer the second composition to a separate unit or reactor, in which a post-process 215 occurs. In addition, adding LER to the product mixture can help to remove the salt and brine formed during glycidylation, remove the by-products formed by glycidylation, remove unreacted epihalohydrin or its combination, and other materials. In this way, the embodiments described herein can use non-conventional substrates to form epoxy resin compositions.

[0114] Adding LER during glycidylation is not obvious, at least because LER is exposed to reaction conditions, alkaline conditions, hydrolysis conditions, which one generally wants to avoid. However, adding LER during glycidylation can achieve various benefits as described herein.

[0115] Epoxy resins that can be used as LERs for operation 315 include polymers based on epoxy compounds, which can be the reaction product of a polyfunctional hydroxy compound and an epihalohydrin (e.g., epichlorohydrin, epibromohydrin, and others). Crosslinking of the polymer matrix occurs by polyaddition on the epoxy groups.

[0116] The epoxy resin that can be used as the LER of operation 315 can include epoxy resins based on bisphenol A, bisphenol F, advanced resins produced therefrom; epoxy resins based on tetraglycidyl-methylenedianiline (TGMDA); epoxy resins based on epoxidized halogenated bisphenols; epoxy resins based on epoxidized novolacs; epoxy resins based on epoxidized o-aminophenols or p-aminophenols; epoxy resins based on epoxidized polyaddition products of dicyclopentadiene and phenol; epoxy resins based on fluorenone bisphenols; or combinations thereof. In some embodiments, the epoxy resin that can be used as the LER of operation 315 is derived from bisphenol A, bisphenol F, tetraglycidyl-methylenedianiline, halogenated bisphenols, novolacs, o-aminophenols, p-aminophenols, cyclopolyaddition products of dicyclopentadiene and phenol, fluorenone bisphenols, or combinations thereof. Such materials can react with epoxide-containing reactants (such as epihalohydrins) to form epoxides or epoxy resins. For example, the epoxy resin may include epoxidized phenol novolac (a condensation product of phenol with, for example, formaldehyde, glyoxal, or a combination thereof), epoxidized cresol novolac, bisphenol A-based epoxy resins (e.g., the product of bisphenol A and tetraglycidyl methylene dianiline), epoxidized halogenated bisphenols (e.g., an epoxy resin based on tetrabromobisphenol A), bisphenol F-based epoxy resins, epoxidized novolacs, or a combination thereof.

[0117] Other epoxy resins that can be used as LERs in operation 315 include epoxides of aliphatic monoalcohols, epoxides of aliphatic diols. Such aliphatic alcohols have low viscosities. The aliphatic monoalcohols or diols can contain cyclic components, linear components, or a combination thereof. Illustrative but non-limiting examples include glycidyl ether of 1,4-butanediol, glycidyl ether of 1,6-hexanediol, monoglycidyl ethers of C6 to C14 aliphatic chains, and others.

[0118] In some embodiments, epoxy resins suitable as LERs for operation 315 include liquid epoxy resins having low viscosity. In the context of epoxy resins, "low viscosity" means that the epoxy resin has a viscosity of less than about 15 Pa·s at 25° C. (ASTM D-445).

[0119] The epoxy resin used as the LER may have a viscosity of about 0.002 Pa·s to about 15 Pa·s, such as about 0.01 Pa·s to about 6.5 Pa·s, such as about 0.02 Pa·s to about 3 Pa·s, although other viscosities are also contemplated. The viscosity of the epoxy resin used as the LER is measured at 25° C. using ASTM D-445.

[0120] Suitable low viscosity liquid epoxy resins include aromatic epoxy resins and aliphatic epoxy resins. Illustrative but non-limiting examples of such aromatic epoxy resins may include, but are not limited to, Epikote 828 (difunctional bisphenol-A-diglycidyl ether, commercially available from Westlake Epoxy), Epikote 828LVEL (difunctional bisphenol-A-diglycidyl ether, commercially available from Westlake Epoxy), Epikote 827 (difunctional bisphenol-A-diglycidyl ether, commercially available from Westlake Epoxy), Epikote 862 (difunctional bisphenol-F-diglycidyl ether, commercially available from Westlake Epoxy), Epikote 496 (tetraglycidyl methylene dianiline, commercially available from Westlake Epoxy), Epikote 1031 (epoxidized tetraphenylethane, commercially available from Westlake Epoxy), EPON 826 (difunctional bisphenol-A-diglycidyl ether, commercially available from Westlake Epoxy), and Epikote 1031 (epoxidized tetraphenylethane, commercially available from Westlake Epoxy). Epoxy), EPON 828 (difunctional bisphenol-A diglycidyl ether, commercially available from Westlake Epoxy), DER 330 (liquid epoxy resin reaction product of epichlorohydrin and bisphenol A, commercially available from Olin).

[0121] Illustrative but non-limiting examples of aliphatic epoxy resins having low viscosity can include, but are not limited to, Heloxy Z8 (aliphatic monoglycidyl ether of C12 / C14-fatty alcohols, commercially available from Westlake Epoxy), Heloxy BD (diglycidyl ether of 1,4-butanediol, commercially available from Westlake Epoxy), and Heloxy HD (diglycidyl ether of 1,4-hexanediol, commercially available from Westlake Epoxy).

[0122] The type of LER added can be matched to the application in which the final epoxy resin composition is used. In some embodiments, the selection of the LER can be based on its ability to form a homogeneous mixture with the second composition, its ability to mix with the second composition, and other factors or combinations thereof.

[0123] In some embodiments, the amount of LER added to the second composition is based on the amount of epoxy content formed by the reaction sub-process 205 (e.g., the epoxy content of the second composition). Here, the weight ratio of LER:epoxy resin in the second composition can be from about 0.02:1 to about 1.5:1, such as from about 0.05:1 to about 1.25:1, such as from about 0.25:1 to about 1:1, such as from about 0.5:1 to about 1:1, although other amounts are also contemplated. Any of the foregoing numbers can be used alone to describe an open-ended range or in combination to describe a closed range.

[0124] At this stage, the resin mixture comprises, consists essentially of, or consists of the LER and the glycidyl ether (as an example desired product, such as the glycidyl ether of formula (V-1)). The resin mixture may also include one or more optional components, such as a halohydrin reaction product (e.g., a halohydrin reaction product of formula (V-2)), unreacted epihalohydrin, solvent, water, salt, combinations thereof, and other components.

[0125] Process 300 may further include removing unreacted epihalohydrin from a resin mixture (e.g., a liquid resin mixture) during operation 320. The removal of unreacted epihalohydrin can be performed by, for example, evaporation or distillation (under suitable conditions) and other methods. Here, for example, and depending on the epihalohydrin, the distillation temperature can be from about 70°C to about 150°C, such as from about 90°C to about 130°C; the distillation pressure can be from about 20mbara (about 2kPa (absolute)) to about 500mbara (about 50kPa (absolute)), such as from about 50mbara (about 5kPa (absolute)) to about 200mbara (about 20kPa (absolute)); or a combination thereof. Any of the aforementioned numbers can be used alone to describe an open range or in combination to describe a closed range. Depending on the epihalohydrin used, other distillation temperatures and pressures are considered.

[0126] Another method may include evaporating the halohydrin (and optionally other volatile components) from the resin mixture using a flash evaporator, falling film evaporator, boiling tube evaporator, wiped film evaporator, stripping column, stripping with an inert gas, stripping with steam, or other suitable technique. A combination of removal operations may be performed.

[0127] After unreacted epihalohydrin is removed by the removal process of operation 320 , the resin mixture may comprise, consist essentially of, or consist of the desired glycidyl ether (epoxy resin composition), the added LER, and residual salts formed from the glycidylation reaction.

[0128] In contrast to conventional processes that are not suitable for bio-derived substrates (or other non-conventional substrates), the embodiments described herein utilize the addition of an LER to the second composition to enable, for example, the second composition (as a resin mixture) to be fed to a separate unit where further operations (such as post-processing sub-process 215, including the final reaction of optional operation 325 described below) can be performed. In contrast, conventional processes observe gelation or solidification of the products from the glycidylation reaction. In addition, the use of an LER helps solubilize components of the second composition (e.g., glycidyl ethers and byproducts produced from non-conventional substrates) in organic solvents, whereas such components would otherwise be insoluble by conventional processes. Here, the insolubility of the components of the second composition formed by conventional processes would, for example, prevent the second composition from being fed to a separate reactor for post-processing and further processing, as gelation or solidification would make mixing impossible (or at least difficult and inefficient). Furthermore, insolubility prevents subsequent closed-loop reactions of the halohydrin reaction product (e.g., the halohydrin reaction product of formula (V-2)) because the halohydrin reaction product must react with an alkaline reagent in solution to achieve a closed-loop reaction. In other words, conventional processes cannot use, for example, bio-derived materials or resin waste / recycle streams as substrates.

[0129] Here, soluble means that one or more components (eg, glycidyl ether and halohydrin reaction product made from non-conventional substrates) can be in the form of a slurry in which one or more components are partially or completely dissolved.

[0130] In embodiments where a single reactor, vessel, or unit is used to form an epoxy resin composition from a non-conventional substrate (e.g., one reactor is used for both the reaction sub-process 205 and the post-treatment sub-process 215), the LER can prevent the glycidyl ether and halohydrin reaction products in the second composition from gelling or solidifying. By preventing these materials from gelling or solidifying, the halohydrin reaction products can react in a closed loop and form glycidyl ethers in higher yields.

[0131] In some embodiments, and after operation 320, the resin mixture can be optionally processed to separate the salt formed by the glycidylation reaction. Here, for example, the salt can be removed from the resin mixture by any suitable method such as filtration, centrifugation or other solid / liquid separation techniques. Additionally or alternatively, the salt can be separated from the resin mixture by adding an organic solvent and water to the resin mixture. The water dissolves the salt and can separate the resulting aqueous phase and organic phase. Suitable organic solvents for separation include ketones, aromatic hydrocarbons and halogenated aliphatic compounds, such as methyl isobutyl ketone, methyl ethyl ketone, toluene, xylene, methylene chloride, ethylene dichloride or mixtures thereof, as well as other. Combinations of solvents can be used. The amount of organic solvent and water used for separation can vary widely depending on the properties of the solvent and resin mixture utilized, as well as other factors.

[0132] As an illustrative but non-limiting example of phase separation, the amount of organic solvent used can be from about 25 wt % to about 75 wt %, such as from about 40 wt % to about 60 wt %, which provides 100 wt % of the total weight of the solvent and the resin mixture when used in combination with the resin mixture, but other amounts are also considered. A certain amount of water is added to dissolve the salt. The amount of water utilized can be based on the brine solution formed, such as the amount of water to form a brine solution of from about 0.1 wt % to about 30 wt %, such as from about 1 wt % to about 26 wt %, such as from about 5 wt % to about 23 wt %, such as from about 15 wt % to about 20 wt % salt in water, but other amounts are also considered. After the addition of the organic solvent and water, the mixture is separated into a salt water phase and a phase containing the organic resin, and the two phases are separated.

[0133] Separation of the organic and aqueous phases can be accomplished by any suitable liquid-liquid separation, including decanters, coalescers, and decanting centrifuges, among others.

[0134] Operation 320 may optionally include utilizing a non-reactive gas, such as nitrogen, argon, or a combination thereof. For example, during operation 320, a non-reactive gas may be used to remove residual solvent or residual excess epihalohydrin from the reaction mixture.

[0135] Return to see Figure 3 Process 300 may further include, at optional operation 325, optionally converting the residual halohydrin reaction product into a third composition comprising an epoxy resin composition. As described herein, the resin mixture formed by operation 320 may also include a halohydrin reaction product in addition to the epoxy resin composition. The optional reaction of operation 325 is then performed, for example, to complete the dehydrohalogenation of the residual halohydrin reaction product (e.g., the halohydrin reaction product of Formula (V-2)) and form a closed-loop product that is the desired glycidyl ether (such as the glycidyl ether of Formula (V-1)). When residual halohydrin reaction product remains, it is typically present in only about 10% or less.

[0136] The conversion reaction of optional operation 325 is referred to herein as the "final reaction". The final reaction can include forming a mixture comprising the second composition, an alkaline reagent, and a solvent, and reacting the mixture under reaction conditions. Suitable alkaline reagents and solvents that can be used in optional operation 325 include those described herein, as well as others.

[0137] When the reaction of operation 310 does not produce a composition having a halohydrin reaction product (e.g., a halohydrin reaction product of formula (V-2)), the process may be performed without optional operation 325. Additionally or alternatively, the epoxy resin composition containing the residual halohydrin reaction product may be used as is.

[0138] In some embodiments, the amount of residual halohydrin reaction product in the epoxy resin composition may be about 10% or less, about 5 wt% or less, about 1 wt% or less, about 0.5 wt% or less, or about 0.3 wt% or less, based on the total weight of the epoxy resin composition.

[0139] When process 300 includes optional salt separation, the organic solvent used for salt separation can be used as the solvent for the final reaction of optional operation 325. Suitable organic solvents for the final reaction of optional operation 325 include ketones, aromatic hydrocarbons, and halogenated aliphatic compounds, such as methyl isobutyl ketone, methyl ethyl ketone, toluene, xylene, dichloromethane, dichloroethane, or mixtures thereof, among others. Combinations of solvents can be used.

[0140] The amount of organic solvent used in the final reaction of optional operation 325 can be from about 25 wt % to about 80 wt %, such as from about 30 wt % to about 70 wt %, such as from about 45 wt % to about 65 wt %, the weight percentage being based on the total wt % of the resin mixture and the solvent, with the total wt % not exceeding 100 wt %. Any of the aforementioned numbers can be used alone to describe an open-ended range or in combination to describe a closed-ended range. Other amounts of solvent are contemplated.

[0141] The alkaline reagent used for the final reaction of optional operation 325 can be the same as those described herein, such as alkali metal hydroxides, alkaline earth metal hydroxides, or combinations thereof. If desired, a mixture of alkaline reagents (e.g., NaOH and KOH) can be used.

[0142] The amount of the alkaline reagent for the final reaction of optional operation 325 can be any suitable quantity, such as the quantity of the residual halohydrin reaction product of ring closure suitably.In some embodiments, based on the total amount of alkaline reagent, resin mixture and solvent, the amount of alkaline reagent is about 1wt% to about 10wt%, such as about 2wt% to about 8wt%, such as about 3wt% to about 5wt%, and total amount is no more than 100wt%.Any aforementioned numeral can be used alone to describe open range or be used in combination to describe closed range.Consider other amounts.Catalyst can be added in resin mixture and solvent as solid or solution.

[0143] The reaction conditions of the final reaction of optional operation 325 can include feeding time (or injection time), feeding time after time (or injection time) and total reaction time. The feeding time of the final reaction is the period in which alkaline reagent is added to resin mixture and solvent. The feeding time of the final reaction of optional operation 325 can be approximately 10 minutes to approximately 5 hours, such as approximately 40 minutes to approximately 4 hours, such as approximately 1 hour to approximately 3 hours, but also consider other periods. Any aforementioned numeral can be used alone to describe open range or be used in combination to describe closed range.

[0144] The time after feeding of the final reaction of optional operation 325 is the period from the time when all alkaline reagents are added during optional operation 325 to the time when the final reaction of optional operation 325 ends. The end of the final reaction can be based on the time point at which a certain percentage of conversion occurs in substrate. The end of the final reaction can be based on the time point at which a certain percentage of conversion occurs in halohydrin reaction product. For example, the time after feeding of the final reaction of optional operation 325 is the time between the end of the feeding time and the point at which about 70% or higher conversion has occurred in the residual halohydrin reaction product, such as about 75% or higher conversion, such as about 80% or higher conversion, such as about 85% or higher conversion, such as about 90% or higher conversion, such as about 95% or higher conversion, such as about 96% or higher conversion, such as about 97% or higher conversion, such as about 98% or higher conversion, such as about 99% or higher conversion, but other conversion amounts are also considered. Any of the aforementioned numerals can be used alone to describe open-ended ranges or used in combination to describe closed-ended ranges. In some examples, the time after charging of optional operation 325 can be about 20 minutes to about 4 hours, such as about 40 minutes to about 3 hours, such as about 1 hour to about 2 hours, but other time periods are also contemplated. Any of the aforementioned numbers can be used alone to describe an open-ended range or in combination to describe a closed range.

[0145] The total reaction time of the final reaction of optional operation 325 is the sum of the feeding and post-feeding time of optional operation 325. In some embodiments, the total reaction time of the final reaction of optional operation 325 can be from about 0.5 hours to about 8 hours, such as from about 1.5 hours to about 6 hours, from about 2.5 hours to about 4.5 hours, from about 0.5 hours to about 8 hours, or from about 1 hour to about 3 hours, but other time periods are also contemplated. Any of the aforementioned numbers can be used alone to describe an open range or in combination to describe a closed range.

[0146] The reaction conditions of the final reaction of optional operation 325 may include a reactor temperature of about 20°C to about 100°C, such as about 35°C to about 95°C, such as about 50°C to about 90°C, although other temperatures are also contemplated. Any of the aforementioned numbers can be used alone to describe an open range or in combination to describe a closed range. The reactor temperature is the temperature monitored by a temperature probe.

[0147] The reaction conditions of the optional final reaction of operation 325 may also include a reactor pressure measured in absolute pressure. The reactor pressure may be from about 1 bara (about 100 kPa (absolute)) to about 20 bara (about 2000 kPa (absolute)), such as from about 2 bara (about 200 Pa (absolute)) to about 15 bara (about 1500 Pa (absolute)), from about 5 bara (about 500 kPa (absolute)) to about 10 bara (about 1000 kPa (absolute)), or from about 7 bara (about 700 kPa (absolute)) to about 9 bara (about 900 kPa (absolute), although other pressures are contemplated. Any of the foregoing numbers may be used alone to describe an open-ended range or in combination to describe a closed range.

[0148] The reaction conditions of the final reaction of optional operation 325 can include stirring, mixing, agitation or its combination. The device for stirring, mixing or agitation can include batch reaction vessel, semi-batch reaction vessel, continuous static mixer or other suitable devices. Mechanical agitation or jet mixing can be used. In some embodiments, water can be removed from the organic phase (for example, continuously or periodically) by distillation during at least a portion of the final reaction of optional operation 325. Distillation can be azeotropic distillation, so that reaction water is removed from the organic phase.

[0149] The reaction conditions for the final reaction of optional operation 325 may optionally include the use of a non-reactive gas such as nitrogen, argon, or a combination thereof. For example, a mixture comprising a resin mixture, a catalyst, and a solvent may be used with these or other non-reactive gases to degas the various components or otherwise remove oxygen from the mixture.

[0150] At this stage (after optional operation 325), a third composition is provided. The third composition comprises an epoxy resin composition and one or more optional additional components, consists of or is substantially composed of an epoxy resin composition and one or more optional additional components. The epoxy resin composition comprises glycidyl ether, consists of glycidyl ether or is substantially composed of glycidyl ether (as an example of a desired product, such as the glycidyl ether of formula (V-1)). This glycidyl ether can be included in a glycidyl ether obtained during operation 305, a glycidyl ether obtained during operation 310, a glycidyl ether obtained during optional operation 325, or a combination thereof. The one or more additional components in the third composition can include solvents, salts, water, combinations thereof, and other components such as residual halogen alcohol reaction products, consist essentially of them, or consist of them. The final reaction also produces a small amount of water, and this water can remain in the reaction mixture until the final reaction ends and is removed by washing and liquid-liquid separation.

[0151] In some embodiments, and after the optional operation 325, the third composition can be subjected to optional operations to reclaim or otherwise purify the epoxy resin composition present in the third composition. For example, the salt can be separated from the third composition by any suitable method such as filtration, centrifugation or other solid / liquid separation techniques. In addition, or alternatively, the salt can be separated from the third composition by adding an organic solvent and water to the third composition. The water dissolves the salt and the resulting aqueous phase and organic phase can be separated. Suitable organic solvents for separation include ketones, alcohols, aromatic hydrocarbons and halogenated aliphatic compounds, such as methyl isobutyl ketone, methyl ethyl ketone, isopropanol, ethanol, methanol, toluene, xylene, dichloromethane, dichloroethane or mixtures thereof and other. A combination of solvents can be used. The amount of organic solvent and water used for separation can vary widely depending on the properties of the solvent used and the third composition and other factors. The separation of the organic phase and the aqueous phase can be completed by any suitable liquid-liquid separation, including decanters, coalescers and decanting centrifuges and other technologies. If necessary, multiple separation operations can be performed.

[0152] As an illustrative but non-limiting example, water can be added to the third composition and the resulting two-phase mixture can be stirred. Agitation can be stopped and the mixture can be separated into a brine phase and a phase containing the organic resin. The two phases can be separated by any suitable liquid-liquid separation, including decanters, coalescers, and decanting centrifuges, among other techniques. Multiple separation operations can be performed, if desired.

[0153] In addition to the optional separation of the salt, water and organic solvent may also be removed from the third composition. The removal of water and organic solvent is largely dominated by the presence of organic solvent. The removal of water and organic solvent can be carried out by, for example, evaporation or distillation (under appropriate conditions) and other methods. Here, for example, and depending on the material to be removed, the distillation temperature may be from about 50°C to about 150°C, such as from about 70°C to about 160°C, such as from about 80°C to about 130°C; the distillation pressure may be from about 20 mbara (about 2 kPa (absolute)) to about 500 mbara (about 50 kPa (absolute)), such as from about 100 mbara (about 10 kPa (absolute)) to about 400 mbara (about 40 kPa (absolute), such as from about 200 mbara (about 20 kPa (absolute)) to about 300 mbara (about 30 kPa (absolute)); or a combination thereof. Any of the foregoing numbers may be used alone to describe an open range or in combination to describe a closed range. Depending on the epihalohydrin used, other distillation temperatures and pressures are contemplated. Multiple removal operations may be performed.

[0154] The residue remaining after the optional separation / removal operation is the epoxy resin composition (eg, the desired glycidyl ether).

[0155] In some embodiments, a process for forming a resin composition such as an epoxy resin composition (e.g., process 300) can be performed according to the following non-limiting procedure. A mixture of a substrate (or glycidyl substrate) comprising an alcohol (such as bisphenol A), an epihalohydrin (such as epichlorohydrin, ECH), and a solvent (such as an organic solvent as described herein, such as an alcohol, for example, isopropyl alcohol) can be loaded into a reactor. The reactor can be set to a temperature of about 50° C. to about 95° C. and a pressure of about 300 mbara (about 30 kPa (absolute)) to about 500 mbara (about 50 kPa (absolute)). Glycidylation can be initiated by adding a catalyst (such as tetramethylammonium chloride) and an alkaline agent (such as sodium hydroxide) and continuously removing water and ECH from the reactor by azeotropic distillation. The ECH can be recycled back to the reactor. Reaction products are formed and can include glycidyl substrate, halohydrin reaction product, and salt. After the amount of time or conversion level required for the substrate to be converted to the reaction product, a liquid epoxy resin (such as Epikote 828) is added to the reaction mixture containing the reaction product. The resulting resin mixture containing the glycidyl substrate, halohydrin reaction product, salt, and unreacted ECH is subjected to distillation to remove unreacted ECH. The above process can be the reaction sub-process 205.

[0156] The resin mixture can be discharged from the reactor (via a line, such as line 210) and pumped to a different reactor where a post-processing sub-process (e.g., post-processing sub-process 215) can occur. An organic solvent, such as methyl isobutyl ketone (MIBK), is added to the resin mixture and water washed to remove salts from the resin mixture. The aqueous phase is separated from the organic phase. The organic phase, which includes at least a portion of the resin mixture, is then subjected to a final reaction. Here, the reactor can be set to a temperature of about 50° C. to about 95° C. and a pressure of about 700 mbara (about 70 kPa (absolute)) to about 1100 mbara (about 110 kPa (absolute)). The final reaction can be initiated by adding an alkaline agent (such as sodium hydroxide). The halohydrin reaction product of the resin mixture is closed-circulated to form the desired glycidylation product. The composition containing the glycidylation product also includes salts, which can be removed by adding an organic solvent (such as MIBK), washing with water, and recovering the organic phase. The organic phase can then be distilled to remove residual organic solvent and water to provide an epoxy resin composition. The resulting epoxy resin composition can be a liquid epoxy resin.

[0157] Resin compositions (eg, those formed by process 300 ) may be used with any suitable type of polymer in which epoxide reactants are commonly used, including, for example, polymers used in the coatings, composites, or adhesives industries.

[0158] The resin compositions formed by the processes described herein can be used as adhesives, paints, sealants, and other applications. For example, the compositions can be used in construction, concrete, and cement installation, such as high-gloss concrete installation. Another use includes coating metals. Other end-use applications of the compositions described herein include, but are not limited to: cellulose, lignocellulose, and wood products; plastics; fabrics (woven and non-woven); and glass. The resin compositions can generally be used to produce composite materials, adhesives, insulation materials, molded products, adhesives, laminates, and other articles and products.

[0159] The embodiments described herein also relate to processes for separating desired and available substrates from raw materials, waste streams, and recycle streams. As described above, non-conventional substrates are typically derived from very crude and complex mixtures. For example, the bio-derived alcohol may be derived from a lignin source or a lignin waste stream (such as industrial lignin, kraft lignin, organosolv lignin, hydrolyzed lignin, and others) and the alcohol present in the epoxy resin or phenolic resin may be derived from recycled epoxy resin and phenolic resin, respectively. Unlike conventional techniques for extracting alcohol (e.g., glycidylated substrates) from complex mixtures (such as bio-derived crude materials and recycled or waste streams of epoxy and phenolic resins), the embodiments described herein may not require a depolymerization operation. Furthermore, the embodiments described herein may not require separation or fractionation techniques, which at least involve the use of solvents that are not used in the downstream glycidylation process. However, it is contemplated that the embodiments described herein may be used in conjunction with depolymerization operations and separation or fractionation techniques that utilize solvents.

[0160] The embodiment of separation process as herein described (for example, following process 400 and process 500) utilizes epihalohydrin to dissolve the required substrate existing in crude feed as extraction agent.As known to the inventors, epihalohydrin (such as epichlorohydrin) is not yet as extraction agent or extraction solvent due to for example its relatively high reactivity.Epihalohydrin is not considered to be typical extraction solvent, is not also considered to be attractive selection in every other available solvent, because for example it is difficult to use it.But, when epihalohydrin was used for the production of composition epoxy resin, using it as extraction agent / solvent required substrate is separated for subsequent glycidylation with crude feed, waste stream and circulation stream and can provide advantage.

[0161] In addition, use epihalohydrin to extract the substrate for glycidylation in substrate source and ensure the solubility of the substrate for downstream glycidylation operation, wherein usually only use epihalohydrin as solvent and reagent.When using other solvents, such guarantee cannot be obtained, because the solubility of the fraction extracted in epihalohydrin may still be lower, making downstream glycidylation become loaded down with trivial details and very difficult to operate.

[0162] In addition, because epihalohydrin is used for extracting required base material in crude material, therefore do not need extra solvent to produce epoxy resin, because epihalohydrin is used for producing epoxy resin.Herein, embodiment as herein described can need not complicated additional separation process and storage facility, if use the solvent beyond epihalohydrin, then will need such complicated additional separation process and storage facility.Therefore, production cost and lower energy cost can be realized.When extracting (or separating) required base material (such as phenolic material) from base material source after not removing epihalohydrin and by the mixture of epihalohydrin and required base material as it is for glycidylation reaction, especially so.

[0163] In addition, the separation process can be applied to various types of alcohols (such as alkyl alcohols, polyols, phenols and polyphenols). Like other fractionation techniques and depolymerization techniques, the separation process can be applied without complex catalysts, complex parameters and complex equipment.

[0164] The embodiments described for separating substrates (e.g., alcohols and phenols) from complex mixtures can be combined with embodiments for forming glycidyl ethers. Furthermore, the process of separating substrates (e.g., alcohols and phenols) from complex mixtures can be combined with conventional processes for forming glycidyl ethers. That is, the substrates separated by the embodiments described herein can be fed to downstream upgrading processes, such as conversion into epoxy resin compositions, and other upgrading processes.

[0165] Figure 4 is a flow chart illustrating selected operations of a process 400 for separating a substrate from a substrate source, in accordance with at least one embodiment of the present disclosure.

[0166] Process 400 is included in when operation 405 epihalohydrin is introduced together with substrate source.Suitable substrate source for operation 405 can comprise raw material, waste stream or circulating stream, and other mixtures and complex mixture.This type of substrate source can comprise any suitable substrate source, and this substrate source comprises the substrate (compound) containing at least one hydroxyl (-OH), is basically made up of or by the substrate (compound) comprising at least one hydroxyl (-OH).That is, the substrate source for operation 405 can contain substrate or compound, such as alcohol, polyol, phenol and polyphenol.This type of substrate source can be biological origin or non-biological origin.

[0167] The substrate source can be a mixture of complex compositions. As a mixture or complex mixture, the substrate source includes unwanted materials or components, such as very high molecular weight polymers, insolubles, salts, and other materials and components. Such unwanted materials or components are commonly found in kraft lignin, hydrolyzed lignin, recycle streams from pyrolysis or solvolysis processes, and other substrate sources.

[0168] Although for simplicity, this article refers to Figure 4 and Figure 5 The described embodiments are discussed with reference to phenols, polyphenols, or phenolic moieties, but it will be understood that any suitable substrate containing at least one hydroxyl group (-OH) may be used, such as alkyl alcohols and aliphatic alcohols (where the hydroxyl group is attached to a non-aromatic carbon), as well as aromatic alcohols (such as phenols, where the hydroxyl group is attached to an aromatic carbon).

[0169] The substrate source that can be used for the embodiments described herein may include biomass. Illustrative but non-limiting examples of biomass include, for example, materials, by-products and wastes generated from agricultural and forestry processes, such as agricultural materials and residues (e.g., straw and corn), energy crops (e.g., straw and bamboo), forest residues (e.g., by-products and wastes from forest harvesting, such as wood chips), plant- and algae-based materials and residues and the like, and combinations thereof. In some embodiments, biomass includes wood, leaves, pulp, stems, grass materials, shrubs, branches, energy crops, vegetables, fruits, flowers, grains, herbaceous crops, bark, needles, logs, trees and combinations thereof. Additionally or alternatively, biomass includes municipal solid waste, by-products and wastes from wood processing, by-products and wastes from papermaking or wood processing, by-products and wastes from agricultural and forestry activities, rotational crops, wood, wood chips, sawdust, straw, firewood, wood materials, paper, waste paper, yard waste and the like. Thus, alcohols (eg, polyphenols) present in such materials (biomass) can be used with the embodiments described herein.

[0170] Suitable substrate sources for operation 405 include any suitable lignin sources, including lignin sources that may not be completely dissolved in epihalohydrins. Suitable substrate sources for operation 405 include industrial lignin, kraft lignin, organosolv lignin, hydrolyzed lignin, its combination, and other lignin sources. Industrial lignin refers to natural lignin or original lignin derivatives obtained due to lignocellulosic biomass delignification process. Kraft lignin refers to industrial lignin obtained from kraft pulp by converting bio-based substrates (such as one of them mentioned above, such as wood) into pulp. Organosolv lignin refers to the lignin obtained by organosolv, and organosolv is a pulping technology using an organic solvent to dissolve lignin and hemicellulose. Hydrolyzed lignin refers to the by-products of their pre-treatment processes from pre-treatment processes such as cellulosic ethanol plants, and generally includes lignin, unreacted cellulose, monosaccharides and oligosaccharides. Except lignin, other suitable phenol-rich fractions also can be substrate sources for operation 405.

[0171] Suitable substrate sources for operation 405 include waste streams and recycle streams comprising resins such as epoxy resins, phenolic resins, or combinations thereof, as well as other resins. Such waste streams and recycle streams can come from pyrolysis or solvent decomposition processes designed for recycling polymer waste. Such waste streams and recycle streams include alcohols (such as phenols and alkyl alcohols) that can be separated. Such waste streams and recycle streams can be waste / recycle streams used or generated during resin processing or manufacturing. A mixture of substrate sources can be used as the substrate source for process 400.

[0172] Suitable epihalohydrins for use in operation 405 include those represented by formula (VI):

[0173]

[0174] In formula (VI), R 5 R of the epihalohydrin shown in formula (VI) is hydrogen, an unsubstituted hydrocarbon group or a substituted hydrocarbon group. 5 The group may include 1 to 20 carbon atoms, such as 1 to 10 carbon atoms, such as 1 to 4 carbon atoms. The X group in formula (VI) is a halogen, such as fluorine, chlorine, bromine or iodine, such as chlorine or bromine. In some embodiments, the epihalohydrin comprises epichlorohydrin (X in formula (VI) = Cl and R 5 =H; CAS No. 106-89-8), epibromohydrin (X=Br and R in formula (VI) 5 =H; CAS No. 3132-64-7) or a combination thereof.

[0175] In some embodiments, the mass ratio of the substrate source and epihalohydrin for process 400 is about 10: 1 to about 1: 10, such as about 5: 1 to about 1: 5, such as about 3: 1 to about 1: 3, such as about 2: 1 to about 1: 2, such as about 1: 1. In at least one embodiment, the mass ratio of the substrate source and epihalohydrin is about 1: 1 to about 1: 10, such as about 1: 2 to about 1: 9, such as about 1: 3 to about 1: 8, such as about 1: 4 to about 1: 7, such as about 1: 5 to about 1: 6. Consider other mass ratios. Any of the aforementioned numerals can be used alone to describe open-ended scopes or used in combination to describe closed-ended scopes.

[0176] Introduction of the epihalohydrin with the substrate causes at least a portion of the epihalohydrin to contact the desired substrate present in the substrate source, enabling separation of the desired substrate.

[0177] Operation 405 can further include a mixing subprocess. The mixing subprocess of operation 405 can include any suitable condition so that the substrate source can fully contact with epihalohydrin. For example, epihalohydrin and substrate source can use any suitable device to stir, mix, stir or its combination. The device for stirring, mixing or stirring can include batch reaction vessel, semi-batch reaction vessel, continuous static mixer or other suitable devices. Mechanical agitation or jet mixing can be used.

[0178] The effective conditions of the mixed subprocess of operation 405 also can comprise mixing, stirring or agitating mixture under selected temperature and pressure.For example, epihalohydrin and substrate source are positioned at the container wherein and can be set to for about-10 ℃ to about 100 ℃ container temperature, such as about 0 ℃ to about 80 ℃, such as about 10 ℃ to about 60 ℃, such as about 20 ℃ to about 50 ℃, such as about 25 ℃ to about 40 ℃, but also consider other temperatures.Any aforementioned numeral can be used alone to describe open range or be used in combination to describe closed range.Container temperature is the temperature monitored by temperature probe.

[0179] The container pressure measured in absolute pressure units can be from about 500 mbara (about 50 kPa (absolute)) to about 3,000 mbara (about 300 kPa (absolute)), such as from about 700 mbara (about 70 kPa (absolute)) to about 2,500 (about 250 kPa (absolute)), such as from about 800 mbara (about 80 kPa (absolute)) to about 2,000 (about 200 kPa (absolute)), such as from about 850 mbara (about 85 kPa (absolute)) to about 1,200 mbara (about 120 kPa (absolute)). (absolute)), such as about 900 mbara (about 90 kPa (absolute)) to about 1,100 mbara (about 110 kPa (absolute)), such as about 900 mbara (about 90 kPa (absolute)) to about 1,000 mbara (about 100 kPa (absolute)) or about 1,000 mbara (about 100 kPa (absolute)) to about 1,100 mbara (about 110 kPa (absolute)), although other pressures are also contemplated. Any of the foregoing numbers can be used alone to describe an open-ended range or in combination to describe a closed range.

[0180] The total time for mixing, stirring, or agitating during the mixing sub-process of operation 405 can be from about 10 minutes to about 24 hours, such as from about 30 minutes to about 15 hours, for example, from about 1.5 hours to about 6 hours, from about 2.5 to about 4.5 hours, from about 30 minutes to about 8 hours, from about 45 minutes to about 3 hours, or from about 1 hour to about 2 hours, although other time periods are also contemplated. Any of the foregoing numbers can be used alone to describe an open-ended range or in combination to describe a closed range.

[0181] After substrate source, epihalohydrin and acid fully mix, can separate gained mixture.Therefore, process 400 is further included in when operation 410 substrate (required substrate) and epihalohydrin are separated with substrate source.In operation 410, the substrate separated with substrate source comprises at least one hydroxyl, such as alcohol of biological origin, the alcohol present in the resin waste stream, the alcohol present in the resin circulation flow or its combination.This type of alcohol can comprise phenol and aliphatic alcohol and other.In operation 410, the substrate separated with substrate source can be the substrate (for example, glycidyl substrate) for process 300.

[0182] Operation 410 is carried out under the condition that effectively substrate is separated from substrate source.The condition of operation 410 may include any suitable condition and technology.For example, the separation process of operation 410 may include any suitable separation technology, such as solid / liquid technology, including mechanical or gravity separation, such as filtration, vacuum filtration, centrifuge, decanter, decanting centrifuge, its combination, and other technologies.Can be assisted by the solid filter cake formed by suppressing separation.Separation can be carried out one or more, and each filtration optionally uses extra epihalohydrin.Porous surface can be used to filter, filtrate (liquid containing required substrate) is pumped to a side of porous surface from the mixture of epihalohydrin and substrate source, and substrate source is stayed on the opposite side of substrate surface as retentate (solid or filter cake).As an example, epihalohydrin and substrate source can be separated by, for example, filtering, to provide the filtrate containing epihalohydrin soluble substrate and the retentate containing epihalohydrin insoluble fraction.

[0183] The porous surface can be a membrane or frit made of any suitable material such as ceramic, glass or other materials.The pores of the porous membrane can be selected to separate substrates of a specific size or range (eg, weight average molecular weight or range) from a substrate source.

[0184] The separation process of operation 410 may be performed one or more times. After the desired number of separations, the filtrate containing the epihalohydrin and the desired substrate is retained, and the retentate (the filter cake containing the coarse component of the substrate source) may be discarded or used for other purposes.

[0185] If desired, the resulting mixture of epihalohydrin and substrate can be used directly in an upgrading process, such as glycidylation, such as those described herein for forming the resin composition.

[0186] Additionally or alternatively, the epihalohydrin may be removed from the substrate at optional operation 415. The epihalohydrin may be removed from the substrate by any suitable technique, such as distillation or evaporation, among others. Here, for example, and depending on the epihalohydrin to be removed or other factors, optional operation 415 may include a distillation temperature of about 50°C to about 160°C, such as about 70°C to about 140°C, such as about 80°C to about 120°C, such as about 90°C to about 110°C; the distillation pressure may be about 100 mbara (about 10 kPa (absolute)) to about 700 mbara (about 70 kPa (absolute)), such as about 200 mbara (about 20 kPa (absolute)) to about 500 mbara (about 50 kPa (absolute)); or a combination thereof. Any of the foregoing numbers can be used alone to describe an open range or in combination to describe a closed range. Depending on the epihalohydrin used, other distillation temperatures and pressures are contemplated. The removal process of optional operation 415 may be performed one or more times. The epihalohydrin may be recovered and used in other separation processes, in glycidylation reactions (e.g., process 300), and other uses. After distillation, the desired substrate (hydroxyl-containing substrate) is provided.

[0187] Additionally or alternatively, partial distillation can be used for optional operation 415 to obtain a suitable epihalohydrin / substrate ratio for subsequent glycidylation reaction.After partial distillation, the mixture of epihalohydrin and substrate can undergo glycidylation (e.g., process 300).

[0188] In some embodiments, a process for separating a substrate comprising at least one hydroxyl group from a substrate source (e.g., process 400) can be performed according to the following non-limiting procedure. A substrate source (e.g., lignin) and an epihalohydrin (e.g., ECH) are added to a batch reaction vessel and stirred for about 1 hour at a temperature of about 25° C. and a pressure of about 1,000 mbar (about 100 kPa (absolute)). The resulting mixture is filtered by vacuum. The filtrate containing the epichlorohydrin-soluble substrate and ECH is distilled at a temperature of about 90° C. to about 110° C. and a pressure of about 200 mbara (about 20 kPa (absolute)) to about 500 mbara (about 50 kPa (absolute)) to remove ECH from the desired substrate. The retentate contains an epihalohydrin-insoluble portion.

[0189] Process 400 is capable of separating hydroxyl-containing substrates (e.g., glycidylated substrates) from substrate sources (such as feedstocks, recycle streams, and waste streams). Substrates having hydroxyl groups attached to aromatic carbons, hydroxyl groups attached to non-aromatic carbons (e.g., alkyl hydroxyl groups) can be separated. In some examples, the bio-derived alcohols separated by process 400 and alcohols present in recycle / waste streams can include polyols (compounds containing more than one alcohol), polyphenols (compounds containing more than one phenol, such as bisphenols, triphenols, tetraphenols, etc.), combinations thereof, and others. The substrates separated by the processes described herein (e.g., process 400) can be fed to downstream upgrading processes, such as conversion into resin compositions (such as epoxy resin compositions, such as by process 300), and other upgrading processes. Additionally or alternatively, the separated substrates can be fed to conventional processes for forming resin compositions.

[0190] Figure 5 is a flow chart illustrating selected operations of a process 500 for separating a substrate from a substrate source, in accordance with at least one embodiment of the present disclosure.

[0191] Process 500 includes introducing acid and epihalohydrin together with a substrate source when operating 505. Suitable substrate sources for operating 505 can include those substrate sources as described herein (e.g., substrate sources for operation 405 of process 400). Generally speaking, the substrate source for operating 505 includes, consists essentially of, or consists of a substrate (compound) such as alcohol, polyol, phenol and polyphenol comprising at least one hydroxyl group (-OH). The substrate source can be biologically derived or non-biologically derived.

[0192] Suitable epihalohydrins for operation 505 include those represented by formula (VI) as described herein. For example, epichlorohydrin (X=Cl and R in formula (VI)) can be used. 5 =H; CAS No. 106-89-8), epibromohydrin (X=Br and R in formula (VI) 5 =H; CAS No. 3132-64-7) or a combination thereof.

[0193] In some embodiments, the mass ratio of the substrate source and epihalohydrin for process 500 is about 10: 1 to about 1: 10, such as about 5: 1 to about 1: 5, such as about 3: 1 to about 1: 3, such as about 2: 1 to about 1: 2, such as about 1: 1. In at least one embodiment, the mass ratio of the substrate source and epihalohydrin is about 1: 1 to about 1: 10, such as about 1: 2 to about 1: 9, such as about 1: 3 to about 1: 8, such as about 1: 4 to about 1: 7, such as about 1: 5 to about 1: 6. Consider other mass ratios. Any of the aforementioned numerals can be used alone to describe open-ended scopes or used in combination to describe closed-ended scopes.

[0194] The acid used in operation 505 may include any suitable acid, such as an inorganic acid, an organic acid, an ion thereof, or a combination thereof. Illustrative but non-limiting examples of inorganic acids include hydrochloric acid (HCl), sulfuric acid (H2SO4), nitric acid (HNO3), hydrobromic acid (HBr), hydroiodic acid (HI), phosphoric acid (H3PO4), an ion thereof, or a combination thereof. Illustrative but non-limiting examples of organic acids include C1-C 25 Carboxylic acids, such as C3-C 10 Carboxylic acids, such as C3-C7 carboxylic acids, such as oxalic acid, citric acid, formic acid, lactic acid, acetic acid, uric acid, malic acid, tartaric acid, trifluoroacetic acid, ions thereof, or combinations thereof. Additionally or alternatively, sulfonic acids such as C1-C 25 Sulfonic acids, such as C3-C 10 Sulfonic acid, such as C3-C7 sulfonic acid, such as trifluorosulfonic acid, or p-methyl benzenesulfonic acid or its combination.In some embodiments, pH can maintain the pH value higher than the decomposition pH (at a specific temperature) of epihalohydrin in water.The decomposition pH of epihalohydrin in water depends on temperature, and can be easily checked by monitoring heat release and measuring temperature.

[0195] Acid solution can be added in substrate source, until pH reaches desired value and maintains this value so that one or more hydroxyl moieties (such as phenolic hydroxyl moiety) in substrate source are protonated.Herein, as mentioned above, the epihalohydrin temperature in the monitoring water should be such that for example pH is not less than the pH when observing the exothermic decomposition of epihalohydrin.The suitable pH value of acid solution can be approximately 7.5 or less, such as approximately 7 or less, such as approximately 1 to approximately 6.5, such as approximately 1 to approximately 5, approximately 2 to approximately 4, approximately 1 to approximately 3, or approximately 2 to approximately 3, but also considers other pH values ​​or scopes.Any aforementioned numeral can be used separately to describe open range or be used in combination to describe closed range.Can select pH to make epihalohydrin not very reactive.

[0196] The use of acid can improve the extraction yield from various substrate sources, such as lignin sources, such as kraft lignin. Acidification lowers the pH, causing the hydroxyl moieties of the substrate source, such as phenolic hydroxyl moieties, to be protonated, resulting in higher solubilization of the desired substrate having hydroxyl moieties.

[0197] Since epihalohydrins are unstable under acidic conditions, the use of acids in the presence of epihalohydrins can be problematic. However, it has been unexpectedly discovered that the acid can selectively protonate the hydroxyl moieties of the substrate source rather than undergoing ring opening of the epihalohydrin.

[0198] In some embodiments, the acid can be added as a solution in a suitable solvent (e.g., water or an organic solvent that effectively dissolves the acid) at any suitable concentration, such as from about 0.01 M to about 18 M, from about 0.1 M to about 9 M, from about 3 M to about 12 M, from about 6 M to about 15 M. Higher or lower concentrations can be utilized. Any of the foregoing numbers can be used alone to describe an open-ended range or in combination to describe a closed range.

[0199] In some embodiments, the mass ratio of the acid solution to the substrate source is from about 0.01:1 to about 1:1, such as from about 0.1:1 to about 0.5:1, such as from about 0.2:1 to about 0.4:1.

[0200] In some embodiments, the acid can be added to the substrate source before, during, after, or a combination thereof. The introduction of the epihalohydrin can be carried out in the same or different apparatus as that used to introduce the acid into the substrate source.

[0201] Operation 505 can further include a mixing subprocess. The mixing subprocess of operation 505 can include any suitable condition so that the substrate source can fully contact with epihalohydrin. For example, the mixture can use any suitable device to stir, mix, agitate or its combination. The device for stirring, mixing or stirring can include batch reaction vessel, semi-batch reaction vessel, continuous static mixer or other suitable devices. Mechanical agitation or jet mixing can be used.

[0202] The effective conditions of the mixing sub-process of operation 505 may also include mixing, stirring, or agitating the mixture at a selected temperature and pressure. For example, the container may be set to a container temperature of about -10°C to about 100°C, such as about 0°C to about 80°C, such as about 10°C to about 60°C, such as about 20°C to about 50°C, such as about 25°C to about 40°C, although other temperatures are also contemplated. Any of the aforementioned numbers may be used alone to describe an open range or in combination to describe a closed range. The container temperature is the temperature monitored by a temperature probe.

[0203] The vessel pressure (measured in absolute pressure units) during the mixing sub-process of operation 505 can be from about 500 mbara (about 50 kPa (absolute)) to about 3,000 mbara (about 300 kPa (absolute)), such as from about 700 mbara (about 70 kPa (absolute)) to about 2,500 (about 250 kPa (absolute)), such as from about 800 mbara (about 80 kPa (absolute)) to about 2,000 (about 200 kPa (absolute)), such as from about 850 mbara (about 85 kPa (absolute)) to about 1,200 mbara (about 1,200 kPa (absolute)). (about 120 kPa (absolute)), such as about 900 mbara (about 90 kPa (absolute)) to about 1,100 mbara (about 110 kPa (absolute)), such as about 900 mbara (about 90 kPa (absolute)) to about 1,000 mbara (about 100 kPa (absolute)) or about 1,000 mbara (about 100 kPa (absolute)) to about 1,100 mbara (about 110 kPa (absolute)), but other pressures are also contemplated. Any of the foregoing numbers can be used alone to describe an open-ended range or in combination to describe a closed range.

[0204] The total time for mixing, stirring, or agitating during the mixing sub-process of operation 505 can be from about 10 minutes to about 24 hours, such as from about 30 minutes to about 15 hours, such as from about 1.5 hours to about 6 hours, from about 2.5 to about 4.5 hours, from about 30 minutes to about 8 hours, from about 45 minutes to about 3 hours, or from about 1 hour to about 2 hours, although other time periods are also contemplated. Any of the foregoing numbers can be used alone to describe an open-ended range or in combination to describe a closed range.

[0205] After substrate source, epihalohydrin and acid fully mix, gained mixture can be separated.Therefore, process 500 is further included in when operation 510 substrate (required substrate) and epihalohydrin are separated with substrate source.In operation 510, the substrate separated with substrate source comprises at least one hydroxyl, such as alcohol of biological origin, the alcohol present in the resin waste stream, the alcohol present in the resin circulation stream or its combination.This type of alcohol can comprise phenol and aliphatic alcohol and other.In operation 510, the substrate separated with substrate source can be the substrate (for example, glycidyl substrate) for process 300.

[0206] Operation 510 is carried out under the condition that effectively substrate is separated from substrate source.The condition of operation 510 may comprise any suitable condition and technology, such as those conditions described in this paper about the operation 410 of process 400.For example, the separation process of operation 510 may comprise any suitable separation technology, such as solid / liquid technology, comprises machinery or gravity separation, such as filtration, vacuum filtration, centrifuge, decanter, decanting centrifuge, its combination and other technologies.Can assist separation by the solid filter cake formed by suppressing.Separation can be carried out one or more, and each filtration optionally uses extra epihalohydrin.The filtration of operation 510 can use any suitable porous surface to complete, such as those described in the operation 410 of process 400 above.

[0207] The separation process of operation 510 can be performed one or more times. After the required number of separations, the filtrate comprising epihalohydrin and required substrate is retained, and the retentate (comprising the filter cake of the coarse component with substrate source) can be discarded or used for other purposes. When using acid, the filtrate also can contain acid.

[0208] If desired, the mixture comprising the epihalohydrin and the substrate can be used directly in an upgrading process such as glycidylation, such as those described herein for forming the resin composition.

[0209] Additionally or alternatively, epihalohydrin may be removed from the substrate at optional operation 515. Epihalohydrin may be removed from the substrate by any suitable technique, such as distillation or evaporation, as discussed above with respect to optional operation 415 of process 400. Here, for example, and depending on the epihalohydrin to be removed or other factors, optional operation 415 may include a distillation temperature of about 50° C. to about 160° C., such as about 70° C. to about 140° C., such as about 80° C. to about 120° C., such as about 90° C. to about 110° C.; the distillation pressure may be about 100 mbara (about 10 kPa (absolute)) to about 700 mbara (about 70 kPa (absolute)), such as about 200 mbara (about 20 kPa (absolute)) to about 500 mbara (about 50 kPa (absolute)); or a combination thereof. Any of the foregoing numbers may be used alone to describe an open range or in combination to describe a closed range. For optional operation 515, other ranges and values ​​of the above variables such as temperature, pressure, and time may be considered, such as those described herein for optional operation 415 of process 500.

[0210] The optional removal process of operation 515 may be performed one or more times. The epihalohydrin may be recovered and used in other separation processes, for glycidylation reactions (e.g., process 300), and other uses. After distillation, the desired substrate (hydroxyl-containing substrate) is provided.

[0211] Additionally or alternatively, partial distillation can be used for optional operation 515 to obtain a suitable epihalohydrin / substrate ratio for subsequent glycidylation reaction.After partial distillation, the mixture of epihalohydrin and substrate can undergo glycidylation (e.g., process 300).

[0212] In some embodiments, the acid can be removed by a suitable process. For example, when the acid is volatile (such as acetic acid, HCl, and others), the excess acid can be removed by distillation. Additionally or alternatively, when the desired substrate (hydroxyl-containing substrate) undergoes glycidylation, the acid can be quenched by adding a large amount of an alkaline reagent for glycidylation. Because the alkaline reagent can quench the acid, and in some embodiments, process 500 may not require an acid removal operation.

[0213] In some embodiments, a process (e.g., process 500) for separating a substrate comprising at least one hydroxyl group from a substrate source can be performed according to the following non-limiting procedures. A substrate source (e.g., lignin) can be mixed with an acetic acid solution (pH of about 3) in a batch reaction vessel. An epihalohydrin, such as epichlorohydrin, can be added, and the resulting mixture can be stirred for about 1 hour at a temperature of about 25° C. and a pressure of about 1,000 mbara (about 100 kPa (absolute)). The resulting mixture can be filtered by means of a vacuum. The filtrate containing substrate, acetic acid, and epichlorohydrin can be distilled at a temperature of about 90° C. to about 110° C. and a pressure of about 100 mbara (about 10 kPa (absolute)) to about 500 mbara (about 50 kPa (absolute)) to remove epichlorohydrin and acetic acid from the desired substrate.

[0214] Process 500 is capable of separating hydroxyl-containing substrates (e.g., glycidylated substrates) from substrate sources such as feedstocks, recycle streams, and waste streams. Substrates having hydroxyl groups attached to aromatic carbons, hydroxyl groups attached to non-aromatic carbons (e.g., alkyl hydroxyl groups) can be separated. In some examples, the bio-derived alcohols separated by process 500 and the alcohols present in the recycle / waste streams can include polyols (compounds containing more than one alcohol), polyphenols (compounds containing more than one phenol such as bisphenols, triphenols, tetraphenols, etc.), combinations thereof, and others. The substrates separated by the processes described herein (e.g., process 500) can be fed to downstream upgrading processes, such as conversion into resin compositions (such as epoxy resin compositions, such as by process 300), and other upgrading processes. Additionally or alternatively, the separated substrates can be fed to conventional processes for forming resin compositions.

[0215] The separation processes described herein (eg, process 400 and process 500 ) can be used to extract hydroxyl-containing substrates (eg, alcohols, polyols, phenols, polyphenols, or combinations thereof) of various molecular weights.

[0216] The following examples are set forth so as to provide those skilled in the art with a complete disclosure and description of how to make and use the embodiments of the present disclosure and are not intended to limit the scope of the embodiments of the present disclosure. Efforts have been made to ensure accuracy of the numerical values ​​used, but some experimental errors and deviations should be accounted for.

[0217] Examples

[0218] Test Method

[0219] Characterization of Products Formed by Example Processes

[0220] Epoxy group content (EGC) is determined according to ASTM D1652-11. This method allows the determination of 1,2-epoxy groups in epoxy resins in a range of 200 to 8000 mmol / kg. Perchloric acid is used as a titrant together with the quaternary ammonium halide tetraethylammonium bromide (TEAB). For the EGC titration, the required mass of sample is dissolved in a fixed amount of DCM and acetic acid with the addition of an excess of TEAB. This solution is titrated with a 0.01 M solution of perchloric acid in acetic acid until the inflection point is reached. The amount of epoxy functionality (in mmol / kg) is calculated using the volume of perchloric acid added.

[0221] Hydrolyzable chlorine and inorganic chlorine were determined according to ASTM-D1726. This method describes the determination of hydrolyzable chlorine in epoxy resins down to a concentration of 7 mg / kg. For the titration, the required mass of sample (after dissolution in tetrahydrofuran if the resin is solid) is mixed with a fixed amount of toluene and 0.1 mol / L methanolic potassium hydroxide solution. The solution is then refluxed for the specified time. After adding acetic acid, the liberated chloride is potentiometrically titrated with standard silver nitrate solution, and the hydrolyzable chlorine content of the sample is calculated based on the data obtained.

[0222] The viscosity of epoxy resins was determined according to ASTM D-445, which describes the standard test method for measuring the kinematic viscosity, ν, of petroleum products.

[0223] Example 1: Glycidylation

[0224] After the reaction sub-process, LER is added for glycidylation to realize the post-treatment sub-process. The general reaction scheme for glycidylation of lignin phenol moiety (example alcohol-containing substrate) to lignin glycidyl ether moiety is shown in Scheme 2. In Scheme 2, A is lignin phenol moiety, B is halohydrin reaction product, and C is lignin glycidyl ether. L refers to lignin, R a and R b is an R group as described herein, and the alkaline agent is aqueous sodium hydroxide (stoichiometric).

[0225] Option 2

[0226]

[0227] Example 1A. For this glycidylation experiment, a bio-derived polyphenol was used as the substrate (Extracted Kraft Lignin #1). Here, the substrate was removed from the substrate source (kraft lignin) by extraction as described herein and as shown in the following non-limiting Example 2.

[0228] The synthesis of the glycidyl ether of Example 1A was carried out according to the following procedure. A polyphenol (approximately 5 g) and a stoichiometric excess of epichlorohydrin (approximately 20 g) were added to a 100 mL round-bottom flask equipped with an overhead condenser. The resulting mixture was stirred at approximately 450 rpm using a magnetic stirrer and the reactor was heated to the desired reaction temperature (approximately 70° C.). The coupling catalyst, tetrabutylammonium chloride (TBAC, approximately 50% aqueous solution, approximately 0.4 g), was added and the reaction mixture was stirred for approximately 30 minutes. Sodium hydroxide (approximately 50% aqueous solution, approximately 2.6 g) was then added to the reaction mixture over a period of approximately 2 hours. The reaction mixture was allowed to continue stirring for a post-reaction period of approximately 30 minutes. A liquid epoxy resin (Epikote 862, approximately 5.5 g) was added to the reaction mixture at a weight ratio of approximately 1:1 relative to the formed epoxy product. Excess epichlorohydrin and water were removed using rotary evaporation. The solvent and water were added to the mixture, stirred, and the phases separated. The water wash was repeated two more times to remove more water-soluble components. The solvent was removed from the organic phase by rotary evaporation (about 90° C. and about 60 mbara).The sample was then heated in an oven to about 120° C. and stripped with nitrogen for about 30 minutes to provide the bioderived glycidyl ether.

[0229] Example 1B. For this glycidylation experiment, a biosourced polyphenol was used as the substrate (Extracted Kraft Lignin #1). Here, the substrate was removed from the substrate source (Kraft Lignin) by extraction as described herein and as shown in the following non-limiting Example 2.

[0230] The synthesis of the glycidyl ether of Example 1B was carried out according to the following procedure. A polyphenol (approximately 25 g) and a stoichiometric excess of epichlorohydrin (approximately 100 g) were added to a round-bottom flask equipped with an overhead condenser. The resulting mixture was stirred at approximately 450 rpm using a magnetic stirrer and the reactor was heated to the desired reaction temperature (approximately 70° C.). A coupling catalyst, tetramethylammonium chloride (TMAC, approximately 50% aqueous solution, approximately 2 g), was added and the reaction mixture was stirred for approximately 30 minutes. Sodium hydroxide (approximately 50% aqueous solution, approximately 13.0 g) was then added to the reaction mixture over a period of approximately 2 hours. The reaction mixture was allowed to continue stirring for a post-reaction time of approximately 30 minutes. A liquid epoxy resin (Epikote 862, approximately 27.8 g) was added to the reaction mixture at a weight ratio of approximately 1:1 relative to the formed epoxy product. Excess epichlorohydrin and water were removed using rotary evaporation. The solvent and water were added to the mixture, stirred, and the phases separated. The water wash was repeated two more times to remove more water-soluble components. The solvent was removed from the organic phase by rotary evaporation (about 90° C. and about 60 mbara).The sample was then heated in an oven to about 120° C. and stripped with nitrogen for about 30 minutes to provide the bioderived glycidyl ether.

[0231] Example 1C. For this glycidylation experiment, a biosourced polyphenol was used as the substrate (acid-extracted kraft lignin #3). Here, the substrate was removed from the substrate source (kraft lignin) by extraction using acidification as described herein and as shown in the following non-limiting Example 2.

[0232] The synthesis of the glycidyl ether of Example 1C was carried out according to the following procedure. A polyphenol (approximately 5 g) and a stoichiometric excess of epichlorohydrin (approximately 20 g) were added to a round-bottom flask equipped with an overhead condenser. The resulting mixture was stirred at approximately 450 rpm using a magnetic stirrer and the reactor was heated to the desired reaction temperature (approximately 70° C.). A coupling catalyst, TMAC (approximately 50% aqueous solution, approximately 0.4 g), was added and the reaction mixture was stirred for approximately 30 minutes. Sodium hydroxide (approximately 50% aqueous solution, approximately 1.72 g) was then added to the reaction mixture over a period of approximately 2 hours. The reaction mixture was allowed to continue stirring for a post-reaction time of approximately 30 minutes. A liquid epoxy resin (Epikote 862, approximately 5.5 g) was added to the reaction mixture at a weight ratio of approximately 1:1 relative to the formed epoxy product. Excess epichlorohydrin and water were removed using rotary evaporation. The solvent and water were added to the mixture, stirred, and the phases separated. The water wash was repeated two more times to remove more water-soluble components. The solvent was removed by rotary evaporation (about 90° C. and about 60 mbara).The sample was then heated in an oven to about 120° C. and stripped with nitrogen for about 30 minutes to provide the bioderived glycidyl ether.

[0233] Example 1D. For this glycidylation experiment, a biosourced polyphenol was used as the substrate (acidified, extracted kraft lignin #3). Here, the substrate was removed from the substrate source (kraft lignin) by extraction using acidification as described herein and as shown in the following non-limiting Example 2.

[0234] The synthesis of the glycidyl ether of Example 1D was carried out according to the following procedure. A polyphenol (approximately 30 g) and a stoichiometric excess of epichlorohydrin (approximately 120 g) were added to a round-bottom flask equipped with an overhead condenser. The resulting mixture was stirred at approximately 450 rpm using a magnetic stirrer and the reactor was heated to the desired reaction temperature (approximately 70° C.). A coupling catalyst, TMAC (approximately 50% aqueous solution, approximately 2.4 g), was added and the reaction mixture was stirred for approximately 30 minutes. Sodium hydroxide (approximately 50% aqueous solution, approximately 12 g) was then added to the reaction mixture over a period of approximately 2 hours. The reaction mixture was allowed to continue stirring for a post-reaction time of approximately 30 minutes. A liquid epoxy resin (Epikote 862, approximately 35 g) was added to the reaction mixture at a weight ratio of approximately 1:1 relative to the formed epoxy product. Excess epichlorohydrin and water were removed using rotary evaporation. The solvent and water were added to the mixture, stirred, and the phases separated. The water wash was repeated two more times to remove more water-soluble components. The solvent was removed by rotary evaporation (about 90° C. and about 60 mbara).The sample was then heated in an oven to about 120° C. and stripped with nitrogen for about 30 minutes to provide the bioderived glycidyl ether.

[0235] Example 1E. For this glycidylation experiment, a biosourced polyphenol was used as the substrate (acidified, extracted kraft lignin #3). The substrate was removed from the substrate source (kraft lignin) by extraction using acidification as described herein and as shown below in non-limiting Example 2. No water was removed from the reactor during the reaction.

[0236] The synthesis of the glycidyl ether of Example 1E was carried out according to the following procedure. A polyphenol (approximately 100 g) and a stoichiometric excess of epichlorohydrin (approximately 500 g) were added to a reactor equipped with an overhead condenser. The resulting mixture was stirred using an overhead stirrer and the reactor was heated to the desired reaction temperature (between approximately 65° C. and approximately 75° C.). A coupling catalyst, TMAC (approximately 50% aqueous solution, approximately 8.4 g), was added and a vacuum was applied until the reaction mixture began to boil. Reflux was maintained for approximately 1 to 3 hours. Sodium hydroxide (approximately 50% aqueous solution, approximately 34.4 g) was then added to the reaction mixture over a period of approximately 4 to 6 hours. The reaction mixture was allowed to continue stirring for a post-reaction time of approximately 15 to 45 minutes. A liquid epoxy resin (Epikote 862, approximately 111 g) was added to the reaction mixture at a weight ratio of approximately 1:1 relative to the formed epoxy product. Excess epichlorohydrin and solvent were removed by vacuum distillation, and the reaction mixture was stripped with nitrogen for approximately 30 to 60 minutes. The solvent and water are added to the mixture, stirred, and the phases are separated. The water wash is repeated once to remove more water-soluble components. The solvent is removed by vacuum distillation and stripping with nitrogen for about 30 minutes to about 60 minutes to provide a bio-derived glycidyl ether.

[0237] Selected results from the glycidylation of Examples 1A-1E are shown in Table 1-1. The products of the glycidylation reactions were measured for epoxy content, hydrolyzable chlorine, and viscosity, and included liquid epoxy resin (LER). The liquid epoxy resin (Epikote 862) used in the examples had an epoxy content of 5,350 mmol / kg, a hydrolyzable chlorine content of less than 300 mg / kg, and a viscosity of 0.59 Pa·s (@40°C).

[0238] Table 1-1

[0239]

[0240] The data in Table 1-1 indicate that the lignin source and extraction method have a significant impact on the viscosity of the final product. For example, Examples 1A and 1B utilize lignin #1 and undergo epichlorohydrin extraction, while Examples 1C, 1D, and 1E utilize lignin #3 and undergo acidified epichlorohydrin extraction (described below). Examples 1A and 1B were measured to have average epoxy group content (EGC) values ​​of approximately 4,300 mmol / kg and viscosities of approximately 659 Pa·s and approximately 678.8 Pa·s, respectively (@40°C). In comparison, Examples 1C, 1D, and 1E were measured to have EGC values ​​of approximately 3,741 mmol / kg to approximately 4,700 mmol / kg and viscosities of approximately 7.4 Pa·s to approximately 8.5 Pa·s (@40°C). Examples 1A-1E indicate good results for EGC. Such EGC values ​​are commercially viable.

[0241] On a laboratory scale, when liquid epoxy resin is not used, the inventors have observed that the product is a solid and sticky, viscous mass or ball that is difficult to remove from a flask or reactor. That is, when liquid epoxy resin is not used, the product will be solid or the viscosity is so high that the product cannot be properly removed from a reactor or flask, and is therefore not suitable for commercial settings. In contrast, and as described herein, embodiments of the present disclosure utilize liquid epoxy resin to, for example, prevent (or at least alleviate) the gelling or solidification of the epoxy resin product mixture (glycidyl product) when removing epihalohydrins. Adding liquid epoxy resin can help dissolve the product mixture and reduce the viscosity of the product mixture. Adding liquid epoxy resin to the product mixture can also help discharge the product mixture from the unit or reactor for reaction. In addition, adding liquid epoxy resin to the product mixture can help remove the salt and brine formed during glycidylation, remove the by-products formed by glycidylation, remove unreacted epihalohydrins, or a combination thereof, and other materials. In this manner, embodiments described herein enable the use of non-conventional substrates to form epoxy resin compositions.

[0242] Without the addition of LER, the glycidylation product mixture would gel or solidify due to the use of a non-conventional substrate (in this case, kraft lignin). In contrast, the low viscosity of the product enables easy post-processing, transfer to another reactor, and other further uses that are not possible with the product mixture that does not include LER. Overall, the results indicate that the glycidylation process described herein can be used to glycidylate non-conventional substrates.

[0243] The higher hydrolyzable chlorine values ​​are likely due to the difficulty of measuring them, the large margin of error, and the fact that ASTM-D1726 is designed to measure values ​​as low as approximately 7 mg / kg. Furthermore, byproducts present in the product can contribute to the hydrolyzable chlorine content. Furthermore, these samples were not subjected to a final reaction.

[0244] Example 2: Separating a substrate from a substrate source

[0245] The separation of hydroxyl-containing substrates according to the embodiments described herein was performed using kraft lignin as the substrate source and epichlorohydrin (ECH) as the epihalohydrin. Three different kraft lignin samples were obtained from three different commercial suppliers. The kraft lignin substrate source was not depolymerized or pre-reacted in any other way, meaning that the high molecular weight (M w ) molecules are present in each kraft lignin sample.

[0246] Examples 2A-2C ECH was added to each kraft lignin sample (lignin 1, lignin 2, and lignin 3), and the resulting mixture was mixed at approximately room temperature and atmospheric pressure for approximately 1 hour. The mass ratio of lignin to ECH for each of the three samples was approximately 1:5. The mixture was filtered by vacuum filtration, and the ECH was then removed by distillation at approximately 90°C and a pressure of approximately 100 mbara (approximately 10 kPa (absolute)) to provide isolated lignin as the desired substrate.

[0247] Each of Examples 2A-2C was repeated three times, and selected results from the separation of Examples 2A-2C are shown in Table 2-1. The isolated yield in percentage form was determined based on mass by the following equation:

[0248] (Weight of dried extraction substrate / Weight of dried substrate source)×100

[0249] Table 2-1

[0250] Instance number Lignin source Isolated yield, % 2A Lignin 1 50 2B Lignin 2 4 2C Lignin 3 26

[0251] When the mass ratio of lignin:ECH is 1:5, it is observed that lignin is well dispersed in ECH. As shown in Table 2-1, about half of the lignin of Example 2A is dissolved in epichlorohydrin, while the proportion of dissolved lignin in Examples 2B and 2C is significantly lower. That is, Example 2A shows an isolated yield of about 50%, while Examples 2B and 2C show an isolated yield of about 4% and about 26%, respectively. Overall, the results indicate that epihalohydrin can be used to separate the desired substrate from a complex kraft lignin mixture.

[0252] Examples 2D and 2EAcidification is performed, for example, to improve isolation yield. For these experiments, lignin 2 and lignin 3 were used as kraft lignin samples. Acetic acid (about 98%, about 17 M) was used. ECH was added to the kraft lignin samples (lignin 2 and lignin 3) at a lignin:ECH mass ratio of about 1:5, and the resulting mixture was stirred. Acetic acid was then added to the mixture of ECH and lignin, and the resulting mixture was stirred until the pH reached a value of about 2, and then stirred for about 1 hour at a temperature of about room temperature and a pressure of about atmospheric pressure. The mixture was filtered by vacuum filtration, and the ECH and acetic acid were then removed by distillation at about 90° C. and a pressure of about 100 mbara (about 10 kPa (absolute)) to provide isolated lignin as the desired substrate.

[0253] Each of Examples 2D and 2E was repeated three times, and selected results from the isolation of Examples 2D and 2E are shown in Table 2-2. The isolated yields were determined as described above.

[0254] Table 2-2

[0255] Instance number Lignin source Isolated yield, % 2D Lignin 2 55 2E Lignin 3 65-70

[0256] As shown in Table 2-2, the use of acid significantly improved the isolation yield in both cases. Here, the isolation yield of lignin 2 increased from about 4% to about 55% (Example 2D), and the isolation yield increased from about 26% to a range of about 65% to about 70% (Example 2E). Overall, the results shown in Table 2-2 indicate that acidification can be used to improve the separation of desired substrates from complex kraft lignin mixtures.

[0257] The desired substrate was also separated from kraft lignin (the substrate source) on a large scale. While ECH could be removed from the desired lignin substrate using kraft lignin sources 1 and 3, it was difficult to remove ECH from the desired lignin substrate using kraft lignin source 2 under the test conditions. In cases where ECH removal was difficult, the mixture of ECH and the desired lignin (the filtrate after filtration) could be directly used for glycidylation to obtain the corresponding epoxy resin.

[0258] Embodiments described herein generally relate to the process of forming epoxy resin composition.The process of forming epoxy resin composition can be used for non-conventional substrates, such as substrates of biological origin, and waste streams or circulating streams comprising resin.The embodiments of the present disclosure are also about the process of separating substrate from complex mixture.Separation process can use epihalohydrin to extract glycidyl substrate from complex mixture.

[0259] List of implementation methods

[0260] The present disclosure provides the following aspects, as well as other aspects, each of which may be considered to include any alternative embodiments as appropriate:

[0261] Clause A1. A process for forming an epoxy resin composition, the process comprising:

[0262] reacting a mixture comprising a substrate containing at least one hydroxyl group, an epihalohydrin, and a catalyst to form a first composition comprising a halohydrin reaction product;

[0263] introducing an alkaline agent with the first composition to form a second composition comprising the epoxy resin product, residual halohydrin reaction product, and a salt;

[0264] introducing a liquid epoxy resin with the second composition to form a liquid resin mixture; and

[0265] Unreacted epihalohydrin is removed from the liquid resin mixture to form an epoxy resin composition.

[0266] Clause A2. The process of Clause A1, wherein, after removing unreacted epihalohydrin from the liquid resin mixture, the process further comprises: converting at least a portion of any residual halohydrin reaction product in the liquid resin mixture into an epoxy resin.

[0267] Clause A3. The process of Clause A1 or Clause A2, wherein the substrate comprising at least one hydroxyl group comprises a bioderived alcohol, an alcohol present in a resin waste stream, an alcohol present in a resin recycle stream, or a combination thereof.

[0268] Clause A4. The process of Clause A3, wherein the substrate comprises a polyphenol.

[0269] Item A5. The process of Item A3 or Item A4, wherein the substrate comprises aliphatic hydroxyl groups.

[0270] Clause A6. The process of any of clauses A1-A5, wherein the substrate comprises a polyphenol, an aliphatic alcohol, or a combination thereof.

[0271] Clause A7. The process of any of clauses A1-A6, wherein the catalyst is selected from the group consisting of alkali metal hydroxides, alkaline earth metal hydroxides, ammonium salts, phosphonium salts, sulfonium salts, lithium salts, and combinations thereof.

[0272] Clause A8. The process of any of clauses A1-A7, wherein:

[0273] The catalyst is selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, tetramethylammonium chloride, tetrabutylammonium chloride, tetrabutylammonium bromide, and combinations thereof;

[0274] The alkaline agent is selected from the group consisting of sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide, and combinations thereof, and the catalyst and the alkaline agent are the same or different; or

[0275] Its combination.

[0276] Item A9. A process as in Item A8, wherein the catalyst and the alkaline reagent are different.

[0277] Clause A10. The process of any of clauses A1-A9, wherein the epihalohydrin comprises epichlorohydrin.

[0278] Clause A11. The process of any of clauses A1-A10, wherein the liquid epoxy resin has a viscosity of about 15 Pa·s or less at 25°C.

[0279] Clause B1. A process for preparing a liquid epoxy resin composition, the process comprising:

[0280] reacting a mixture comprising a bioderived alcohol, an epihalohydrin, and a catalyst to form a first composition comprising a halohydrin reaction product;

[0281] introducing an alkaline reagent with the first composition to form a second composition comprising a glycidylation product, residual halohydrin reaction product, and a salt;

[0282] introducing a liquid epoxy resin with the second composition to form a liquid resin mixture;

[0283] removing unreacted epihalohydrin from the liquid resin mixture;

[0284] separating the salt from the liquid resin mixture; and

[0285] The liquid epoxy resin composition is formed by the following steps:

[0286] converting at least a portion of the residual halohydrin reaction product in the liquid resin mixture into an epoxy resin; performing a liquid-liquid separation on the liquid resin mixture; or

[0287] Its combination.

[0288] Clause B2. A process as in clause B1, wherein

[0289] The catalyst is selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, tetramethylammonium chloride, tetrabutylammonium chloride, tetrabutylammonium bromide, and combinations thereof;

[0290] The alkaline agent is selected from the group consisting of sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide, and combinations thereof, and the catalyst and the alkaline agent are the same or different; or

[0291] Its combination.

[0292] Item B3. A process as in Item B2, wherein the catalyst and the alkaline reagent are different.

[0293] Clause B4. The process of any of clauses B1-B3, wherein the bioderived alcohol comprises a phenol, an aliphatic hydroxyl group, or a combination thereof.

[0294] Clause B5. The process of any of clauses B1-B4, wherein the bioderived alcohol comprises a lignin selected from the group consisting of industrial lignin, kraft lignin, organosolv lignin, hydrolyzed lignin, or a combination thereof.

[0295] Clause B6. The process of any of clauses B1-B5, wherein the epihalohydrin is epichlorohydrin.

[0296] Clause B7. The process of any one of clauses B1-B6, wherein the mixture comprises:

[0297] The molar ratio of the epoxy groups of the epihalohydrin to the hydroxyl groups of the bioderived alcohol is from about 1:1 to about 50:1;

[0298] a molar ratio of catalyst to hydroxyl groups of the bioderived alcohol of from about 0.01:1 to about 0.15:1; or

[0299] Its combination.

[0300] Clause C1. A process for converting a substrate into a liquid epoxy resin composition, the process comprising:

[0301] reacting a mixture comprising a substrate, an epihalohydrin, and a catalyst to form a first composition comprising a halohydrin reaction product and a salt, the substrate comprising a bioderived alcohol, an alcohol present in a resin waste stream, an alcohol present in a resin recycle stream, or a combination thereof;

[0302] introducing an alkaline reagent with the first composition to form a second composition comprising a glycidylation product, residual halohydrin reaction product, and a salt;

[0303] introducing a liquid epoxy resin with the second composition to form a liquid resin mixture, the liquid epoxy resin having a viscosity of about 15 Pa·s or less at 25° C.;

[0304] removing unreacted epihalohydrin from the liquid resin mixture; and

[0305] The salt is separated from the liquid resin mixture to form a liquid epoxy resin composition.

[0306] Clause C2. The process of Clause C1, wherein the substrate is derived from a substrate source by:

[0307] introducing a substrate source together with the epihalohydrin and separating the substrate and epihalohydrin from the substrate source; or

[0308] A substrate source is introduced along with the epihalohydrin and the acid, and the substrate and epihalohydrin are separated from the substrate source.

[0309] Clause D1. A process comprising:

[0310] introducing an epihalohydrin with a substrate source comprising a substrate comprising at least one hydroxyl group; and

[0311] The epihalohydrin and substrate are separated from the substrate source.

[0312] Item D2. The process of Item D1, further comprising removing the epihalohydrin from the substrate.

[0313] Item D3. The process of Item D1 or Item D2, wherein the substrate comprises a phenol, a polyphenol, an aliphatic alcohol, or a combination thereof.

[0314] Clause D4. The process of any of clauses D1-D3, wherein the mass ratio of substrate source to epihalohydrin is from about 1:1 to about 1:10.

[0315] Clause D5. The process of any of clauses D1-D4, wherein the epihalohydrin comprises epichlorohydrin, epibromohydrin, or a combination thereof.

[0316] Clause E1. A process comprising:

[0317] introducing an acid solution and an epihalohydrin along with a substrate source comprising a substrate comprising at least one hydroxyl group; and

[0318] The epihalohydrin and substrate are separated from the substrate source.

[0319] Item E2. The process of Item E1, wherein the acid solution has a pH of about 1 to about 3.

[0320] Item E3. The process of Item E1 or Item E2, wherein the mass ratio of substrate source to epihalohydrin is from about 1:1 to about 1:10.

[0321] Clause E4. The process of any of clauses E1-E3, wherein:

[0322] The mixture comprising the acid solution, the epihalohydrin, and the substrate source has a pH of about 2 to about 3 before separation; the molar concentration of the acid solution is about 0.01 M to about 18 M; or

[0323] Its combination.

[0324] Clause E5. The process of any of clauses E1-E4, wherein the mass ratio of acid solution to substrate source is from about 0.1:1 to about 1:1.

[0325] Clause E6. The process of any of clauses E1-E5, wherein the acid solution comprises acetic acid, hydrochloric acid, oxalic acid, phosphoric acid, p-toluenesulfonic acid, ions thereof, or combinations thereof.

[0326] Clause E7. The process of any of clauses E1-E6, wherein the substrate comprising at least one hydroxyl group comprises a phenol, a polyphenol, an aliphatic alcohol, or a combination thereof.

[0327] Clause F1. A process for preparing an epoxy resin composition, the process comprising:

[0328] introducing a first epihalohydrin with a substrate source, the substrate source comprising a substrate comprising at least one hydroxyl group;

[0329] separating at least a portion of the first epihalohydrin and the substrate from the substrate source; and

[0330] The substrate is converted into an epoxy resin composition.

[0331] Clause F2. The process of clause F1, wherein converting the substrate into the epoxy resin composition comprises:

[0332] reacting a mixture comprising a substrate, a second epihalohydrin, and a catalyst to form a first composition comprising a halohydrin reaction product, the first epihalohydrin and the second epihalohydrin being the same or different; and

[0333] An alkaline reagent is introduced with the first composition to form a second composition comprising the epoxy resin product, residual halohydrin reaction product, and a salt.

[0334] Clause F3. The process of clause F2, wherein, after introducing an alkaline agent with the first composition to form the second composition, the process further comprises:

[0335] introducing a liquid epoxy resin with the second composition to form a liquid resin mixture; and

[0336] Unreacted epihalohydrin is removed from the liquid resin mixture.

[0337] Clause F4. The process of Clause F2 or Clause F3, wherein the second epihalohydrin is fresh epihalohydrin.

[0338] Clause F5. The process of any of clauses F2-F4, wherein:

[0339] Each of the first epihalohydrin and the second epihalohydrin is independently selected from the group consisting of epichlorohydrin, epibromohydrin, or a combination thereof;

[0340] a mass ratio of the substrate source to the first epihalohydrin of about 1:1 to about 1:10; or

[0341] Its combination.

[0342] Clause F6. The process of any of clauses F1-F5, further comprising: introducing an acid solution to the substrate source before, during, or after introducing the first epihalohydrin with the substrate source.

[0343] Clause F7. A process as in Clause F6, wherein:

[0344] The mixture comprising the acid solution, the first epihalohydrin, and the substrate source has a pH of about 2 to about 3 before separation;

[0345] The acid solution has a molar concentration of about 0.01 M to about 18 M; or

[0346] Its combination.

[0347] Item F8. The process of Item F6 or Item F7, wherein the mass ratio of acid solution to substrate source is from about 0.01:1 to about 1:1.

[0348] As used herein, reference to an R group, an alkyl group, a substituted alkyl group, a hydrocarbyl group, or a substituted hydrocarbyl group without specifying a particular isomer (such as butyl) explicitly discloses all isomers (such as n-butyl, isobutyl, secondary butyl, and tertiary butyl). For example, reference to an R group having 4 carbon atoms explicitly discloses all isomers thereof. When a compound is described herein such that no particular isomer, enantiomer, or diastereomer of the compound is specified, for example, in a formula or chemical name, the description is intended to include each isomer and enantiomer of the compound described individually or in any combination.

[0349] It is obvious from the general description and specific aspects above that, although the forms of various aspects have been illustrated and described, various modifications can be made without departing from the spirit and scope of the present disclosure. Therefore, the present disclosure is not intended to be limited in this way. Similarly, the term "comprising" is considered to be synonymous with the term "including". Similarly, whenever a composition, an element or an element group is preceded by the transition phrase "comprising", it should be understood that we also consider the same composition or element group with the transition phrase "essentially consisting of", "consisting of", "selected from a group consisting of" or "is" before the description of the composition, element or multiple elements, and vice versa, such as the terms "comprising", "essentially consisting of", "consisting of" also include the product of the element combination listed after the term.

[0350] For the purposes of this disclosure, and unless otherwise specified, all numerical values ​​in the embodiments and claims herein are modified by the values ​​indicated by "about" or "approximately", and take into account the experimental errors and variations expected by those skilled in the art. For the sake of brevity, only certain ranges are explicitly disclosed herein. However, the range of any lower limit can be combined with any upper limit to describe the range that is not explicitly described, and the range of any lower limit can be combined with any other lower limit to describe the range that is not explicitly described, and in the same way, the range of any upper limit can be combined with any other upper limit to describe the range that is not explicitly described. For example, the description of the numerical range 1 to 5 includes subranges 1 to 4, 1.5 to 4.5, 1 to 2 and other subranges. As another example, the description of the numerical range 1 to 5 (such as 2 to 4) includes subranges 1 to 4 and 2 to 5 and other subranges. In addition, each point or single value between its endpoints is included in the range, even if it is not explicitly described. For example, the description of the numerical range 1 to 5 includes the numbers 1, 1.5, 2, 2.75, 3, 3.80, 4, 5 and other numbers. Thus, each point or single value can be combined with any other point or single value or any other lower or upper limit as its own lower or upper limit to recite a range not explicitly recited.

[0351] As used herein, the indefinite article "a" or "an" shall mean "at least one," unless specified to the contrary or the context clearly indicates otherwise. For example, aspects comprising "a catalyst" include aspects comprising one, two, or more catalysts, unless specified to the contrary or the context clearly indicates that only one catalyst is included.

[0352] While the foregoing is directed to various aspects of the present disclosure, other and further aspects of the disclosure may be devised without departing from the basic scope thereof, the scope of which is determined by the claims that follow.

Claims

1. A process comprising: introducing an epihalohydrin with a substrate source comprising a substrate comprising at least one hydroxyl group; and The epihalohydrin and the substrate are separated from the substrate source.

2. The process of claim 1 , further comprising: The epihalohydrin is removed from the substrate.

3. The process of claim 1 , wherein: The substrate comprises phenol, polyphenol, aliphatic alcohol or a combination thereof; The mass ratio of the substrate source to the epihalohydrin is about 1:1 to about 1:10; The epihalohydrin comprises epichlorohydrin, epibromohydrin or a combination thereof; or Its combination.

4. A process comprising: introducing an acid solution and an epihalohydrin along with a substrate source comprising a substrate comprising at least one hydroxyl group; and The epihalohydrin and the substrate are separated from the substrate source.

5. The process of claim 4, wherein the acid solution has a pH of about 1 to about 3.

6. The process of claim 4, wherein the mass ratio of the substrate source to the epihalohydrin is from about 1:1 to about 1:

10.

7. The process of claim 4, wherein: The mixture comprising the acid solution, the epihalohydrin, and the substrate source has a pH of about 2 to about 3 before separation; The acid solution has a molar concentration of about 0.01 M to about 18 M; or Its combination.

8. The process of claim 4, wherein: The mass ratio of the acid solution to the substrate source is from about 0.1:1 to about 1:1; The acid solution comprises acetic acid, hydrochloric acid, oxalic acid, phosphoric acid, p-toluenesulfonic acid, ions thereof, or a combination thereof; and the substrate comprising at least one hydroxyl group comprises phenol, polyphenol, aliphatic alcohol, or a combination thereof.

9. A process for preparing an epoxy resin composition, the process comprising: introducing a first epihalohydrin with a substrate source, the substrate source comprising a substrate comprising at least one hydroxyl group; separating at least a portion of the first epihalohydrin and the substrate from the substrate source; and The substrate is converted into an epoxy resin composition.

10. The process of claim 9, wherein converting the substrate into the epoxy resin composition comprises: reacting a mixture comprising the substrate, the second epihalohydrin, and a catalyst to form a first composition comprising a halohydrin reaction product, the first epihalohydrin and the second epihalohydrin being the same or different; and An alkaline reagent is introduced with the first composition to form a second composition comprising epoxy resin product, residual halohydrin reaction product, and a salt.

11. The process of claim 10, wherein After introducing the alkaline agent with the first composition to form the second composition, the process further comprises: introducing a liquid epoxy resin with the second composition to form a liquid resin mixture; and Unreacted epihalohydrin is removed from the liquid resin mixture.

12. The process of claim 10, wherein the second epihalohydrin is fresh epihalohydrin.

13. The process of claim 10, wherein: Each of the first epihalohydrin and the second epihalohydrin is independently selected from the group consisting of epichlorohydrin, epibromohydrin, or a combination thereof; The mass ratio of the substrate source to the first epihalohydrin is about 1:1 to about 1:10; or Its combination.

14. The process of claim 9, further comprising: The acid solution is introduced into the substrate source before, during, or after the first epihalohydrin is introduced with the substrate source.

15. The process of claim 14, wherein: The mixture comprising the acid solution, the first epihalohydrin, and the substrate source has a pH of about 2 to about 3 before the separating; The acid solution has a molar concentration of about 0.01 M to about 18 M; The mass ratio of the acid solution to the substrate source is from about 0.01:1 to about 1:1; or Its combination.

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