Process for forming bisphenol, epoxy resin compositions

Abstract

Embodiments of the present disclosure generally relate to processes for forming bisphenol and epoxy resin compositions. In one embodiment, a process for making an epoxy resin composition is provided. The process includes reacting a mixture comprising a catalyst, a monophenol, and an aldehyde or ketone, the mixture comprising a stoichiometric excess of the aldehyde or ketone relative to the monophenol, and forming a reaction product with the reaction mixture, the reaction product comprising a bisphenol. The process further includes removing water and unreacted aldehyde or ketone from the reaction product, and converting the reaction product comprising the bisphenol to an epoxy resin composition, wherein the process does not perform washing, drying, solid-liquid separation, or a combination thereof after reacting the mixture and before converting the reaction product.

Description

Technical Field

[0001] Embodiments of this disclosure generally relate to processes for forming bisphenol and epoxy resin compositions. Background Technology

[0002] Bisphenols, such as tetramethyl bisphenol F (TMBPF), are used as feedstock components in various polymers such as epoxy resins and polycarbonate resins. Typically, the formation of TMBPF requires a reaction in the liquid phase, where 2,6-xylenol condenses with formaldehyde. When TMBPF forms, it crystallizes into a slurry in the liquid phase. Conventional techniques convert the TMBPF slurry into pure, dry TMBPF powder before it can be used to produce resins. To form pure, dry TMBPF powder, the slurry undergoes various purification operations such as solid-liquid separation and washing, followed by drying. Therefore, conventional TMBPF production is expensive in terms of manufacturing and operating costs. In addition to these costly operations, TMBPF is conventionally produced using an excess of 2,6-xylenol. For the production of epoxy resins, such as tetramethyl bisphenol F diglycidyl ether (TMBPF-DGE), pure, dry TMBPF powder is then fed into the reactor. Such feedstock production is both time-consuming and challenging because the powder is difficult to handle. Overall, the production of TMBPF and other bisphenols, and their subsequent use in the manufacture of epoxy resins, is inefficient and expensive.

[0003] Therefore, there is a need for novel and improved processes for forming bisphenols such as TMBPF and epoxy resin compositions formed from such bisphenols. Summary of the Invention

[0004] Embodiments of this disclosure generally relate to processes for forming bisphenol, epoxy resin compositions, and TMBPF. Compared to prior art, embodiments of this disclosure can reduce the production costs of bisphenol (such as TMBPF), epoxy resin compositions, and TMBPF. Furthermore, the embodiments described herein enable the integration of bisphenol production with epoxy resin composition production, for example, integrating TMBPF production with subsequent TMBPF glycidylation to produce TMBPF-DGE.

[0005] In one embodiment, a process for manufacturing an epoxy resin composition is provided. The process includes reacting a mixture comprising a catalyst, a monophenol, and an aldehyde or ketone, the mixture comprising an aldehyde or ketone in stoichiometric excess relative to the monophenol, and forming a reaction product with the reaction mixture, the reaction product comprising bisphenol. The process further includes removing water and unreacted aldehyde or ketone from the reaction product, and converting the reaction product containing bisphenol into an epoxy resin composition, wherein washing, drying, solid-liquid separation, or a combination thereof are not performed after reacting the mixture and before converting the reaction product.

[0006] In another embodiment, a process is provided for forming a composition comprising bisphenol. The process includes introducing an aldehyde or ketone with a catalyst, a solvent, and a monophenol to form a mixture containing an aldehyde or ketone in excess relative to the stoichiometry of the monophenol. The process further includes reacting the mixture to form a composition comprising bisphenol and one or more components selected as appropriate, wherein about 90% or more of the monophenol is converted to bisphenol and one or more components selected as appropriate.

[0007] In another embodiment, a process for converting a monophenol into a conversion product is provided. The process includes reacting a mixture comprising an aldehyde or ketone, a catalyst, a solvent, and a monophenol to form a reaction product comprising bisphenol, wherein the mixture comprises an aldehyde or ketone in excess relative to the stoichiometry of the monophenol. The process further includes removing water and any remaining aldehyde or ketone from the reaction product, wherein the solvent has a boiling point of about 150°C or higher at 100 kPa (absolute). The process further includes converting the reaction product comprising bisphenol into the conversion product, wherein washing, drying, solid-liquid separation, or a combination thereof are not performed after reacting the mixture and before converting the reaction product. Attached Figure Description

[0008] To gain a more detailed understanding of the features described above, this disclosure can be described in a more specific manner by referring to embodiments, some of which are illustrated in the accompanying drawings. However, it should be noted that the drawings are merely illustrative of exemplary embodiments and are not intended to limit the scope of the disclosure, allowing for other equally effective embodiments.

[0009] Figure 1 A flowchart illustrating an integration process for forming a composition according to at least one embodiment of this disclosure.

[0010] Figure 2 This demonstrates the use of at least one embodiment of the present disclosure. Figure 1 The integration process is used to form a non-limiting reaction diagram of the example resin composition.

[0011] Figure 3AExamples are shown of one or more additional components that may be formed during a process for forming tetramethyl bisphenol F (TMBPF) according to at least one embodiment of the present disclosure.

[0012] Figure 3B Examples are shown of one or more additional components formed during a process for forming tetramethyl bisphenol F diglycidyl ether (TMBPF-DGE) according to at least one embodiment of the present disclosure.

[0013] Figure 4 A flowchart illustrating the conventional process used to form a TMBPF.

[0014] Figure 5 A flowchart illustrating a process for forming a TMBPF according to at least one embodiment of this disclosure.

[0015] Figure 6A This diagram shows a non-limiting reaction diagram for forming bisphenol according to at least one embodiment of the present disclosure.

[0016] Figure 6B This illustrates examples of one or more additional components formed during a process for forming bisphenol, according to at least one embodiment of this disclosure.

[0017] Figure 7A This diagram shows a non-limiting reaction diagram for forming bisphenol diglycidyl ether according to at least one embodiment of the present disclosure.

[0018] Figure 7B Examples are shown of one or more additional components formed during subsequent processing of bisphenol according to at least one embodiment of this disclosure.

[0019] The accompanying drawings included herein illustrate various embodiments of this disclosure. It should be considered that elements and features of one embodiment may be advantageously incorporated into other embodiments without further explanation. Detailed Implementation

[0020] Embodiments of this disclosure generally relate to processes for forming bisphenol and epoxy resin compositions. The inventors have discovered processes for forming bisphenols such as TMBPF that can be further processed into resins without complex separation and purification steps. Unlike conventional processes for forming bisphenols, the bisphenols described herein are in the form of a product mixture that can be used for subsequent processing without purification operations such as solid-liquid separation, washing, and drying. In addition to bisphenols, the product mixture may also contain byproducts and solvents, and may be in the form of a slurry in which bisphenols are partially or completely dissolved. Therefore, the manufacturing and operating costs are significantly lower than conventional methods for forming bisphenols. Furthermore, using a bisphenol-containing product mixture, for example, in slurry form, allows for faster and safer subsequent reactor loading of the bisphenols.

[0021] Compared to conventional techniques for forming bisphenols such as TMBPF, the embodiments described herein provide a high conversion rate of starting phenols with little or no phenolic loss. This high conversion rate of starting phenols can be achieved, at least in part, by using an excess of formaldehyde. The use of excess formaldehyde contrasts with conventional techniques that use excess starting phenols. Furthermore, the excess formaldehyde used to form bisphenols can be readily removed from the reaction products by the water formed during bisphenol formation.

[0022] The title is used for convenience only and does not limit the scope of this disclosure. The embodiments described herein can be combined with other embodiments.

[0023] Although the embodiments described in this disclosure involve formaldehyde, it is also contemplated that other aldehydes and ketones may be used, as further described below with respect to the aldehydes and ketones of formula (III).

[0024] Integrated process

[0025] Figure 1 This is a flowchart illustrating an integration process 100 for forming a composition according to at least one embodiment of this disclosure. The composition formed by the integration process 100 may include polymers, such as resins, thermosetting plastics, thermoplastics, and other materials. In some instances, the composition formed by the integration process 100 comprises, is composed of, or is substantially composed of resin compositions. The resin composition may be an epoxy resin composition, a polycarbonate resin composition, or other resin compositions. Figure 2 A non-limiting reaction diagram 200 is shown for forming example resin composition B, which can be prepared using integrated process 100 according to at least one embodiment of this disclosure. Figure 2 In the example shown, resin composition B includes tetramethyl bisphenol F diglycidyl ether (TMBPF-DGE) 240. Figure 2 In this context, reference numeral 201 refers to the first component, and reference numeral 202 refers to the second component.

[0026] As used herein, "composition" may include components of a composition, reaction products of two or more components of a composition, the balance of remaining starting components, or combinations thereof. The compositions of this disclosure may be prepared by any suitable mixing process.

[0027] See back Figure 1 The integration process 100 may include forming a first composition 201 comprising bisphenol in operation 101. In this example, the bisphenol is tetramethylbisphenol F 225 (TMBPF; CAS No.: 5384-21-4; also known as 4,4'-methylenebis(2,6-dimethylphenol)). Operation 101 may include reacting a mixture comprising a phenol (e.g., 2,6-xylenol 205), formaldehyde 210, and catalyst 215 under conversion conditions 220 to form the first composition 201 comprising TMBPF 225. The first composition 201 may be in the form of a reaction product or a reaction mixture.

[0028] First composition 201 may include one or more additional components besides bisphenol. For example, one or more additional components of first composition 201 may comprise, consist of, or substantially consist of, trimers, tetramers, light components, heavy components, or combinations thereof. When used with first composition 201, the term "light component" includes components in first composition 201 with a boiling point lower than that of the bisphenol formed in operation 101. Examples of light components that may be part of first composition 201 may include 2,6-xylenol, 2,4-xylenol, o-cresol, p-cresol, o-ethylphenol, formaldehyde, or combinations thereof. When used with first composition 201, the term "heavy component" includes components in first composition 201 with a boiling point higher than that of the bisphenol formed in operation 101. Heavy components of first composition 201 may include components with higher boiling points that are not trimers or tetramers, such as higher oligomers. Examples of trimers and tetramers (one or more additional components) that can be part of the first composition 201 may include hexamethylpyrogallol F 302 (an example trimer, also known as a triol) and octamethyltetraphenol F 304a, 304b (example tetramers, also known as tetraphenols), such as Figure 3A As shown in the figure. These trimers and tetramers can be formed in the process of forming TMBPF.

[0029] Unlike conventional techniques for forming TMBPF-DGE, the TMBPF formed during operation 101 can be directly used to form TMBPF-DGE. That is, the integrated process 100 along path 103 between the production of TMBPF (in operation 101) and the production of TMBPF-DGE (in operation 102) does not involve separation, purification, or drying operations. This is due, for example, the use of excess formaldehyde in the reaction. Path 103 may represent, for example, feeding a mixture of products containing the TMBPF formed in operation 101 into a different reactor for subsequent operations (e.g., operation 102). Alternatively, path 103 may represent a subsequent process (e.g., operation 102) to be performed, and the subsequent process may be carried out in the same reactor as the reactor used to form TMBPF, or in situ, or continuously.

[0030] continue Figure 2 As illustrated in the non-limiting example, the integration process 100 may also include forming a second composition 202 comprising glycidylated bisphenol from the first composition 201 (or reaction product) in operation 102. In this example, the glycidylated bisphenol is TMBPF-DGE 240. Alternatively or in some embodiments, acrylation, acylation, alkylation, or any suitable reaction may be performed to form polymerizable groups, for example, chemically bonded to the bisphenol oxygen atom (and, if present, oxygen atoms of one or more trimers, oxygen atoms of one or more tetramers, or combinations thereof) of the first composition 201.

[0031] Operation 102 may include reacting a mixture comprising a first component 201 and a surface haloalcohol (such as epichlorohydrin 230) under conversion conditions 235 to form a second component comprising TMBPF-DGE 240 (CAS No.: 113693-69-9). The second component 202 may also include one or more additional components, such as trimers, tetramers, light components, heavy components, or combinations thereof, when the first component 201 includes one or more additional components. The one or more additional components of the second component 202 may include trimers, tetramers, light components, heavy components, or combinations thereof.

[0032] When used in second composition 202, the term "light component" includes components in second composition 202 with boiling points lower than those of the glycidylated bisphenol formed in operation 102. Examples of light components that may be part of second composition 202 may include glycidylated 2,6-xylenol, glycidylated 2,4-xylenol, glycidylated o-cresol, glycidylated p-cresol, glycidylated o-ethylphenol, or combinations thereof, or consisting of or substantially consisting of thereof. When used in second composition 202, the term "heavy component" includes components in second composition 202 with boiling points higher than those of the glycidylated bisphenol formed in operation 102. The heavy component of second composition 202 may include components having a higher boiling point than glycidylated bisphenol and not being glycidylated trimers or glycidylated tetramers (such as glycidylated higher oligomers). Examples of glycidylated trimers and glycidylated tetramers that can be part of the second composition 202 include hexamethylpyrrolidone F triglycidyl ether 312 (an example trimer, also known as triphenol) and octamethyltetraphenol F tetraglycidyl ether 314a, 314b (example tetramers, also known as tetraphenol), such as Figure 3B As shown in the diagram. These glycidylated trimers and glycidylated tetramers can be formed during the process used to form TMBPF-DGE. Figure 3B In the diagram, the wavy bond represents the connection with an oxygen atom.

[0033] The above about Figure 2 , Figure 3A and Figure 3B The described embodiments are shown for illustrative purposes and are not intended to be limiting. For example, TMBPF-DGE resin is an illustrative but non-limiting example of an epoxy resin composition that can be formed according to one or more embodiments described herein. Similarly, phenols other than 2,6-xylenol, associative bisphenol, and associative glycidylated bisphenol can be used or formed according to one or more embodiments described herein. For example, phenols such as eugenol, associative biseugenol, and associative glycidylated biseugenol can be utilized or formed by the embodiments described herein. As another example, phenols such as eugenol, associative biseugenol, and associative glycidylated biseugenol can be utilized or formed by the embodiments described herein.

[0034] Prior techniques and methods for forming resin compositions (such as epoxy resin compositions) are not integrated, or even lack the capacity to be integrated. Here, regarding the synthesis of TMBPF-DGE, prior techniques require converting TMBPF slurry into a pure, dry powder before forming TMBPF-DGE. Such separation, purification, and drying operations are inefficient and expensive. Furthermore, the pure, dry powder of TMBPF must be fed into the reactor to form TMBPF-DGE. The following... Figure 4The present invention further describes these and other drawbacks of the conventional method. In contrast, the embodiment of the integrated process 100 described herein can proceed along path 103 between the production of TMBPF (in operation 101) and the production of TMBPF-DGE (in operation 102) without separation, purification, drying, or combinations thereof.

[0035] In some embodiments, operations 101 and 102 can be carried out in the same reactor or in different reactors. As a non-limiting example, when catalyst 215 is sodium hydroxide (NaOH), at least a portion of the NaOH remaining after the formation of the first composition 201 can be used during glycidization (e.g., conversion condition 235) to form the second composition 202. This example further illustrates the unique advantages of the integrated process described herein.

[0036] Figure 4 This is a flowchart illustrating a conventional process 400 for forming TMBPF. Conventional process 400 includes mixing 2,6-xylenol, a catalyst, and a solvent in step 405 to form a mixture. Then, in step 410, formaldehyde is added to the mixture over approximately 50 minutes, while TMBPF crystallizes and forms a slurry. Here, conventional techniques for producing bisphenols (TMBPF in this example) require an excess of monophenol (2,6-xylenol in this example). Some conventional techniques also discard the remaining monophenol or purify and recycle the remaining monophenol (e.g., in one or more of steps 425, 431, or 432). In contrast, the process described herein can be performed using an excess of formaldehyde. Here, the excess formaldehyde can be easily removed by boiling or evaporation.

[0037] The conventional process 400 further includes a post-reaction period 415 from the addition of all formaldehyde to the reactor until the end of the reaction. The slurry is then cooled in step 420 to prepare for further processing to form a pure, dry powder of TMBPF. In step 425, the slurry exiting line 421 undergoes solid-liquid separation to separate the solid fraction exiting line 426 from the liquid fraction exiting line 427. The solid fraction exiting line 426 is further washed at least twice with water or other solvents (steps 430, 435) to remove residual solvent from the solid fraction. Water / solvent from the washing step is added to the liquid fraction exiting line 427, and the resulting solvent-water mixture is separated in step 431. The solvent fraction formed in step 431 undergoes solvent evaporation to remove residual components, such as byproducts or reactants (such as 2,6-xylenol), and then the solvent is recycled in step 433. After washing the solid fraction in steps 430, 435, the solid is dried into a pure, dry powder of TMBPF in step 440. Then, in step 445, the pure, dry powder of TMBPF is discharged from the processing unit.

[0038] Overall, this conventional process 400 for forming bisphenols (e.g., TMBPF) is inefficient and expensive. For example, the slurry leaving line 421 must be converted into pure, dry TMBPF powder before it can be used to produce resin. Here, to form pure, dry TMBPF powder, the slurry undergoes various purification operations, such as solid-liquid separation (in step 425) and washing (in steps 430 and 435), followed by drying (in step 440). Furthermore, the pure, dry TMBPF powder formed in step 440 must be discharged from the reactor (in step 445) before subsequent processing (such as the production of epoxy resins including TMBPF-DGE). Moreover, feeding this pure, dry TMBPF powder is both time-consuming and challenging due to the difficulty of movement and handling.

[0039] Figure 5 A flowchart illustrating a process 500 for forming TMBPF according to at least one embodiment of this disclosure is provided. Although an embodiment of process 500 is described with reference to TMBPF and TMBPF-DGE, other bisphenol and resin compositions are also contemplated. For example, bisphenol A (BPA) can be prepared using acetone. As described above, and compared to conventional techniques, the process for forming bisphenols as described herein may eliminate various purification operations, such as solid-liquid separation (e.g., step 425 above), washing (e.g., steps 430 and 435 above), and subsequent drying (e.g., step 440 above). Furthermore, unlike conventional techniques that convert TMBPF slurry leaving pipeline 421 into a pure, dry powder, the product mixture containing bisphenol (e.g., TMBPF) does not need to be discharged from the reactor before subsequent processing (e.g., step 445 above) of epoxy resins including TMBPF-DGE.

[0040] Process 500 includes mixing 2,6-xylenol, a catalyst, and a solvent in operation 505 to form a mixture. Then, in operation 510, formaldehyde (or other aldehydes or ketones) is added to the mixture while TMBPF crystallizes to form a product mixture containing TMBPF. A stoichiometric excess of formaldehyde is used. In such cases, the excess formaldehyde can be easily removed in operation 520 by boiling, evaporation, distillation, or a combination thereof. The use of a stoichiometric excess of formaldehyde to form bisphenol contrasts with conventional techniques that use excess monophenols during bisphenol production. Therefore, the embodiments described herein can remove excess monophenols without purification and recycling processes. Although embodiments of this disclosure are described in relation to formaldehyde, the use of other aldehydes and ketones, as further described below, is also contemplated. For example, acetone can be used as a ketone to manufacture BPA. Additionally, when using ketones to manufacture bisphenols, a stoichiometric excess of the ketone relative to the monophenol is used.

[0041] Process 500 further includes a post-reaction period 515. The post-reaction period is the time from when all formaldehyde is added to the reactor until the reaction is complete or considered finished. Process 500 further includes the removal of, for example, water and formaldehyde in operation 520. The removal process in operation 520 can be carried out by suitable techniques such as distillation, but other techniques are also possible. As mentioned above, the product mixture containing bisphenol (e.g., TMBPF) can be in the form of a slurry in which bisphenol is partially or completely dissolved. At this stage, the bisphenol (e.g., TMBPF) can be used for subsequent processing, such as glycidylation to form TMBPF-DGE (in operation 102), depending on the catalyst used in operation 505.

[0042] When the catalyst used to form bisphenols (e.g., TMBPF) is a base catalyst, the product mixture containing TMBPF then exits operation 520 via line 521 and can be used as is for subsequent processing, such as TMBPF-DGE formation (e.g., operation 102). When the catalyst used to form bisphenols is an acid catalyst, the acid catalyst can be removed, neutralized, or a combination thereof via operation 525, as appropriate. The removal process in operation 525, as appropriate, can be carried out by heating, distillation, neutralizing or quenching the acid, or a combination thereof, by introducing a base, to form a product mixture containing TMBPF exiting operation 525 via line 526, ready for subsequent processing if desired.

[0043] For example, when oxalic acid is used to form bisphenol, the oxalic acid decomposes into a light gas at a temperature of about 160°C or higher. Depending on the conditions, such a light gas may include carbon dioxide, carbon monoxide, formic acid, water, or a combination thereof. In this example, the reaction product containing bisphenol may be heated during operation 525, as appropriate, to decompose the oxalic acid. When an inorganic acid, such as hydrochloric acid, is used to form bisphenol, the hydrochloric acid may be removed by distillation during operation 525, as appropriate. Alternatively or additionally, during operation 525, the inorganic acid may be neutralized by a base, such as sodium hydroxide, to form a salt, such as sodium chloride. Unlike conventional methods, the presence of the resulting salt, such as sodium chloride, in the reaction product containing bisphenol is acceptable for further processing such as glycidization (e.g., operation 102).

[0044] Overall, the embodiment of process 500 for forming bisphenols (e.g., TMBPF) suitable for further processing is a significant improvement over the conventional process 400 because it is much simpler. Furthermore, the embodiment of process 500 can be integrated with subsequent processing (e.g., operation 102), such as glycidylation, acrylation, acylation, alkylation, or any suitable reaction. Here, for example, the product mixture containing TMBPF formed during process 500 can be directly used to form TMBPF-DGE. That is, the synthesis of TMBPF can be readily integrated with the synthesis of TMBPF-DGE, thereby allowing an integrated process for the formation of TMBPF-DGE from 2,6-xylenol.

[0045] Processes for forming bisphenol monomers

[0046] The embodiments described herein also typically relate to processes for forming bisphenols. These processes generally involve reacting a mixture of formaldehyde (or a formaldehyde source), a catalyst, and at least one phenol under reaction conditions to form a reaction product containing bisphenols. Figure 6A The reaction diagram 600 shows the formation of a bisphenol of formula (II) from one or more phenols of formula (I). The reaction diagram 600 is merely an example and not a limitation. As described above, the formation of the bisphenol of formula (II) occurs with formaldehyde 210 and catalyst 215 under reaction conditions 620 to form a reaction product comprising the bisphenol of formula (II). This reaction can be termed a condensation reaction, producing water.

[0047] Although the embodiments described in this disclosure involve formaldehyde, it is also contemplated that other aldehydes and ketones may be used, as further described below with respect to the aldehydes and ketones of formula (III).

[0048] Suitable phenols that can be used as at least one phenol include those represented by formula (I):

[0049] .

[0050] The phenol of formula (I) includes at least one hydrogen atom (H) such that z is at least 1. In formula (I), R is a group that substitutes for a hydrogen atom on the aromatic ring, and OH is a hydroxyl group that substitutes for a hydrogen atom on the aromatic ring.

[0051] In some embodiments, z is 1 to 4, such as 1, 2, 3, or 4; x is 1 to 4 (such as 1, 2, 3, or 4); y is 1 to 4 (such as 1, 2, 3, or 4); and combinations thereof. The total number of x, y, and z on the aromatic ring of formula (I) is 6. When x is greater than 1, the R groups can be the same or different.

[0052] Each R group in formula (I) can be an unsubstituted hydrocarbon group, a substituted hydrocarbon group, or a functional group containing at least one element from Groups 13-17 of the periodic table. When the R group is a functional group containing at least one element from Groups 13-17, the R group can be a halogen (F, Cl, Br, or I), O, N, Se, Te, P, As, Sb, S, B, Si, Ge, Sn, Pb, 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*, SOx (where 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 at least one heteroatom is inserted into the unsubstituted hydrocarbon group.

[0053] Each R group in Formula (I) may independently have any suitable number of carbon atoms, such as 1 to 20 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, the number of carbon atoms in each R group in Formula (I) may 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 may be used alone to describe an open range or in combination to describe a closed range. Each R group in Formula (I) may independently be straight-chain or branched, saturated or unsaturated, cyclic or acyclic, aromatic or non-aromatic. Regarding saturation, each R group in Formula (I) may independently be fully saturated, partially unsaturated, or fully unsaturated.

[0054] In some instances, one or more R groups of formula (I) may be unsubstituted hydrocarbon groups. "Unsubstituted hydrocarbon group" refers to a group consisting only 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, dibutyl and tributyl, 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. In some embodiments, one or more R groups of formula (I) may be straight-chain or branched alkenyl groups having 1 to 20 carbon atoms, such as 3 to 10 carbon atoms. The term "alkenyl" refers to a hydrocarbon group having at least one double bond. Illustrative but non-limiting examples of alkenyl groups include allyl groups (such as -CH2CH=CH2).

[0055] In some embodiments, one or more R groups of formula (I) may be substituted hydrocarbon groups. “Substituted hydrocarbon group” means an unsubstituted hydrocarbon group in which at least one hydrogen atom of the unsubstituted hydrocarbon group has been substituted by at least one heteroatom or heteroatom-containing group, such as one or more elements from groups 13-17 of the periodic table, such as halogens (F, Cl, Br or I), O, N, Se, Te, P, As, Sb, S, B, Si, Ge, Sn, Pb 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*, SOx (where 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.

[0056] Non-limiting examples of substituted hydrocarbon groups include -OR*, wherein an oxygen atom is attached to a ring and wherein R* may comprise 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 their isomers.

[0057] In some embodiments, each R group in formula (I) is a group that does not react with reactants containing epoxides. For example, in at least one embodiment, each R group in formula (I) is independently -(C1-C5)alkyl or -O(C1-C5)alkyl.

[0058] In at least one embodiment, the phenol in formula (I) is a monophenol (y is 1).

[0059] In formula (I), and in some embodiments, at least one R group is located on the aromatic ring at an ortho position relative to a hydroxyl group. In some embodiments, the R group is located on the ring at each ortho position relative to a hydroxyl group.

[0060] Illustrative but non-limiting examples of phenols of formula (I) include 2,6-xylenol (formula (Ia)), 2,6-diethylphenol (formula (Ib)), 2,6-diisopropylphenol (formula (Ic)), 2,6-di-tert-butylphenol (formula (Id)), 2,6-dimethoxyphenol (formula (Ie); also known as eugenol), 2,6-diethoxyphenol (formula (If)), 2-methoxy-4-prop-2-enylphenol (formula (Ig); also known as eugenol), and others:

[0061] .

[0062] As used herein, references to chemical substances, R groups, alkyl groups, substituted alkyl groups, hydrocarbon groups, or substituted hydrocarbon groups without specifying a particular isomer (such as butyl) explicitly disclose all isomers (such as n-butyl, isobutyl, dibutyl, and tributyl). For example, references to R groups having four carbon atoms explicitly disclose all their isomers. When a compound is described herein such that a particular isomer, mirror isomer, or non-mirror isomer of that compound is not specified, for example, in a formula or chemical name, the description is intended to include all isomers and mirror isomers of the compound described alone or in any combination.

[0063] Formaldehyde reacts with at least one phenol of formula (I) to form a methylene unit located between two phenyl rings, as shown by bisphenol of formula (II):

[0064] .

[0065] In formula (II), each H is a hydrogen atom on the aromatic ring; each R is a group that substitutes for a hydrogen atom on the aromatic ring; each OH is a hydroxyl group that substitutes for a hydrogen atom on the aromatic ring; each x is 1 to 4, and each x may be the same or different; each y is 1 to 4, and each y may be the same or different; and each z is 0 to 4. Suitable R groups are as described above.

[0066] Besides formaldehyde, paraformaldehyde ((CH2O)) n (I) can be used as a formaldehyde source. Alternatively, formalin (an aqueous solution of formaldehyde) can be used as a formaldehyde source. In some embodiments, formaldehyde (or a formaldehyde source) is introduced into a mixture comprising at least one phenol of formula (I). The mixture comprising at least one phenol of formula (I) may also include a solvent, a catalyst or both, and other components.

[0067] Other aldehydes and ketones, such as those represented by formula (III), are also considered:

[0068] .

[0069] In equation (III), R a and R b Each of them can be independently hydrogen, an unsubstituted hydrocarbon group, a substituted hydrocarbon group, or a functional group containing at least one element from Groups 13-17 of the periodic table. For R in formula (III) a and R bEach suitable R group may include those described above with respect to formula (I). 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, dibutyl and tributyl, pentyl, hexyl, heptyl, octyl, ethyl-2-hexyl, isooctyl, nonyl, n-decyl, isodecyl or 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.

[0070] R in equation (III) a and R b Each of them can independently have any suitable number of carbon atoms, such as 1 to 20 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, R in formula (III) a and R b The number of carbon atoms in each of them can be independently 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 may be used alone to describe an open range or in combination to describe a closed range. R in Equation (III) a and R b Each of them can independently be straight-chain or branched, saturated or unsaturated, cyclic or acyclic, aromatic or non-aromatic. Regarding saturation, R in equation (III) a and R b Each of them can be independently fully saturated, partially unsaturated, or completely unsaturated.

[0071] Illustrative but non-limiting examples of aldehydes include formaldehyde, acetaldehyde, crotonaldehyde, pentanal, butyraldehyde, 3-methyl-butenal, acrolein, benzaldehyde, furfural, glyoxal, their derivatives and combinations thereof.

[0072] Illustrative but non-limiting examples of ketones include propanone, acetone, benzophenone, 2-pentanone, 3-methyl-2-butanone, 3-hexanone, and their derivatives and combinations thereof.

[0073] Catalyst 215 may include any suitable acid or base catalyst, such as Brønsted acids and Brønsted bases. Illustrative but non-limiting examples of catalyst 215 include organic acids, inorganic acids, or combinations thereof. Organic acids include, but are not limited to, methanesulfonic acid, p-toluenesulfonic acid, trifluoroacetic acid, oxalic acid (CAS No. 144-62-7), or combinations thereof, and others. Non-limiting examples of inorganic acids include hydrochloric acid, sulfuric acid, phosphoric acid, or combinations thereof, and others. The acid catalyst can be removed by heating the reaction product of the bisphenol containing formula (II) at a high temperature. For example, oxalic acid decomposes into carbon dioxide at about 160°C or higher, such as about 165°C or higher. Alternatively or additionally, the acid catalyst can also be removed from the reaction product of the bisphenol containing formula (II) by distillation of the reaction product, neutralization with sodium hydroxide (NaOH), or a combination thereof. The salt formed after acid neutralization (e.g., sodium chloride (NaCl)) is suitable for subsequent reactions of bisphenol 105, such as glycidization.

[0074] Non-limiting examples of base catalysts include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, basic amines, or combinations thereof. The base catalyst used may be an aqueous solution of about 5% to about 50% by weight, such as about 10% to about 40% by weight, such as about 20% to about 30% by weight.

[0075] Mixtures comprising at least one phenol of formula (I) may also include one or more solvents. Suitable solvents include organic solvents. Organic solvents may include, but are not limited to, aliphatic hydrocarbons, cyclic aliphatic hydrocarbons, aromatic hydrocarbons, alcohols, ethers, esters, nitriles, or combinations thereof. Illustrative but non-limiting examples of organic solvents include tert-butylbenzene (tBB), toluene, ethylbenzene, xylene (one or more of 1,2-dimethylbenzene, 1,3-dimethylbenzene, or 1,4-dimethylbenzene), 1,3,5-trimethylbenzene (also known as mesitylene), decane, diethylene glycol monomethyl ether, ethylene glycol monobutyl ether, tetrahydrofuran alcohol, ethylene glycol monomethyl ether, ethyl acetate, isopropyl acetate, butyl acetate, amyl acetate, isomers thereof, or combinations thereof. Other solvents may be considered. In some embodiments, the organic solvent includes tert-butylbenzene (tBB), toluene, ethylbenzene, xylene, 1,3,5-trimethylbenzene, isomers thereof, or mixtures thereof.

[0076] In some embodiments, the solvent used to remove or neutralize the catalyst can be selected based on its boiling point. For example, a solvent with a boiling point of about 100°C or higher at 1 bar (100 kPa (absolute)) can be selected to decompose or neutralize the acid or base. As a non-limiting example, solvents with boiling points between about 160°C and about 170°C (such as tert-butylbenzene, 1,3,5-trimethylbenzene, or other solvents) can be used with the oxalic acid catalyst, and after the formation of bisphenol, the oxalic acid can be removed from the bisphenol / solvent / oxalic acid mixture at a temperature of about 165°C to about 170°C. Heating at this temperature causes the oxalic acid to decompose and sublimate.

[0077] In some instances, the solvent may have a boiling point of about 100°C to about 210°C, such as about 110°C to about 200°C, such as about 120°C to about 190°C, such as about 130°C to about 180°C, such as about 140°C to about 170°C, such as about 150°C to about 160°C, or about 165°C to about 170°C (at 1 bara (100 kPa (absolute))). In at least one embodiment, the boiling point of the solvent (at 1 bara (100 kPa (absolute)); in °C) may be 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, 170, 175, 180, 185, 190, 195, or 200, or a range thereof. 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 may be used alone to describe an open range or in combination to describe a closed range.

[0078] The total amount of components in the mixture other than the solvent (total amount of formaldehyde, catalyst and at least one phenol) is based on dry weight percentage and the total amount of formaldehyde, catalyst and at least one phenol does not exceed 100 wt%.

[0079] Based on the total wt% of at least one phenol, formaldehyde, and catalyst, the total amount of at least one phenol of formula (I) used in the reaction to form bisphenol of formula (II) can be from about 74 wt% to about 86 wt%, such as from about 76 wt% to about 85 wt%, such as from about 78 wt% to about 82 wt%. In some embodiments, the total amount (wt%) of at least one phenol of formula (I) used in the reaction to form bisphenol of formula (II) can be 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, or 86 or a range thereof, but other amounts may also be considered. Each of the foregoing figures may be preceded by the words “about,” “at least about,” “less than about,” or “greater than about,” and any of the foregoing figures may be used alone to describe an open range or in combination to describe a closed range.

[0080] The amount of formaldehyde used in the reaction of bisphenol of formula (II) can be from about 11 wt% to about 23 wt%, such as from about 12 wt% to about 21 wt%, such as from about 15 wt% to about 19 wt%, based on the total wt% of formaldehyde, catalyst, and at least one phenol. In some embodiments, the total amount (wt%) of formaldehyde used in the reaction of bisphenol of formula (II) can be 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, or 23, or a range thereof, but other amounts may also be considered. Each of the foregoing figures may be preceded by the words “about,” “at least about,” “less than about,” or “greater than about,” and any of the foregoing figures may be used alone to describe an open range or in combination to describe a closed range.

[0081] Based on the total wt% of formaldehyde, catalyst, and at least one phenol, the total amount of catalyst used for the reaction to form bisphenol of formula (II) can be from about 0.6 wt% to about 14 wt%, such as from about 1.25 wt% to about 7 wt%, such as from about 2.5 wt% to about 3.5 wt%. In some embodiments, the total amount (wt%) of catalyst used for the reaction to form bisphenol of formula (II) can be 0.6, 1, 1.25, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14 or a range thereof, but other amounts may also be considered. Each of the foregoing figures may be preceded by the words “about,” “at least about,” “less than about,” or “greater than about,” and any of the foregoing figures may be used alone to describe an open range or in combination to describe a closed range.

[0082] The weight ratio of the solvent used to react and form the bisphenol of formula (II) to at least one phenol of formula (I) can be from about 0.7 to about 1.6, such as from about 0.75 to about 1.3, such as from about 0.8 to about 1. In some embodiments, the weight ratio of the solvent used to react and form the bisphenol of formula (II) to at least one phenol of formula (I) can be 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1, 1.05, 1.1, 1.15, 1.2, 1.25, 1.3, 1.35, 1.4, 1.45, 1.5, 1.55 or 1.6 or a range thereof, but other amounts may also be considered. Each of the foregoing figures may be preceded by the words “about,” “at least about,” “less than about,” or “greater than about,” and any of the foregoing figures may be used alone to describe an open range or in combination to describe a closed range.

[0083] Monophenols react with aldehydes (or ketones) to form bisphenols, with a stoichiometric ratio of monophenol to aldehyde (or ketone) of 2:1. However, according to this disclosure, the reaction involves an aldehyde (or ketone) in excess of the monophenol in stoichiometric proportion.

[0084] The amount of aldehyde (or ketone) used in the reaction is stoichiometrically excess relative to the monophenol, such as an aldehyde (or ketone) in excess of about 1.05 to about 5 stoichiometric moles relative to the monophenol, such as an aldehyde (or ketone) in excess of about 1.5 to about 4 stoichiometric moles relative to the monophenol, such as an aldehyde (or ketone) in excess of about 1.75 to about 3 stoichiometric moles relative to the monophenol, such as an aldehyde (or ketone) in excess of about 2 to about 2.5 stoichiometric moles relative to the monophenol, but other stoichiometric excesses may also be considered. In at least one instance, an aldehyde (or ketone) in excess of about 1.5 to about 2 stoichiometric moles relative to the monophenol is used, such as about 1.6 to about 1.9, such as about 1.7 to about 1.8, such as about 1.7 to about 1.75, or about 1.75 to about 1.8, such as about 1.75. Any of the foregoing figures may be used alone to describe an open range or in combination to describe a closed range. As mentioned above, when using a ketone to produce bisphenol, a ketone in excess relative to the monophenol is used. Therefore, when using a ketone, the above-mentioned stoichiometric excess can be applied.

[0085] A stoichiometric excess of formaldehyde (or ketone) allows for the high conversion of at least formula (I) phenols into reaction products comprising bisphenols of formula (II). The use of a stoichiometric excess of formaldehyde (or ketone) also contrasts with conventional methods for forming bisphenols (such as TMBPF). Here, previous methods for forming bisphenols (such as TMBPF) use excess phenol, which requires washing or other purification techniques (such as high-energy distillation) to remove the phenol after the reaction. Furthermore, the use of the stoichiometric excess of formaldehyde (or ketone) described herein eliminates the need for recycling the phenol of formula (I) in the embodiments described herein. Recycling can be performed if necessary. Additionally, the choice of solvent allows for the removal of excess formaldehyde (or ketone) and water by distillation without significant solvent loss. The choice of solvent also allows for the thermal decomposition of the catalyst used.

[0086] In some embodiments, formaldehyde may be used in the form of an aqueous solution (e.g., formalin) with a concentration of about 10% to about 60% by weight, such as an aqueous solution with a concentration of about 20% to about 50% by weight, and most commonly an aqueous solution with a concentration of about 30% to about 40% by weight. In some embodiments, paraformaldehyde is used.

[0087] The molar ratio of the total amount of catalyst to the total amount of at least one phenol can be from about 0.005 to about 0.5, such as from about 0.01 to about 0.24, such as from about 0.02 to about 0.12, such as from about 0.04 to about 0.06, such as from about 0.045 to about 0.055, such as about 0.05, but other molar ratios are also possible. In some embodiments, the molar ratio of the total amount of catalyst to the total amount of at least one phenol can be 0.005, 0.01, 0.015, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, or 0.5, or a range thereof. 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 may be used alone to describe an open range or in combination to describe a closed range.

[0088] Bisphenol of formula (II) can be prepared by feeding at least one phenol of formula (I), formaldehyde 210, catalyst 215, and solvent into a reactor. The resulting mixture can be reacted under reaction conditions 620, which are effective in forming bisphenol of formula (II). In some examples, at least one phenol of formula (I), catalyst 215, and solvent are first fed into the reactor, and formaldehyde 210 is added to the reactor at a suitable rate to form bisphenol of formula (II).

[0089] Reaction conditions 620 may include the mixing time (or injection time), the time after mixing (or the time after injection), and the total reaction time. The mixing time is the period during which formaldehyde 210 is added to the reactor. The mixing time can be from about 30 minutes to about 20 hours, such as from about 40 minutes to about 10 hours, such as from about 50 minutes to about 2 hours, but other time periods may also be considered.

[0090] The post-reaction time in reaction condition 620 is the period from the addition of all formaldehyde to the reactor until the end of the reaction. The end of the reaction can be based on the point in time when at least one phenol has undergone a certain percentage conversion. For example, the post-reaction time in reaction condition 620 can be the amount of time between the end of the addition time and the point where at least one phenol has undergone approximately 90% or higher conversion, such as approximately 91% or higher conversion, such as approximately 92% or higher conversion, such as approximately 93% or higher conversion, such as approximately 94% or higher conversion, such as approximately 95% or higher conversion, such as approximately 96% or higher conversion, such as approximately 97% or higher conversion, such as approximately 98% or higher conversion, such as approximately 99% or higher conversion, such as approximately 99.9% or higher conversion, such as approximately 100% conversion. The post-reaction time can correspond to... Figure 5The post-reaction period 515. The total reaction time of reaction condition 620 is the sum of the inoculation time and the post-reaction time. The total reaction time of reaction condition 620 can be from about 1 hour to about 40 hours, such as from about 10 hours to about 25 hours, such as from about 15 hours to about 20 hours, but other time periods may also be considered.

[0091] Reaction conditions 620 may include reactor temperatures of about 50°C to about 200°C, such as about 70°C to about 120°C, such as about 90°C to about 100°C, but other temperatures may also be considered. The reactor temperature may be the boiling point (or temperature range) of the reaction mixture, or the azeotropic boiling point (or range) of the water-solvent combination. In some instances, tBB is used as the solvent under atmospheric conditions, and the reactor temperature may be about 75°C to about 100°C, such as about 80°C to about 96°C, such as about 96°C. Higher temperatures and higher pressures may result in shorter reaction times, but may also increase the amount of trimers, tetramers, and other heavy substances in the reaction products containing bisphenols of formula (II). The reactor temperature is monitored by a temperature probe.

[0092] Reaction conditions 620 may also include reactor pressure measured in absolute pressure. Reactor pressure may be from about 1 bara (about 100 kPa (absolute)) to about 4.5 bara (about 450 kPa (absolute)), such as from about 1.05 bara (about 105 kPa (absolute)) to about 1.8 bara (about 180 kPa (absolute)), such as from about 1.1 bara (about 110 kPa (absolute)) to about 1.2 bara (about 120 kPa (absolute)), but other pressures may also be considered. In at least one embodiment, the reactor pressure of reaction conditions 620 may be from about 1 bara (about 100 kPa (absolute)) to about 1.8 bara (about 180 kPa (absolute)), such as from about 1 bara (about 100 kPa (absolute)) to about 1.2 bara (about 120 kPa (absolute)). Select a pressure (or pressure range) to match a temperature (or temperature range) based on the reaction mixture that boils at a pressure ≥ 1 bara and a temperature ≥ 96°C.

[0093] Reaction conditions 620 take into account other temperatures, times, and pressures, and may vary depending on, for example, the at least one phenol, solvent, or catalyst used in the reaction. Conditions for the effective formation of bisphenols of formula (II) may include stirring, mixing, agitation, or a combination thereof. Conditions may, where appropriate, include the use of non-reactive gases, such as nitrogen, argon, or a combination thereof. For example, a reaction mixture containing at least one phenol, solvent, catalyst, and formaldehyde may be used with such or other non-reactive gases to degas the components or otherwise remove oxygen from the reaction mixture.

[0094] As described herein, the reaction products of bisphenols comprising formula (II) may also include one or more reaction product components selected as appropriate, such as trimers, tetramers, light compounds, heavy compounds, and combinations thereof. Water may also be formed or present in the reaction products. Light compounds are reaction product components with boiling points lower than the boiling point of the desired bisphenol. Heavy compounds are reaction product components with boiling points higher than the boiling point of the desired bisphenol (excluding trimers, tetramers, or combinations thereof).

[0095] After the reaction is considered complete (e.g., after the post-reaction time or post-reaction period 515), water and formaldehyde can be removed from the reaction product containing the bisphenol of formula (I). This removal of water and formaldehyde can correspond to Figure 5 Operation 520. The removal of water and formaldehyde can be carried out, for example, by distillation (under suitable conditions) of the reaction products containing bisphenol of formula (I), solvent, water, formaldehyde, and other components selected as appropriate.

[0096] In some embodiments, the removal of water and formaldehyde is carried out at a temperature below the boiling point of the solvent. In cases where formaldehyde and water are removed simultaneously by solvent evaporation or distillation, the solvent and aqueous phase can be separated in a phase separator, such as a condenser or phase separation vessel, and then returned to the reactor containing the reaction products.

[0097] In some embodiments, the catalyst used to form the bisphenol of formula (II) may be removed, neutralized, or a combination thereof as described above with respect to operation 525, which may be selected as appropriate. In at least one embodiment, such as when the catalyst is a base catalyst, operation 525, which may be selected as appropriate, is not performed. Depending on, for example, the catalyst used to form the bisphenol, the bisphenol-containing product mixture may be prepared for subsequent processing (if desired) after operation 520 (e.g., the bisphenol-containing product mixture leaving pipeline 521), after operation 525, which may be selected as appropriate (e.g., the bisphenol-containing product mixture leaving pipeline 526), ​​or a combination thereof.

[0098] The mixture of bisphenol-containing products formed after the reaction period 515, operation 520, operation 525 (as appropriate), or a combination thereof, may correspond to the first composition 201.

[0099] As described herein, the reaction products of bisphenols comprising formula (II) may include one or more additional components, such as trimers, tetramers, light compounds, and heavy compounds. Figure 6B As shown, the trimers and tetramers of the reaction products of bisphenols comprising formula (II) may include trimer 602, tetramer 604a, tetramer 604b, or combinations thereof. In trimer 602, tetramer 604a, tetramer 604b, or combinations thereof, A is a group that substitutes for a hydrogen atom on the aromatic ring, and can be represented by the following structures:

[0100] ,

[0101] in:

[0102] H, OH, R, x, y, and z are as described above; and

[0103] Tilde keys indicate connections to aromatic rings.

[0104] Functionalized trimers in reaction products or resin compositions of functionalized bisphenols comprising formula (II) may include trimers in which one or more oxygen atoms of the trimer are functionalized, such as one, two, or all three oxygen atoms of the trimer being functionalized. For example, consider monoglycidylated trimers, diglycidylated trimers, and triglycidylated trimers, wherein the epoxy functional groups are respectively attached to only one, two, or three oxygen atoms.

[0105] Similarly, functionalized tetramers in reaction products or resin compositions containing functionalized bisphenols of formula (II) may include tetramers in which one or more oxygen atoms of the tetramer are functionalized, such as 1, 2, 3 or all four oxygen atoms of the tetramer are functionalized.

[0106] The amount of bisphenol represented by formula (II) in the reaction product (based on the total amount of bisphenol, trimer, and tetramer in the reaction product, not exceeding 100 wt%) can be about 75 wt% or more, such as about 76% or more, such as about 77% or more, such as about 78% or more, such as about 79% or more, such as about 80% or more, such as about 81% or more, such as about 82% or more, such as about 83% or more, such as about 84% or more, such as about 85% or more, such as about 86% or more, such as about 87% or more, such as about 88% or more, such as about 89% or more, such as about 90% or more. wt% or more, such as about 91% or more, such as about 92% or more, such as about 93% or more, such as about 94% or more, such as about 95% or more, such as about 96% or more, such as about 97% or more, such as about 98% or more, such as about 99% or more, such as about 99.9% or more, such as about 100%, but other amounts may also be considered.

[0107] In some embodiments, the amount of trimer in the reaction product containing bisphenol of formula (II) may be about 25 wt% or less, such as about 20 wt% or less, such as about 15 wt% or less, such as about 10 wt% or less, such as about 5 wt% or less, such as about 1 wt% or less, such as about 0 wt%, and the amount of bisphenol, trimer and tetramer in the reaction product shall not exceed 100 wt%.

[0108] In some embodiments, the total amount of the tetramer in the reaction product containing the bisphenol of formula (II) may be about 25 wt% or less, such as about 20 wt% or less, such as about 15 wt% or less, such as about 10 wt% or less, such as about 5 wt% or less, such as about 1 wt% or less, such as about 0 wt%, and the total amount of the bisphenol, trimer and tetramer in the reaction product shall not exceed 100 wt%.

[0109] The formation of the bisphenol of formula (II) is characterized by a high conversion of at least one phenol of formula (I) into a reaction product comprising the bisphenol of formula (II), one or more additional components (e.g., trimers, tetramers, light components, heavy components, and others) or combinations thereof (e.g., first composition 201). The conversion of at least one phenol of formula (I) may be about 90% or higher, such as about 91% or higher, such as about 92% or higher, such as about 93% or higher, such as about 94% or higher, such as about 95% or higher, such as about 96% or higher, such as about 97% or higher, such as about 98% or higher, such as about 99% or higher, such as about 99.9% or higher, such as about 100% conversion, but other conversion percentages may also be considered.

[0110] Subsequent processing

[0111] Embodiments of this disclosure generally also involve using the bisphenols described herein as raw material components of resin compositions, such as epoxy resin compositions, polycarbonate resin compositions, and other resin compositions and polymers. For example, when the bisphenol of formula (II) includes TMBPF, TMBPF can be converted to TMBPF-DGE.

[0112] In some embodiments, a mixture of products (or reaction products) comprising bisphenol of formula (II)—which may be formed by operation 520, operation 525, or both, if selected as appropriate—may be integrated with the reactor for subsequent processing. Alternatively, and depending on, for example, the catalyst used to form the bisphenol, subsequent processing may occur directly in the same reactor where the bisphenol is formed.

[0113] The product mixture (or reaction product) containing bisphenol of formula (II) formed after the post-reaction period 515, operation 520, operation 525 (if applicable), or a combination thereof, may correspond to the first composition 201. As described above, and as a non-limiting example, the first composition 201 may be converted into a second composition 202 containing glycidylated bisphenol. Generally, the product mixture containing bisphenol may undergo subsequent processing, which may include converting the reaction product containing bisphenol of formula (II) with a reactant that chemically links one or more polymerizable groups to the oxygen atom of the bisphenol. For example, glycidylation can be used to form diglycidyl ethers (e.g., TMBPF-DGE).

[0114] As other non-limiting examples of subsequent processing, mixtures of products containing bisphenols of formula (II) can be acrylated, acylated, alkylated, or subjected to any suitable reaction to form polymerizable groups chemically bonded to the oxygen atoms of the bisphenols in the first composition (and, if present, oxygen atoms in one or more trimers, one or more tetramers, or combinations thereof). Examples of bisphenols having polymerizable groups (functionalized bisphenols) are represented by formula (IV):

[0115] .

[0116] In formula (IV), each (OG) is a group that replaces a hydrogen atom on a respective aromatic ring; G represents a polymerizable group chemically bonded to an oxygen (O) atom, and each of H, R, x, y, and z is as described above. The G groups may be the same or different. In some embodiments, each G group may independently include an epoxide, olefin, acrylate, nitrile, or other polymerizable functional group.

[0117] Figure 7A A reaction diagram 700 shows an example conversion process following the formation of a bisphenol of formula (II). In this example, a glycidylation reaction is shown. Reaction diagram 700 is merely an example and is not limiting. As shown, and in some embodiments, the process described herein may further include converting at least a portion of the reaction product containing the bisphenol of formula (II) into a conversion product, such as an epoxy resin composition containing a diglycidylation product of formula (IVa). This conversion process typically involves reacting the reaction product containing the bisphenol of formula (II) with epihalool 701 under conversion conditions 720.

[0118] Non-limiting examples of epihaloalcohols 701 include epihaloalcohols in which X is a halogen such as F, Cl, Br, or I (such as Cl or Br); R 1 It is a hydrogen atom, an unsubstituted hydrocarbon group, or an unsubstituted hydrocarbon group; or a combination thereof. Table 701 shows the R of haloalcohols. 1The group may include 1 to 20 carbon atoms, such as 1 to 10 carbon atoms, such as 1 to 4 carbon atoms. In some embodiments, epihalohydrin 701 comprises epichlorohydrin (X=Cl and R...). 1 =H; CAS No. 106-89-8), epibromool (in formula (II) X=Br and R 1 =H; CAS No. 3132-64-7) or a combination thereof.

[0119] In some embodiments, conversion condition 720 may include the use of an excess of epihalool 701 relative to the stoichiometric amount of bisphenol of formula (II). The epihalool and bisphenol may be in a molar ratio of about 7:1 to about 1:1, such as about 6:1 to about 1.01:1, such as about 5:1 to about 3:1, such as about 4:1, but other molar ratios may also be considered.

[0120] Conversion condition 720 may also include the use of a coupling catalyst. The coupling catalyst can be used to promote the reaction of epihaloalcohol 701 and bisphenols of formula (II). Non-limiting examples of suitable coupling catalysts are ammonium halide salts, such as ammonium chloride or ammonium bromide salts, such as butyltrimethylammonium chloride or tetrabutylammonium bromide, or hydroxyl salts, such as sodium hydroxide, lithium hydroxide, or potassium hydroxide, and other salts. More than one coupling catalyst may be used. If used, the coupling catalyst may be included in the reaction mixture at any suitable concentration level, such as from about 2 wt% to about 10 wt% by weight relative to the bisphenol reactant (e.g., TMBPF) in the reaction mixture.

[0121] In some instances, the bisphenol of formula (II) (or the reaction product containing a bisphenol of formula (II)) may include one or more of the following operations after the reaction with the epihalohydrin has begun: (i) removal of excess epihalohydrin in one or more operations (e.g., by applying a vacuum, heating, or both); (ii) dehydrohalogenation of the composition in one or more operations (before, after, or both before and after removal of any excess epihalohydrin) to achieve a suitably low level of hydrolyzable chloride content; and (iii) washing away any salts that may be generated during any dehydrohalogenation operation (e.g., by aqueous treatment with NaCl). Suitable dehydrohalogenating agents that may be employed include alkali metal hydroxides, such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and mixtures thereof.

[0122] As discussed above, the reaction products of bisphenols comprising formula (II) may include one or more components, selected as appropriate, including trimers, tetramers, light compounds, heavy compounds, or combinations thereof. In some instances, these one or more components, selected as appropriate, may be present in the reaction products, which undergo a transformation reaction such that the reaction products of functionalized bisphenols comprising formula (IV) may include functionalized trimers, functionalized tetramers, light compounds, heavy compounds, or combinations thereof. The functionalized trimers and functionalized tetramers are functionalized at the oxygen atom of the phenolic group in a manner similar to that discussed above with respect to functionalized bisphenols of formula (IV). The reaction products of functionalized bisphenols comprising formula (IV) may be resin compositions.

[0123] Functionalized trimers in reaction products or resin compositions containing functionalized bisphenols of formula (IV) may include trimers in which one or more oxygen atoms are functionalized, such as one, two, or all three oxygen atoms of the trimer being functionalized. Similarly, functionalized tetramers in reaction products or resin compositions containing functionalized bisphenols of formula (IV) may include tetramers in which one or more oxygen atoms are functionalized, such as one, two, three, or all four oxygen atoms of the tetramer being functionalized.

[0124] In some embodiments, a resin composition (e.g., an epoxy resin composition) is provided comprising a functionalized bisphenol of formula (IV) (such as TMBPF-DGE) and one or more components selected as appropriate. The amount of the functionalized bisphenol of formula (IV) in the resin composition or reaction product (based on the total amount of functionalized bisphenol, functionalized trimer, and functionalized tetramer in the reaction product, the total amount of bisphenol, functionalized trimer, and functionalized tetramer in the reaction product not exceeding 100%). wt%) can be, for example, about 76% or more, such as about 77% or more, such as about 78% or more, such as about 79% or more, such as about 80% or more, such as about 81% or more, such as about 82% or more, such as about 83% or more, such as about 84% or more, such as about 85% or more, such as about 86% or more, such as about 87% or more, such as about 88% or more, such as about 89% or more, such as about 90wt% or more, such as about 91% or more, such as about 92% or more, such as about 93% or more, such as about 94% or more, such as about 95% or more, such as about 96% or more, such as about 97% or more, such as about 98% or more, such as about 99% or more, such as about 99.9% or more, such as about 100%, but other amounts are taken into consideration.

[0125] In some embodiments, the amount of functionalized trimer in the resin composition or reaction product containing the functionalized bisphenol of formula (IV) may be about 25 wt% or less, such as about 20 wt% or less, such as about 15 wt% or less, such as about 10 wt% or less, such as about 5 wt% or less, such as about 1 wt% or less, such as about 0 wt%, and the total amount of bisphenol, trimer and tetramer in the reaction product does not exceed 100 wt%.

[0126] In some embodiments, the total amount of tetramer in the resin composition or reaction product containing the functionalized bisphenol of formula (IV) may be about 25 wt% or less, such as about 20 wt% or less, such as about 15 wt% or less, such as about 10 wt% or less, such as about 5 wt% or less, such as about 1 wt% or less, such as about 0 wt%, and the total amount of bisphenol, trimer and tetramer in the reaction product does not exceed 100 wt%.

[0127] As described herein, the reaction products of functionalized bisphenols comprising formula (IV) may include one or more additional components, such as trimers, tetramers, light compounds, and heavy compounds. Figure 7B As shown, the trimers and tetramers of the reaction products of functionalized bisphenols comprising formula (IV) may include trimer 703, tetramer 704a, tetramer 704b, or combinations thereof. In trimer 703, tetramer 704a, tetramer 704b, or combinations thereof, A 1 A group that replaces a hydrogen atom on an aromatic ring, and can be represented by the following structure:

[0128] ,

[0129] in:

[0130] y and z are as described above; and

[0131] Tilde keys indicate connections to aromatic rings.

[0132] In some embodiments, the reaction product containing formula (IV) of the functionalized bisphenol (such as the reaction product containing formula (IVa) of the diglycidylated bisphenol) may have an epoxy group content of about 1,000 mmol / kg, such as about 3,000 mmol / kg, such as about 4,000 mmol / kg or more, such as about 5,000 mmol / kg. In these and other embodiments, the reaction product containing formula (IV) of the functionalized bisphenol may have an epoxy group content of about 10,000 mmol / kg or less, such as about 8,000 mmol / kg or less, such as about 7,000 mmol / kg or less, such as about 6,000 mmol / kg or less.

[0133] Resin compositions (e.g., reaction products comprising bisphenols having polymerizable groups as represented by formula (IV), reaction products comprising diglycidylated bisphenols of formula (IVa), and second composition 202, and others) can be used to manufacture any suitable type of polymer. For example, reaction products comprising diglycidylated bisphenols of formula (IVa) can be used to manufacture any type of polymer that typically uses diepoxide reactants, including polymers, for example, for use in the coatings, composites, or adhesives industries.

[0134] The resin compositions described herein can be used as adhesives, paints, sealants, and in other applications. For example, these compositions can be used in the installation of concrete and cement structures, such as high-gloss concrete installations. 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. These compositions are commonly used in the production of composite materials, adhesives, insulation materials, molded products, bonding agents, laminates, and other articles and articles.

[0135] The following examples are provided to offer a complete disclosure and description of how to manufacture and use embodiments of this disclosure to those skilled in the art, without limiting the scope of embodiments of this disclosure. Every effort has been made to ensure the accuracy of the numerical values ​​used, but some experimental errors and deviations should be taken into account.

[0136] Example

[0137] Test methods

[0138] 1. Characterization of bisphenols and byproducts of formula (II)

[0139] The bisphenol of formula (II) and the byproducts of the reaction that form the bisphenol of formula (II) are characterized by the following test methods.

[0140] Ultra-high performance liquid chromatography (UHPLC) combined with diode array detection (DAD) was applied to samples to improve the separation of trimers and tetramers from other products, including byproducts, in the reaction products. UHPLC-DAD was performed as follows. Analysis was conducted on an Agilent 1290 Infinity II ultra-high performance liquid chromatograph equipped with a multisampler and 20 μL injection loop, a binary pump, a solvent selection valve, a multilayer column thermostat with an 8-column selection valve, and a diode array detector. Waters Acquity UPLC BEH (extrinsic ethyl-bridged hybrid ultra-high performance liquid chromatography) C18 columns (1.7 μm particles, 2.1 mm x 150 mm) were used.

[0141] Sample preparation for measuring trimer and tetramer products was performed as follows. First, a stock solution of 100 mg anisole and 150 g ACN was prepared. Then, 100 mg TMBPF and 10 g of the stock solution were added to a suitable container and homogenized. All weights are indicated to an accuracy of 0.1 mg. Finally, the sample was filtered through a 0.2 μm disposable polytetrafluoroethylene (PTFE) syringe filter.

[0142] Peak identification was performed using ultra-high performance liquid chromatography combined with mass spectrometry (UHPLC-MS). Unknown components were identified using an Agilent 6120B single quadrupole mass spectrometer with electrolytic ionization capability. The mass spectrometer was directly coupled to the UHPLC.

[0143] The trimer was identified by using CDCl3 as the deuteration solvent. 13 The determination was performed using C NMR (100 MHz) spectroscopy. The weight percentages of other trimers (as byproducts) and tetramers (as byproducts) involved in the formation of TMBPF, as well as the weight percentages of light and heavy components, were determined using the same procedure described above. In the TMBPF formation reaction, the boiling points of the light components were lower than those of TMBPF, and the boiling points of the heavy components were lower than those of the non-trimer or non-tetramer TMBPF.

[0144] 2. Characterization of glycidylation products

[0145] Some glycidylated products are characterized by the following test methods.

[0146] The diglycidyl and triglycidyl trimers of TMBPF-DGE were characterized by UHPLC-DAD analysis using an Agilent 1290 II UHPLC system with a binary pump, 1290 injection system, and 1290 DAD detector. A WatersAcquity UPLC BEH C18 column (1.7 μm, 2.1 mm x 150 mm) was used.

[0147] Sample preparation for measuring diglycidyl and triglycidyl trimers was performed as follows. 750 mg TMBPF-DGE, 50 mg anisole (internal standard), and 25 ml ACN were added to a suitable container and homogenized. All weights are indicated to an accuracy of 0.1 mg. No internal standard was ignored, and 100% calculations were applied; therefore, no weights were recorded. Samples were filtered into 2 mL vials through a 0.2 μm PTFE disposable syringe filter.

[0148] Peak identification was performed using UHPLC-MS. Unknown components were identified using an Agilent 6120B single quadrupole mass spectrometer with an atmospheric pressure electrospray ionization (ESI) interface. The mass spectrometer was directly coupled to the UHPLC.

[0149] For the diglycidyl trimer and triglycidyl trimer, the same UHPLC settings as described above were used. NMR was not applied. Structure was identified based on molar mass.

[0150] Example 1: Bisphenol

[0151] The bisphenols formed by the embodiments described herein utilize various solvents, catalysts, and phenols. In this example, TMBPF is selected as the target bisphenol. In this example, the general reaction scheme for forming TMBPF is shown in Scheme 1.

[0152] Option 1

[0153]

[0154] For all examples 1A-1F below, TMBPF was formed using a 37 wt% aqueous formaldehyde solution.

[0155] Example 1A: Example TMBPF was prepared according to the following non-limiting procedure. A round-bottom flask serving as a reactor was charged with 1,3,5-trimethylbenzene (approximately 50.4 g; approximately 44.9 wt%) as a solvent, 2,6-xylenol (approximately 50.8 g; approximately 45.3 wt%) as a phenol, oxalic acid catalyst (approximately 1.9 g; approximately 1.7 wt%), and formalin (approximately 24.7 g; approximately 8.1 wt% (dry basis)) as a formaldehyde source. The molar ratio of 2,6-xylenol to formaldehyde was approximately 2:1.5. However, the stoichiometric ratio of the monophenol to formaldehyde used in this reaction was 2:1. A molar ratio of 2,6-xylenol to formaldehyde of 2:1.5 implies the addition of 50% excess formaldehyde.

[0156] The mixture was stirred and refluxed for approximately 18 h, and a conversion of approximately 97% of 2,6-xylenol was observed. The reaction mixture became clear and completely dissolved at a temperature above approximately 145°C. Distillation yielded a product mixture containing approximately 53.6 wt% TMBPF and 3.5 wt% trimer (hexamethylpyrogallol F, 302 in Figure 3). The product mixture also contained byproducts based on 1,3,5-trimethylbenzene, characterized as follows:

[0157]

[0158] Other byproducts were also observed, but they were not characterized. Example 1A illustrates that 2,6-xylenol, which can serve as a starting point for phenols, can form TMBPF with high conversion.

[0159] Example 1B: In this example, TMBPF is prepared using tert-butylbenzene as a solvent according to the following non-limiting procedure. A round-bottom flask serving as a reactor is charged with tert-butylbenzene (approximately 50.6 g, approximately 45.2 wt%) as solvent, 2,6-xylenol (approximately 50.3 g, approximately 44.9 wt%) as phenol, oxalic acid catalyst (approximately 1.9 g; approximately 1.7 wt%; approximately 5 mol% relative to 2,6-xylenol), and formalin (approximately 8.2 wt% (dry basis)) as a formaldehyde source. The molar ratio of 2,6-xylenol to formaldehyde is approximately 2:1.5. However, the stoichiometric ratio of the monophenol to formaldehyde used in this reaction is 2:1. A 2:1.5 molar ratio of 2,6-xylenol to formaldehyde means the addition of 50% excess formaldehyde.

[0160] The mixture was stirred and refluxed for approximately 18 h, and a conversion of approximately 99% of 2,6-xylenol was observed. Following distillation (using an oil bath set to approximately 205°C), only trace amounts of oxalic acid were observed in the Dean-Stark setting. Only trace amounts of tert-butylbenzene solvent were distilled off during distillation. No byproducts based on tert-butylbenzene solvent were detected. The product mixture contained approximately 51 wt% TMBPF (bisphenol), approximately 4.8 wt% trimer (hexamethylpyrrolidone F, 302 in Figure 3), and approximately 0.3 wt% 2,6-xylenol.

[0161] Example 1B illustrates that, for example, solvent selection can prevent or at least mitigate solvent-based byproducts. For instance, no byproducts were observed based on the tert-butylbenzene solvent. While not wishing to be bound by theory, this result is believed to be due to the low aromatic reactivity of tert-butylbenzene, as it has only one organic substituent on the aromatic ring, unlike the three organic substituents in the case of 1,3,5-trimethylbenzene. It is also noted that tert-butylbenzene has a similar boiling point (approximately 169°C) to 1,3,5-trimethylbenzene (approximately 165°C). Example 1B also demonstrates that TMBPF can form in high yields, with low amounts of byproducts (trimers, tetramers, light substances, and heavy substances) and high conversion of 2,6-xylenol as the starting phenol.

[0162] Examples 1C-1F: Further experiments were conducted using the procedure of Example 1B to prepare TMBPF (as shown in Examples 1C-1E in Table 1). A similar procedure (Example 1F) was carried out on a large scale using a top-mounted mechanical stirrer and heated with an electric heating pack. Some reaction details are shown in Table 1, including those of Examples 1A and 1B. In Table 1, wt% are on a dry basis, and for formaldehyde, the amounts shown do not include water in a 37% formaldehyde solution. In each example, oxalic acid was approximately 5 mol% relative to 2,6-xylenol. For Example 1A, the solvent was 1,3,5-trimethylbenzene. For Examples 1B-1F, the solvent was tributylbenzene.

[0163] The stoichiometric ratio of monophenol to formaldehyde used in the reaction is 2:1, but the reaction is carried out with excess formaldehyde. A molar ratio of 2,6-xylenol to formaldehyde of 2:1.5 means that 50% excess formaldehyde was added, while a molar ratio of 2,6-xylenol to formaldehyde of 2:1.75 means that 75% excess formaldehyde was used.

[0164] Table 1

[0165] <![CDATA[ Example ]]> <![CDATA[ Example 1A ]]> <![CDATA[ Example 1B ]]> <![CDATA[ Example 1C ]]> <![CDATA[ Example 1D ]]> <![CDATA[ Example 1E ]]> <![CDATA[ Example 1F ]]> Solvent, wt% 44.9 45.2 65.6 55.0 44.4 44.4 2,6-Xylene, wt% 45.3 44.9 28.1 36.8 44.4 44.4 Formaldehyde 100%, wt% 8.1 8.2 5.2 6.8 9.5 9.6 Oxalic acid, wt% 1.7 1.7 1.0 1.4 1.7 1.6 Mohr ratio of 2,6-xylenol to formaldehyde 2:1.5 2:1.5 2:1.5 2:1.5 2:1.75 2:1.75

[0166] The selected results of the reaction that forms TMBPF as an example bisphenol are shown in Table 2. As shown in Table 2, the reaction products include the following: TMBPF, 2,6-xylenol (unreacted phenol), trimer (byproduct), tetramer (byproduct), light product, and heavy product. One of the trimers is hexamethylpyrogallol F. The total weight of these materials is shown as "Total". The percentage conversion of 2,6-xylenol is also presented in Table 2. "Percentage of TMBPF in total (including unreacted phenol)" refers to the percentage of TMBPF obtained based on the total amount of TMBPF, 2,6-xylenol (unreacted phenol), trimer (byproduct), tetramer (byproduct), light product, and heavy product. "Percentage of TMBPF in total (excluding unreacted phenol)" refers to the percentage of TMBPF based on the total wt% excluding 2,6-xylenol (unreacted phenol). "The percentage of TMBPF in the total (excluding light and heavy components)" refers to the percentage of TMBPF based solely on the total amount of TMBPF, trimer, and tetramer. Light and heavy components are not represented.

[0167] Table 2

[0168] <![CDATA[ Example ]]> <![CDATA[ Example 1A ]]> <![CDATA[ Example 1B ]]> <![CDATA[ Example 1F ]]> TMBPF, wt% 53.6 51 50.4 2,6-Xylene, wt% 0.61 0.27 0.04 Trimer, wt% 3.48 4.75 4.02 Tetramer, wt% 0.22 0.34 0.31 Lightweight material, wt% 0.28 0.33 0.35 Heavy matter, wt% 0.4 0.96 0.83 Total, wt% 58.6 57.6 55.9 Percentage of 2,6-xylenol conversion, % 97 ≥99 ≥99 The percentage of TMBPF in the total amount (including unreacted phenols), % 91.5 88.5 90.2 The percentage of TMBPF in the total amount (excluding unreacted phenols), % 92.4 89.0 90.2 The percentage of TMBPF in the total (excluding light and heavy materials), % 93.5 90.9 92.1

[0169] Overall, the non-limiting results shown in Table 2 demonstrate, for example, that TMBPF and other bisphenols can be formed in high yields with low amounts of byproducts (trimers, tetramers, light and heavy products). When tert-butylbenzene was used as the reaction solvent (Examples 1B and 1F), few or no solvent-dominant byproducts were observed. When 1,3,5-trimethylbenzene was used as the reaction solvent (Example 1A), small amounts (approximately 7 wt%) of solvent-dominant byproducts, such as byproducts 1A-1 and 1A-2, were observed.

[0170] For all examples, the conversion of 2,6-xylenol as a phenol was excellent, with a conversion of approximately 97% in Example 1A and ≥99% in Examples 1B and 1F. This high conversion rate of 2,6-xylenol is at least partly achieved by using an excess of formaldehyde relative to the stoichiometry of the monophenol, compared to conventional techniques that use excess 2,6-xylenol. Notably, the high conversion rate of 2,6-xylenol, as demonstrated by the examples, allows the process described herein to avoid costly and time-consuming separation and recycling operations.

[0171] Furthermore, the water formed during the condensation reaction that produces TMBPF can be distilled off along with excess formaldehyde. Additionally, the decomposition of oxalic acid into CO2 at temperatures near the solvent boiling point allows for the removal of the oxalic acid catalyst from the mixture of TMBPF, solvent, and oxalic acid. Here, for example, the oxalic acid can be decomposed or sublimated under solvent reflux as described herein.

[0172] Furthermore, the embodiments for bisphenol formation proposed herein enable the generation of TMBPF (as an example bisphenol) in product mixtures prepared for further processing, such as glycidylation. Such results, achievable through the embodiments described herein, contrast with conventional techniques that utilize solid-liquid separation, washing, and drying operations to produce pure, dry TMBPF powders that are difficult to process. Additionally, the examples demonstrate that the elimination of dry powder treatment of TMBPF makes loading product mixtures containing TMBPF in slurry form (such as example bisphenol slurry) into subsequent processes faster and safer than conventional TMBPF processing.

[0173] Example 2: Glycidylation

[0174] As an example of subsequent processing of TMBPF, glycidization is performed. The general reaction scheme for the glycidization of TMBPF to TMBPF-DGE is shown in Scheme 2.

[0175] Option 2

[0176]

[0177] For this glycidylation experiment, a product mixture from Example 1A or 1B was used as the starting material. Each product mixture comprised a slurry of TMBPF, a trimer, a tetramer, a light component, and a heavy component. The synthesis of TMBPF diglycidyl ether (TMBPF-DGE) was carried out according to the following procedure: A slurry of TMBPF and a stoichiometric excess of epichlorohydrin was added to a reactor equipped with an overhead condenser. The resulting mixture was stirred and the reactor was heated at the desired reaction temperature (between approximately 50°C and approximately 80°C). A coupling catalyst (e.g., butyltrimethylammonium chloride or tetrabutylammonium bromide) was added and a vacuum was applied until the reaction mixture began to boil. Reflux was maintained for approximately 1 hour to approximately 3 hours. Sodium hydroxide was then added to the reaction mixture over a period of approximately 4 hours to approximately 6 hours. Water was then removed by azeotropic distillation. The reaction mixture was allowed to remain for a post-reaction time of approximately 15 minutes to approximately 45 minutes. Excess epichlorohydrin and solvent were removed by vacuum distillation and stripped with nitrogen for approximately 30 minutes to approximately 60 minutes. Solvent and water are added to the mixture, which is then stirred and the phases are separated. Repeated washing with water may be performed to remove further water-soluble components. The solvent is removed by vacuum distillation followed by nitrogen stripping for approximately 30 to 60 minutes to obtain TMBPF-DGE (Example 2A).

[0178] In addition to TMBPF-DGE (Example 2A), the glycidylation products of TMBPF include diglycidylated trimers (Example 2B) and triglycidylated trimers (Example 2C):

[0179] ,

[0180]

[0181] As described above, the product mixture used to form TMBPF-DGE includes a trimer (having three hydroxyl groups), but this trimer was not found in the product mixture including TMBPF-DGE. This result indicates that the trimer having three hydroxyl groups is completely converted into a diglycidylated trimer (Example 2B), a triglycidylated trimer (Example 2C), and a monoglycidylated trimer. This example illustrates that byproducts of the reaction that forms TMBPF (one or more trimers, tetramers, and other byproducts) can also be converted during glycidylation and can become components in the TMBPF-DGE resin.

[0182] The epoxy group content of the TMBPF-DGE product mixture in Example 2 was determined to be approximately 5,430 mmol / kg. The viscosity of the TMBPF-DGE product mixture at 23°C was determined to be approximately 130 Pa·s.

[0183] The synthesis of eugenol diglycidyl ether and eugenol diglycidyl ether was also carried out according to the same glycidization procedure. The epoxy group content of eugenol diglycidyl ether was determined to be approximately 4,200 mmol / kg. The epoxy group content of eugenol diglycidyl ether was determined to be approximately 4,600 mmol / kg. Both eugenol diglycidyl ether and eugenol diglycidyl ether are solids at room temperature, and their viscosity was not measured.

[0184] The embodiments described herein generally relate to processes for forming bisphenol and epoxy resin compositions. Bisphenols, such as TMBPF, have high initial phenol conversion rates and low byproduct amounts, achieved by using, for example, an excess of formaldehyde relative to the stoichiometry of monophenols. For example, a mixture of bisphenol-containing products in slurry form can be subsequently processed into, for example, resin compositions.

[0185] As used herein, references to chemical substances, R groups, alkyl groups, substituted alkyl groups, hydrocarbon groups, or substituted hydrocarbon groups without specifying a particular isomer (such as butyl) explicitly disclose all isomers (such as n-butyl, isobutyl, dibutyl, and tributyl). For example, references to R groups having four carbon atoms explicitly disclose all their isomers. When a compound is described herein such that a particular isomer, mirror isomer, or non-mirror isomer of that compound is not specified, for example, in a formula or chemical name, the description is intended to include all isomers and mirror isomers of the compound described alone or in any combination.

[0186] It is evident from the foregoing general description and specific aspects that, although the forms of various aspects have been described and illustrated, various modifications can be made without departing from the spirit and scope of this disclosure. Therefore, this disclosure is not intended to be limited thereto. Similarly, the term "comprising" is considered synonymous with the term "including." Likewise, whenever a component, process operation, multiple process operations, an element, or a group of elements is preceded by the transitional phrase "comprising," it should be understood that we also consider the same component or group of elements preceded by the transitional phrases "substantially composed of," "composed of," "selected from a group of," or "is"; and vice versa, terms such as "comprising," "substantially composed of," or "composed of" also include the product of the combination of elements listed after the term.

[0187] For the purposes of this disclosure, and unless otherwise specified, all numerical values ​​in the embodiments and claims herein are modified by means of “about” or “approximately” and take into account experimental errors and variations expected by those skilled in the art. For brevity, only certain ranges are explicitly disclosed herein. However, any lower limit range may be combined with any upper limit to enumerate ranges not explicitly enumerated, and any lower limit range may be combined with any other lower limit to enumerate ranges not explicitly enumerated, and similarly, any upper limit range may be combined with any other upper limit to enumerate ranges not explicitly enumerated. For example, the enumeration of numerical ranges 1 to 5 includes subranges 1 to 4, 1.5 to 4.5, 1 to 2, and other subranges. As another example, the enumeration of numerical ranges 1 to 5 (such as 2 to 4) includes subranges 1 to 4 and 2 to 5, and other subranges. Additionally, a range includes points or individual values ​​between its endpoints, even if not explicitly enumerated. For example, the enumeration of numerical ranges 1 to 5 includes the numbers 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, and other numbers. Therefore, each point or individual value can be combined with any other point or individual value or any other lower or upper bound as its own lower or upper bound to enumerate ranges that are not explicitly enumerated.

[0188] As used herein, the indefinite article “a” or “an” shall mean “at least one” unless otherwise specified or the context clearly indicates otherwise. For example, an aspect containing “monophenol” includes an aspect containing one, two or more monophenols, unless otherwise specified or the context clearly indicates that only one monophenol is included.

[0189] While the foregoing is directed at all aspects of this disclosure, other and further aspects of this disclosure may be designed without departing from its essential scope, the scope of which is defined by the appended claims.

Claims

1. A process for manufacturing an epoxy resin composition, the process comprising: A mixture comprising a catalyst, a monophenol, and an aldehyde is reacted, the mixture comprising an excess of the aldehyde relative to the stoichiometry of the monophenol; The mixture forms a reaction product containing bisphenol; Remove water and unreacted aldehydes from the reaction products; and The reaction product containing the bisphenol is converted into an epoxy resin composition, wherein... After the mixture has reacted and before the reaction products have been converted, the process does not involve washing, drying, solid-liquid separation, or a combination thereof. The monophenols mentioned are 2,6-xylenol, 2,6-diethylphenol, 2,6-diisopropylphenol, 2,6-di-tert-butylphenol, 2,6-dimethoxyphenol, 2,6-diethoxyphenol, or 2-methoxy-4-prop-2-enylphenol. The aldehyde mentioned is formaldehyde. The aldehyde is in stoichiometric excess of 1.05 to 5 relative to the monophenol, and The catalyst is oxalic acid.

2. The process of claim 1, wherein the process is carried out in a single reactor, in situ, or continuously.

3. The process as described in claim 1, wherein: Based on the total weight of the aldehyde, the catalyst, and the monophenol, the amount of the monophenol in the mixture before the reaction is 74 wt% or more; and The conversion rate of the monophenol to the reaction product is 97% or higher.

4. The process as described in claim 3, wherein: The reaction product further comprises one or more components, wherein the one or more components include trimers, tetramers, or combinations thereof; and Based on the total amount of the bisphenol, the trimer, and the tetramer, the amount of the bisphenol in the reaction product is 80 wt% or more, and the total weight of the bisphenol, the trimer, and the tetramer does not exceed 100 wt%.

5. A process for converting monophenols into a conversion product, the process comprising: A mixture comprising an aldehyde, a catalyst, a solvent, and a monophenol is reacted to form a reaction product comprising bisphenol, wherein the mixture comprises an excess of the aldehyde relative to the stoichiometry of the monophenol; Water and residual aldehyde are removed from the reaction product, and the solvent has a boiling point of 150°C or higher at 100 kPa (measured in absolute pressure); and The reaction product containing bisphenol is converted into a transformation product, wherein... After the mixture has reacted and before the reaction products have been converted, the process does not involve washing, drying, solid-liquid separation, or a combination thereof. The monophenols mentioned are 2,6-xylenol, 2,6-diethylphenol, 2,6-diisopropylphenol, 2,6-di-tert-butylphenol, 2,6-dimethoxyphenol, 2,6-diethoxyphenol, or 2-methoxy-4-prop-2-enylphenol. The aldehyde mentioned is formaldehyde. The aldehyde is in stoichiometric excess of 1.05 to 5 relative to the monophenol, and The catalyst is oxalic acid.

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