Process for making bisphenol A (BPA) in the presence of at least two impurities

Abstract

The present invention relates to a process for making bisphenol A in the presence of at least two impurities selected from the group consisting of 2-methylbenzofuran, hydroxyacetone, α-methylstyrene, acetophenone, benzene and / or cumene without poisoning a catalyst system comprising an ion exchange resin catalyst and a sulfur-containing cocatalyst, at least a portion of which is not chemically bound to the ion exchange resin catalyst. Additionally, the present invention provides a process for making polycarbonate.

Description

[Technical field]

[0001] The present invention relates to a process for making bisphenol A and to a process for making polycarbonate. [Background technology]

[0002] Bisphenol A, or BPA, is an important monomer in the production of polycarbonate or epoxy resins. BPA is usually used in the form of para,para-BPA (2,2-bis(4-hydroxyphenol)propane; p,p-BPA), but ortho,ortho-BPA (o,o-BPA) and / or ortho,para-BPA (o,p-BPA) may also be formed in the production of BPA. When referring to BPA, it is primarily para,para-BPA, but also includes small amounts of ortho,ortho-BPA and / or ortho,para-BPA.

[0003] According to the current state of the art, BPA is produced by reacting phenol with acetone in the presence of an acid catalyst to obtain bisphenol. Previously, hydrochloric acid (HCl) was used in the commercial process of the condensation reaction. Currently, a heterogeneous continuous process for the production of BPA is used in the presence of an ion exchange resin catalyst, where the ion exchange resin comprises a crosslinked acid-functionalized polystyrene resin. The most important resin is polystyrene crosslinked by sulfonic acid groups. Divinylbenzene is most used as a crosslinking agent, as described in US Pat. No. 5,399,411; US ​​Pat. No. 5,499,523; US Pat. No. 5,599,633; and US Pat. No. 5,633,665, or in Non-Patent Document 1.

[0004] To achieve high selectivity, the reaction of phenol with acetone can be carried out in the presence of a suitable cocatalyst. US Pat. No. 5,399,433 and US Pat. No. 5,499,466 describe a process for making bisphenol A in the presence of an ion exchange catalyst and mercaptopropionic acid or mercaptan as a cocatalyst. It is known that catalysts deactivate over time. Deactivation is described, for example, in US Pat. No. 5,499,433, US Pat. No. 5,499,466 and US Pat. No. 5,599,466. One of the main objectives of the manufacturing process is to maximize the performance and residence time of the catalyst system. Therefore, to accommodate this objective, it is necessary to identify potential poisons, by-products, impurities in educts, etc.

[0005] US Patent No. 5,999,633 teaches that the production of bisphenols can be improved and the life of the bisphenol condensation catalyst can be extended by using a material with less than about 1 ppm hydroxyacetone as the phenol reactant, where the catalyst system includes an ion exchange resin catalyst and a sulfur-containing cocatalyst, the cocatalyst being chemically bonded to the ion exchange resin catalyst.

[0006] US Patent No. 5,399,663 teaches the use of a specific catalyst system including an ion exchange resin catalyst and a sulfur-containing cocatalyst, the cocatalyst being chemically bound to the ion exchange resin catalyst, and also teaches a process for catalyzing the condensation reaction of phenols with ketones using the specific catalyst system. US Patent No. 5,399,663 further discloses a process for catalyzing the condensation reaction of phenols with ketones without utilizing a bulk promoter that is not chemically bound to the ion exchange resin catalyst.

[0007] Similarly, US Pat. No. 5,399,633 describes a process for making bisphenols in the presence of an acidic ion-exchange resin catalyst modified with a specific cationic compound.

[0008] Patent document 13 describes the production of BPA based on bio-derived phenol and / or bio-derived acetone in the presence of bio-derived impurities in the extract. This document only describes the use of promoter-bound ion-exchange resin catalysts, i.e., ion-bound ion-exchange resin catalysts with a promoter chemically bound (i.e., ionically bound). 2-Methylbenzofuran (2-MBF or MBF) was found to be a common impurity not only in fossil fuel-derived phenol but also in bio-derived phenol. It was found that 2-methylbenzofuran reacts completely during the reaction of phenol with acetone, so that no free 2-MBF is detected in the reaction product (BPA). Also, three new MBF reaction products were identified. Moreover, this BPA was visually pink, and polycarbonate made with this BPA also had an unacceptable color. At the same time, it was found that unknown MBF by-products obtained during the reaction of phenol with acetone, and not MBF itself, were responsible for this color. These unknown by-products could not be removed during BPA purification. Therefore, in order to obtain a low-color BPA PC, it is concluded that the amount of MBF in the bio-derived phenol must be as low as possible. This prior art document does not consider catalyst poisoning.

[0009] Thus, the prior art clearly states that the catalyst system containing an ion exchange resin catalyst and a chemically bound sulfur-containing cocatalyst is susceptible to poisoning by hydroxyacetone and / or 2-methylbenzofuran. Therefore, the prior art teaches that the concentration of hydroxyacetone and / or 2-methylbenzofuran as impurities in the raw phenol and / or raw acetone must be as low as possible to avoid catalyst poisoning.

[0010] In addition, there are other impurities present in the feed acetone and / or feed phenol. For example, in the feed acetone, cumene and / or benzene may be present. Also, in the feed phenol, α-methylstyrene, acetophenone and possibly cumene may be present. As mentioned above, it is common to try to avoid these impurities or reduce their amount as much as possible to avoid side reactions, poisoning of catalysts, etc. in the desired reaction.

[0011] However, the removal of these impurities from raw phenol and / or raw acetone (whether fossil-based or bio-based) takes time and money, which makes the raw phenol and / or raw acetone more expensive. Ultimately, the cost of bisphenol A and the respective polymers prepared from this bisphenol A increases. Furthermore, the concentration of various impurities in raw phenol and / or raw acetone varies depending on the source and purification process of these raw materials. This means that different raw material qualities need to be accommodated (e.g., if the specifications exceed a certain threshold, another purification step needs to be performed), reducing flexibility in the selection of process and raw material source. [Prior art documents] [Patent documents]

[0012] [Patent Document 1] British Patent No. 849965 [Patent Document 2] U.S. Patent No. 4,427,793 [Patent Document 3] European Patent Application Publication No. 0007791 [Patent Document 4] European Patent Application Publication No. 0621252 [Patent Document 5] US Patent Application Publication No. 2005 / 0177006 [Patent Document 6] U.S. Patent No. 4,859,803 [Patent Document 7] European Patent Application Publication No. 0583712 [Patent Document 8] European Patent Application Publication No. 10620041 [Patent Document 9] DE 14312038 [Patent Document 10] U.S. Patent No. 5,414,151 [Patent Document 11] International Publication No. 2012 / 150560 [Patent Document 12] European Patent Application Publication No. 1520617 [Patent Document 13] U.S. Patent No. 8,247,619 [Non-patent literature]

[0013] [Non-Patent Document 1] Chemistry and properties of crosslinked polymers, edited by Santokh S. Labana, Academic Press, New York 1977 Summary of the Invention

[0014] The present invention therefore aimed to provide a process for making ortho,para-bisphenol A, ortho,ortho-bisphenol A, and / or para,para-bisphenol A via condensation of phenol with acetone, which is more economical than the prior art processes. Furthermore, the present invention aimed to provide a process for making ortho,para-bisphenol A, ortho,ortho-bisphenol A, and / or para,para-bisphenol A via condensation of phenol with acetone, which is more flexible and / or allows a higher flexibility in the selection of the quality of the raw phenol and / or the raw acetone. This flexibility is preferably provided with respect to the concentration of hydroxyacetone, 2-methylbenzofuran, α-methylstyrene, benzene, cumene, and / or acetophenone as impurities in the raw phenol and / or the raw acetone.

[0015] At least one of the above problems, preferably all of them, has been solved by the present invention. Surprisingly, it has been found that a catalyst system comprising an ion exchange resin catalyst and a sulfur-containing cocatalyst, where at least a portion of the sulfur-containing cocatalyst is not chemically bound to the ion exchange resin catalyst, is not susceptible to catalyst poisoning by any of the substances selected from the group consisting of hydroxyacetone, 2-methylbenzofuran, α-methylstyrene, benzene, cumene, acetophenone, and mixtures thereof. This is surprising, since the prior art suggests that catalyst systems comprising chemically bound sulfur-containing cocatalysts are susceptible to poisoning by at least hydroxyacetone and / or 2-methylbenzofuran. Furthermore, the prior art teaches that the amount of hydroxyacetone and / or 2-methylbenzofuran in at least the feed acetone and / or feed phenol should be as low as possible. Since the particular catalyst system of the present invention is not affected by any of the above substances, cheaper feed acetone and / or feed phenol can be used without the risk of shortening the catalyst life. Two, three, four, five or even six substances selected from the group consisting of hydroxyacetone, 2-methylbenzofuran, α-methylstyrene, benzene, cumene and acetophenone can be used simultaneously without poisoning the catalyst system. This makes the overall process more cost-effective. It also makes the process more environmentally advantageous since less energy is required to purify the feedstock. Furthermore, the process allows more flexibility in the selection of the quality of the feedstock phenol and / or feedstock acetone, in particular the concentration of at least two substances selected from the group consisting of hydroxyacetone, 2-methylbenzofuran, α-methylstyrene, benzene, cumene and acetophenone in these feedstocks.

[0016] Thus, the present invention provides (a) condensing a feed phenol with a feed acetone in the presence of a catalyst system, the catalyst system comprises an ion exchange resin catalyst and a sulfur-containing cocatalyst, and at the start of process step (a) at least a portion, preferably at least 75 mole %, of the sulfur-containing cocatalyst is not covalently or ionically bonded to the ion exchange resin catalyst; 1. A process for making ortho,para-bisphenol A, ortho,ortho-bisphenol A, and / or para,para-bisphenol A, comprising: The present invention provides a process characterized in that at least two of the following (A) to (F) apply: (A) the amount of 2-methylbenzofuran present in step (a) is greater than 1 ppm based on the total weight of the feed phenol; and / or (B) the amount of hydroxyacetone present in step (a) is greater than 1 ppm based on the combined weight of the feed phenol and feed acetone; and / or (C) the amount of α-methylstyrene present in step (a) is greater than 1 ppm, based on the total weight of the feed phenol; and / or (D) the amount of acetophenone present in step (a) is greater than 1 ppm, based on the total weight of the feed phenol; and / or (E) the amount of benzene present in step (a) is greater than 1 ppm based on the total weight of the feed acetone; and / or (F) The amount of cumene present in step (a) is greater than 1 ppm based on the total weight of the acetone feed.

[0017] According to the invention, reference is made to "raw phenol" and / or "raw acetone". The term "raw" is used for the unreacted extractives applied, especially added, in the process of making BPA. In particular, this term is used to distinguish between phenol newly added to the reaction (as raw phenol) and phenol recycled in the process of making BPA (recycled phenol). Such recycled phenol has no possibility of adding additional hydroxyacetone, 2-methylbenzofuran, alpha-methylstyrene, and / or acetophenone to the process. The same is true for acetone newly added to the reaction (as raw acetone) and acetone recycled in the process of making BPA (recycled acetone). Such recycled acetone has no possibility of adding additional hydroxyacetone, cumene and / or benzene. When referring to phenol and / or acetone, it is preferred to mean either the chemical compounds themselves or the sum of both raw phenol and recycled phenol and / or raw acetone and recycled acetone, unless otherwise specified.

[0018] Hydroxyacetone is an impurity in both feedstocks of the reaction of BPA. Both feedstock phenol and feedstock acetone may contain hydroxyacetone impurities. Feedstock phenol may contain 2-methylbenzofuran, α-methylstyrene, and / or acetophenone. In some cases, feedstock phenol may also contain cumene. Feedstock acetone may contain benzene and / or cumene. For example, routes to manufacture acetone or phenol are described in Arpe, Hans-Juergen, Industrielle Organische Chemie, 6. Auflage, January 2007, Wiley-VCH. In particular, the process to make phenol is described in Ullmann's Encyclopedia of Industrial Chemistry, chapter Phenol and Phenol Derivatives. The oxidation of cumene, also known as the Hock process, is by far the major route for the synthesis of phenol. Among the poisons formed during the manufacture of phenol are hydroxyketones, especially hydroxyacetone.

[0019] The process of the invention is characterized in that at least two of (A) to (F) apply. According to the invention, this means that at least one of the following is fulfilled: (A)+(B), (A)+(C), (A)+(D), (A)+(E), (A)+(F), (B)+(C), (B)+(D), (B)+(E), (B)+(F), (C)+(D), (C)+(E), (C)+(F), (D)+(E), (D)+(F) or (E)+(F). It is preferred that at least three of (A) to (F) apply. This means that at least one of the following is satisfied: (A)+(B)+(C), (A)+(B)+(D), (A)+(B)+(E), (A)+(B)+(F), (A)+(C)+(D), (A)+(C)+(E), (A)+(C)+(F), (A)+(D)+(E), (A)+(D)+(F), (A)+(E)+(F), (B)+(C)+(D), (B)+(C)+(E), (B)+(C)+(F), (B)+(D)+(E), (B)+(D)+(F), (B)+(E)+(F), (C)+(D)+(E), (C)+(D)+(F) or (D)+(E)+(F).

[0020] It is more preferable that the present invention is characterized in that at least (A) and / or (B) apply, and additionally at least one of (C) to (F) applies.

[0021] It is more preferable that at least four of (A)-(F) apply. It is even more preferable that at least five of (A)-(F) apply, and it is most preferable that (A)-(F) apply. If (A)-(F) apply, it will be understood that all of the conditions (A)-(F) are mandatory, and all "or"s connecting (A)-(F) must be deleted (more precisely, "and"s are mandatory).

[0022] Hereinafter, we will refer to each of the possibilities (A) to (F), at least two of which are satisfied according to the present invention.

[0023] According to the present invention, "ppm" preferably refers to parts by weight. Furthermore, it is understood that any limit value provided for the amount of any impurity (A)-(F) can be combined with any other limit value provided for the amount of any other impurity (A)-(F).

[0024] (A) 2-Methylbenzofuran According to possibility (A), the process of the invention is characterized in that the amount of 2-methylbenzofuran present in step (a) is greater than 1 ppm, preferably greater than 2 ppm, more preferably greater than 3 ppm, even more preferably greater than 4 ppm, even more preferably greater than 5 ppm, even more preferably greater than 6 ppm, even more preferably greater than 7 ppm, even more preferably greater than 8 ppm, even more preferably greater than 9 ppm, even more preferably greater than 10 ppm, even more preferably greater than 11 ppm, even more preferably greater than 12 ppm, even more preferably greater than 13 ppm, even more preferably greater than 14 ppm, even more preferably greater than 15 ppm, even more preferably greater than 20 ppm, even more preferably greater than 25 ppm and most preferably greater than 50 ppm, based on the total weight of the feed phenol.

[0025] Further, in possibility (A), it is preferred that the amount of MBF present in step (a) is greater than 1 ppm and not more than 5000 ppm, more preferably not more than 4500 ppm, even more preferably not more than 4000 ppm, even more preferably not more than 3500 ppm, even more preferably not more than 3000 ppm, even more preferably not more than 2500 ppm, and most preferably not more than 2000 ppm, based on the total weight of the raw phenol. It is understood that the upper limit values ​​presented here can be combined with the preferred lower limit values ​​presented above. Methods for determining the amount of MBF in the raw phenol are known to those skilled in the art. For example, the amount of 2-methylbenzofuran in the raw phenol can be determined according to ASTM D6142-12 (2013).

[0026] (B) Hydroxyacetone According to the present invention, in possibility (B), it is preferred that the amount of hydroxyacetone present in step (a) is greater than 1.2 ppm, preferably greater than 1.3 ppm, more preferably greater than 1.4 ppm, more preferably greater than 1.5 ppm, more preferably greater than 2 ppm, more preferably greater than 5 ppm, more preferably greater than 10 ppm, and most preferably greater than 50 ppm, based on the total weight of the feed phenol and the feed acetone. Furthermore, in possibility (B), it is preferred that the amount of hydroxyacetone present in step (a) is greater than 1.2 ppm and not greater than 5000 ppm, more preferably not greater than 4500 ppm, more preferably not greater than 4000 ppm, more preferably not greater than 3500 ppm, more preferably not greater than 3000 ppm, more preferably not greater than 2500 ppm, and most preferably not greater than 2000 ppm, based on the total weight of the feed phenol and the feed acetone. It is understood that the upper limit values ​​presented here can be combined with the preferred lower limit values ​​presented above. Methods for determining the amount of hydroxyacetone in the feed phenol and / or the feed acetone are known to those skilled in the art. For example, the amount of hydroxyacetone in raw phenol can be determined according to ASTM D6142-12 (2013). The amount of hydroxyacetone in raw acetone can be determined by gas chromatography. Previously, the purity of acetone was determined, for example, by ASTM D1154, but this has now been discontinued.

[0027] (C) α-Methylstyrene In possibility (C), the process of the invention is characterized in that the amount of α-methylstyrene present in step (a) is greater than 1 ppm, preferably greater than 2 ppm, more preferably greater than 3 ppm, even more preferably greater than 4 ppm, even more preferably greater than 5 ppm, even more preferably greater than 6 ppm, even more preferably greater than 7 ppm, even more preferably greater than 8 ppm, even more preferably greater than 9 ppm, even more preferably greater than 10 ppm, even more preferably greater than 11 ppm, even more preferably greater than 12 ppm, even more preferably greater than 15 ppm, even more preferably greater than 20 ppm, even more preferably greater than 25 ppm, even more preferably greater than 50 ppm, even more preferably greater than 75 ppm, and most preferably greater than 100 ppm, based on the total weight of the feed phenol.

[0028] Further, according to possibility (C), it is preferred that the amount of AMS present in step (a) is greater than 1 ppm and not more than 5000 ppm, more preferably not more than 4500 ppm, even more preferably not more than 4000 ppm, even more preferably not more than 3500 ppm, even more preferably not more than 3000 ppm, even more preferably not more than 2500 ppm, and most preferably not more than 2000 ppm, based on the total weight of the raw phenol. It is understood that the upper limit values ​​presented here can be combined with the preferred lower limit values ​​presented above. Methods for determining the amount of AMS in the raw phenol are known to those skilled in the art. For example, the amount of AMS in the raw phenol can be determined according to ASTM D6142-12 (2013).

[0029] (D) Acetophenone According to possibility (D), the process of the invention is characterized in that the amount of acetophenone present in step (a) is greater than 1 ppm, preferably greater than 1.5 ppm, more preferably greater than 2 ppm, more preferably greater than 2.5 ppm, more preferably greater than 3 ppm, even more preferably greater than 4 ppm, even more preferably greater than 5 ppm, even more preferably greater than 6 ppm, even more preferably greater than 7 ppm, even more preferably greater than 8 ppm, even more preferably greater than 9 ppm, even more preferably greater than 10 ppm, even more preferably greater than 11 ppm, even more preferably greater than 12 ppm, even more preferably greater than 13 ppm, even more preferably greater than 15 ppm, even more preferably greater than 20 ppm and most preferably greater than 50 ppm, based on the total weight of the feed phenol.

[0030] Further, according to possibility (D), it is preferred that the amount of acetophenone present in step (a) is more than 1 ppm and not more than 5000 ppm, more preferably not more than 4500 ppm, more preferably not more than 4000 ppm, more preferably not more than 3500 ppm, more preferably not more than 3000 ppm, more preferably not more than 2500 ppm, and most preferably not more than 2000 ppm, based on the total weight of the raw phenol. It is understood that the upper limit values ​​presented here can be combined with the preferred lower limit values ​​presented above. Methods for determining the amount of MBF in the raw phenol are known to those skilled in the art. For example, the amount of 2-acetophenone in the raw phenol can be determined according to ASTM D6142-12 (2013).

[0031] (E) Benzene According to possibility (E), the process of the present invention is characterized in that the amount of benzene present in step (a) is greater than 1 ppm, preferably greater than 2 ppm, more preferably greater than 3 ppm, even more preferably greater than 4 ppm, even more preferably greater than 5 ppm, even more preferably greater than 6 ppm, even more preferably greater than 7 ppm, even more preferably greater than 8 ppm, even more preferably greater than 9 ppm, even more preferably greater than 10 ppm, even more preferably greater than 11 ppm, even more preferably greater than 12 ppm, even more preferably greater than 13 ppm, even more preferably greater than 14 ppm, even more preferably greater than 15 ppm, even more preferably greater than 20 ppm, even more preferably greater than 25 ppm, even more preferably greater than 50 ppm, even more preferably greater than 250 ppm and most preferably greater than 300 ppm, based on the total weight of the feed acetone.

[0032] Further, according to possibility (E), it is preferred that the amount of benzene present in step (a) is more than 1 ppm and not more than 5000 ppm, more preferably not more than 4500 ppm, even more preferably not more than 4000 ppm, even more preferably not more than 3500 ppm, even more preferably not more than 3000 ppm, even more preferably not more than 2500 ppm, and most preferably not more than 2000 ppm, based on the total weight of the feed phenol. It is understood that the upper limit values ​​presented here can be combined with the preferred lower limit values ​​presented above. Methods for determining the amount of benzene in the feed acetone are known to those skilled in the art. For example, the amount of benzene in the feed acetone can be determined according to ASTM D1154 (now obsolete).

[0033] (F) Kumen According to possibility (F), the process of the invention is characterized in that the amount of cumene present in step (a) is greater than 1 ppm, preferably greater than 2 ppm, more preferably greater than 3 ppm, even more preferably greater than 4 ppm, even more preferably greater than 5 ppm, even more preferably greater than 6 ppm, even more preferably greater than 7 ppm, even more preferably greater than 8 ppm, even more preferably greater than 9 ppm, even more preferably greater than 10 ppm, even more preferably greater than 20 ppm, even more preferably greater than 30 ppm, even more preferably greater than 40 ppm, even more preferably greater than 50 ppm, even more preferably greater than 60 ppm, even more preferably greater than 75 ppm, even more preferably greater than 100 ppm, even more preferably greater than 120 ppm, even more preferably greater than 250 ppm, and most preferably greater than 300 ppm, based on the total weight of the feed phenol and the feed acetone. In one embodiment, these amounts refer to the amount based on the total weight of the feed phenol and the feed acetone.

[0034] Further, according to possibility (F), it is preferred that the amount of cumene present in step (a) is greater than 1 ppm and not more than 5000 ppm, more preferably not more than 4500 ppm, even more preferably not more than 4000 ppm, even more preferably not more than 3500 ppm, even more preferably not more than 3000 ppm, even more preferably not more than 2500 ppm, and most preferably not more than 2000 ppm, based on the total weight of the feed acetone. In one embodiment, these amounts refer to the amount based on the total weight of the feed phenol and the feed acetone. It is understood that the upper limit values ​​presented here can be combined with the preferred lower limit values ​​presented above. Methods for determining the amount of cumene in the feed acetone are known to those skilled in the art. For example, the amount of cumene in the feed acetone can be determined according to ASTM D1154 (now obsolete).

[0035] Preferably, the process according to the invention is characterized in that at least two, preferably at least three, more preferably at least four of the following possibilities (A) to (F) apply: (A) the amount of 2-methylbenzofuran present in step (a) is greater than 1 ppm and not more than 5000 ppm, preferably not more than 2000 ppm, based on the total weight of the starting phenol; and / or (B) the amount of hydroxyacetone present in step (a) is greater than 1 ppm and not more than 5000 ppm, preferably not more than 2000 ppm, based on the total weight of the feed phenol and feed acetone; and / or (C) the amount of α-methylstyrene present in step (a) is greater than 1 ppm and not more than 5000 ppm, preferably not more than 2000 ppm, based on the total weight of the feed phenol; and / or (D) the amount of acetophenone present in step (a) is greater than 1 ppm and not more than 5000 ppm, preferably not more than 2000 ppm, based on the total weight of the starting phenol; and / or (E) the amount of benzene present in step (a) is greater than 1 ppm and not more than 5000 ppm, preferably not more than 2000 ppm, based on the total weight of the feed acetone; and / or (F) The amount of cumene present in step (a) is greater than 1 ppm and not more than 5000 ppm, preferably not more than 2000 ppm, based on the total weight of the acetone feed.

[0036] Preferably, the process according to the invention is characterized in that at least two, preferably at least three, more preferably at least four of the following possibilities (A) to (F) apply: (A) the amount of 2-methylbenzofuran present in step (a) is greater than 5 ppm, preferably greater than 10 ppm, and not more than 5000 ppm, preferably not more than 2000 ppm, based on the total weight of the feed phenol; and / or (B) the amount of hydroxyacetone present in step (a) is greater than 1.5 ppm, preferably greater than 2 ppm, and not more than 5000 ppm, preferably not more than 2000 ppm, based on the combined weight of the feed phenol and feed acetone; (C) the amount of α-methylstyrene present in step (a) is greater than 1 ppm, preferably greater than 1.5 ppm, and not more than 5000 ppm, preferably not more than 2000 ppm, based on the total weight of the feed phenol; and / or (D) the amount of acetophenone present in step (a) is greater than 1 ppm, preferably greater than 2 ppm, and not more than 5000 ppm, preferably not more than 2000 ppm, based on the total weight of the feed phenol; and / or (E) the amount of benzene present in step (a) is greater than 2 ppm, preferably greater than 5 ppm, and not more than 5000 ppm, preferably not more than 2000 ppm, based on the total weight of the feed acetone; and / or (F) The amount of cumene present in step (a) is greater than 5 ppm, preferably greater than 10 ppm, and not greater than 5000 ppm, preferably not greater than 2000 ppm, based on the total weight of the acetone feed.

[0037] Furthermore, the process according to the invention is preferably characterized in that at least one compound from the group consisting of 2-methylbenzofuran, acetophenone, benzene and cumene is present throughout process step (a). It is understood that 2-methylbenzofuran can be present throughout process step (a) only if possibility (B) applies. The same applies for acetophenone and possibility (D), for benzene and possibility (E) and for cumene and possibility (F).

[0038] According to the invention, it has been found that when using the catalyst system of the invention, MBF, acetophenone, benzene and / or cumene are not completely reacted in process step (a) if at least one of possibilities (A), (D), (E) and / or (F) applies. This means that a part of MBF, acetophenone, benzene and / or cumene is still present in the BPA. With respect to the MBF present at the beginning of process step (a), preferably at least 5% by weight, more preferably at least 10% by weight, most preferably at least 15% by weight is also present at the end of process step (a), preferably at the beginning of process step (b) described below. With respect to the MBF present at the beginning of process step (a), preferably at least 5% by weight, more preferably at least 10% by weight, most preferably at least 15% by weight is present in the resulting ortho,para-bisphenol A, ortho,ortho-bisphenol A or para,para-bisphenol A. With respect to MBF, according to the invention, it has been found that due to the presence of MBF in reaction step (a), by-products are formed, but not all MBF reacts to this impurity. This means that MBF does not completely react to this impurity. This new by-product was analyzed by MS and found to have a molecular weight of 226 g / mol. 15 H 14The atomic formula of O2 is suggested. Therefore, it is preferred to carry out step (a) in the additional presence of at least one impurity formed due to the presence of MBF in process step (a). Furthermore, these impurities can be present in process step (a) if the phenol fraction of step (b) is recycled in process step (c). With respect to the acetophenone present at the beginning of process step (a), preferably at least 25% by weight, more preferably at least 50% by weight, most preferably at least 75% by weight is also present at the end of process step (a), preferably at the beginning of process step (b) described below. With respect to the acetophenone present at the beginning of process step (a), preferably at least 25% by weight, more preferably at least 50% by weight, most preferably at least 75% by weight is present in the ortho,para-bisphenol A, ortho,ortho-bisphenol A, or para,para-bisphenol A obtained. With respect to the benzene present at the start of process step (a), preferably at least 20% by weight, more preferably at least 40% by weight, most preferably at least 60% by weight is also present at the end of process step (a), preferably at the start of process step (b) described below. With respect to the cumene present at the start of process step (a), preferably at least 20% by weight, more preferably at least 40% by weight, most preferably at least 60% by weight is also present at the end of process step (a), preferably at the start of process step (b) described below.

[0039] Preferably, the process of the present invention comprises: (b) separating the mixture obtained after step (a) into a bisphenol A fraction comprising at least one of ortho,para-bisphenol A, ortho,ortho-bisphenol A, or para,para-bisphenol A, and a phenol fraction, wherein the phenol fraction contains unreacted phenol and at least two substances selected from the group consisting of 2-methylbenzofuran and / or at least one impurity formed due to the presence of 2-methylbenzofuran in step (a), at least one impurity formed due to the presence of hydroxyacetone in step (a), 4-cumylphenol, acetophenone, benzene and cumene.

[0040] As mentioned above, according to the present invention, it has been found that MBF is at least partially reacted in process step (a). It is believed that in step (b), not all of the MBF and / or impurities formed due to the presence of MBF in step (a) are separated from either the BPA fraction and / or the phenol fraction, in particular the phenol fraction. Thus, a part of this impurity and / or by-product is still present in the phenol fraction. This conclusion also applies to most of the other impurities, depending on which of the possibilities (A) to (F) applies. Furthermore, according to the present invention, it has been found that hydroxyacetone reacts during the process of the present invention and can no longer be detected in subsequent process steps. However, it is believed that at least one new by-product / impurity is formed due to the presence of hydroxyacetone in step (a). It is believed that at least one new impurity is chroman, which may be present in the phenol fraction in process step (b). Furthermore, according to the present invention, it has been found that almost all of the AMS is believed to react during process step (a). This was confirmed by the fact that almost no AMS was detected after process step (a) (see AMS "out" in the experimental part). On the other hand, it was found that AMS appears to be almost completely reacted to 4-cumylphenol (only very small amounts of the unknown compound were detected). Furthermore, additional experiments showed that 4-cumylphenol is a stable molecule in process step (a). This means that 4-cumylphenol appears not to react in process step (a) (see that the same amount of 4-cumylphenol that spiked in process step (a) is found at the completion of process step (a)). Finally, it was found that neither benzene nor cumene react in process step (a). However, it is possible that at least small amounts of either benzene and / or cumene are present in the phenol fraction of process step (b).

[0041] The bisphenol A fraction is preferably recovered as a product and / or further purified. There are several variations in the manufacturing process to provide high purity bisphenol. This high purity is particularly important in the use of BPA as a monomer in the manufacture of polycarbonates. WO 0172677 describes crystals of an adduct of bisphenol with phenol and a method for producing the crystals and ultimately making bisphenol. It has been found that high purity para,para-BPA can be obtained by crystallization of the adduct. EP 1944284 describes a process for producing bisphenol, in which the crystallization comprises a continuous suspension crystallizer. It is stated that there is an increasing demand for the purity of BPA and that the disclosed method allows very pure BPA of more than 99.7% to be obtained. WO 2005075397 describes a process for producing bisphenol A, in which the water formed during the reaction is removed by distillation. In this way, unreacted acetone is recovered and recycled, resulting in an economically advantageous process.

[0042] The process of the invention is preferably characterized in that the separation in step (b) is carried out using a crystallization method, more preferably the separation in step (b) is carried out using at least one continuous suspension crystallizer.

[0043] It was further described that the mother liquor cycle is utilized. After the reaction, the BPA is removed from the solvent by crystallization and filtration. The mother liquor typically contains 5% to 20% of BPA dissolved in unreacted phenol and by-products. Furthermore, water is formed during the reaction, which is removed from the mother liquor in the dehydration section. Without being bound by theory, it is believed that at least a portion of the benzene and / or cumene separated from the BPA is found in the process water. This means that it is preferred to remove the benzene and / or cumene from the process of the present invention by dehydrating the mother liquor. Such dehydration can be performed, for example, by using a dehydration column. Finally, the benzene and / or cumene are believed to be present in the wastewater, which can then be treated in a wastewater stripper. On the other hand, the benzene and / or cumene may also leave the system by off-gassing. Furthermore, according to the present invention, no accumulation of benzene and / or cumene was observed. This means that it is believed that the benzene and / or cumene do indeed leave the system at some point.

[0044] The fraction containing unreacted phenol is preferably recycled for further reaction, which preferably means recycling the mother liquor, which is reused as unreacted phenol in the reaction with acetone to obtain BPA, and the mother liquor stream is preferably recycled to the reaction unit according to conventional methods.

[0045] Typically, by-products in the mother liquor are, for example, o,p-BPA, o,o-BPA, substituted indenes, hydroxyphenylindanols, hydroxyphenylchromans, substituted xanthenes, and higher condensed compounds. Also, as a result of acetone self-condensation and reaction with impurities in the feedstock, further secondary compounds such as anisole, mesityl oxide, mesitylene, and diacetone alcohol may be formed.

[0046] Recycling of the mother liquor can lead to the accumulation of by-products in the circulation stream, which can lead to further deactivation of the catalytic system. This means that when using the catalyst for long periods of time, it is necessary to consider the influence of by-products that may arise in the reaction itself, either from the reaction of phenol with acetone or from the reaction of one of the impurities, as well as the influence of initial impurities in the extract.

[0047] According to the invention, the process of the invention comprises: It is preferred that the method further comprises the additional step of (c) using at least a portion of the phenolic fraction obtained in step (b) as the extract in step (a).

[0048] In order to avoid the accumulation of additional impurities mentioned in (A) to (F), by-products and / or impurities that form due to the presence of some of the impurities mentioned in (A) to (F) in step (a), several options exist in the system. Options include, in particular, purge streams, waste water, off-gas and BPA itself as product. One option, or perhaps even the predominant one, would be a purge stream, for example discharging part of the mother liquor. Another approach involves passing a part of the total amount of the circulating stream after solid-liquid separation and before or after removal of water and residual acetone, through a rearrangement unit, for example filled with an acid ion exchanger. In this rearrangement unit, some of the by-products from the preparation of BPA are isomerized to obtain p,p-BPA. It has been found that the majority of the impurities mentioned in (A) to (F) and / or that form due to the presence of MBF, hydroxyacetone and / or α-methylstyrene in process step (a) can be removed by the purge stream. It is therefore preferred to use at least a portion of the phenol fraction obtained in step (b) as extract in step (a) and to purge at least a portion of this stream. It is preferred to use more than 50% by volume of the phenol fraction obtained in step (b) as extract in step (a), where the volume percentages are relative to the total volume of the phenol fraction.

[0049] Furthermore, it has been found that some of the impurities formed due to the presence of alpha-methylstyrene (AMS) in process step (a), preferably 4-cumylphenol, are still present in the BPA obtained using standard methods for purifying BPA. For example, some of the impurities formed due to the presence of AMS in process step (a), preferably 4-cumylphenol, are still present in the BPA obtained even after carrying out the above-mentioned process step (b).

[0050] The catalyst systems that can be used in the process of the present invention are known to those skilled in the art. The catalyst system is preferably an acidic ion exchange resin. Such an ion exchange resin can have a crosslinking of 2% to 20%, preferably 3% to 10%, most preferably 3.5% to 5.5%. The acidic ion exchange resin can preferably be selected from the group consisting of sulfonated styrene divinylbenzene resin, sulfonated styrene resin, phenol formaldehyde sulfonic acid resin, and benzene formaldehyde sulfonic acid. Furthermore, the ion exchange resin can contain sulfonic acid groups. The catalyst bed can be either a fixed bed or a fluidized bed.

[0051] Furthermore, the catalyst system of the present invention comprises a sulfur-containing cocatalyst, at least a portion of which is not covalently or ionically bonded to the ion exchange resin catalyst. The sulfur-containing cocatalyst can be one substance or a mixture of at least two substances. The cocatalyst is preferably dissolved in the reaction solution of process step (a). More preferably, the cocatalyst is homogeneously dissolved in the reaction solution of process step (a). The process of the present invention is preferably characterized in that the sulfur-containing cocatalyst is selected from the group consisting of mercaptopropionic acid, hydrogen sulfide, alkyl sulfides such as ethyl sulfide, and mixtures thereof. Most preferably, the sulfur-containing cocatalyst is 3-mercaptopropionic acid.

[0052] The catalyst system of the present invention comprises a sulfur-containing cocatalyst, and preferably, all of the sulfur-containing cocatalyst is not covalently or ionically bonded to the ion-exchange resin catalyst. This means that preferably, all of the sulfur-containing cocatalyst is added in process step (a). According to the present invention, the expressions "not chemically bonded" or "not covalently or ionically bonded" refer to a catalyst system in which, at the start of process step (a), there are no covalent or ionic bonds between the ion-exchange resin catalyst and the sulfur-containing cocatalyst. However, this does not mean that at least a part of the sulfur-containing cocatalyst may be fixed to the heterogeneous catalyst matrix via ionic or covalent bonds. In any case, at the start of process step (a), such ionic or covalent bonds of the sulfur-containing cocatalyst are not present and, if they are formed at all, they are formed over time. Therefore, it is preferred to add the sulfur-containing cocatalyst to process step (a). The term "addition" denotes an active process step. This means that, as mentioned above, it is preferred to dissolve the cocatalyst in the reaction solution of process step (a). Additionally, the co-catalyst may be added in any other process step or may be added more than once in process step (a). Furthermore, it is preferred that the majority of the sulfur-containing co-catalyst is not covalently or ionically bonded to the ion exchange resin catalyst. This means that at least 75 mol %, more preferably at least 80 mol %, and most preferably at least 90 mol % of the sulfur-containing co-catalyst is not chemically bonded to the ion exchange resin catalyst, where the mol % is relative to the total co-catalyst present in process step (a).

[0053] Since MBF, hydroxyacetone, α-methylstyrene and / or acetophenone may be impurities in the raw phenol, it is preferred that each of 2-methylbenzofuran, hydroxyacetone, α-methylstyrene and / or acetophenone present in step (a) when at least one of (A), (B), (C) and / or (D) is satisfied is introduced into process step (a) as an impurity in the raw phenol. In this situation, at least a portion of MBF, hydroxyacetone, α-methylstyrene and / or acetophenone may be present in process step (a) for another reason. However, it is also possible that cumene is an impurity in the raw phenol. Therefore, it is even more preferred that each of 2-methylbenzofuran, hydroxyacetone, α-methylstyrene, cumene and / or acetophenone present in step (a) when at least one of (A), (B), (C), (D) and / or (F) is satisfied is introduced into process step (a) as an impurity in the raw phenol. In this situation, at least a portion of the MBF, hydroxyacetone, α-methylstyrene, cumene and / or acetophenone may be present in process step (a) for other reasons.

[0054] Since hydroxyacetone, benzene and / or cumene may be impurities in the feed acetone, it is preferred that each of the hydroxyacetone, benzene and / or cumene present in step (a) when at least one of (B), (E) and / or (F) is satisfied is introduced into process step (a) as an impurity in the feed acetone. In this situation, however, at least a portion of the hydroxyacetone, benzene and / or cumene may be present in process step (a) for another reason.

[0055] In another aspect, the present invention provides a method for producing a pharmaceutical composition comprising: (i) in any embodiment or combination of preferred embodiments, obtaining ortho,para-bisphenol A, ortho,ortho-bisphenol A, and / or para,para-bisphenol A by the process of the present invention; (ii) polymerizing the ortho,para-bisphenol A, ortho,ortho-bisphenol A, and / or para,para-bisphenol A obtained in step (i), optionally in the presence of at least one further monomer, to obtain a polycarbonate; The present invention provides a process for making a polycarbonate comprising:

[0056] As explained above, the process for producing ortho,para-bisphenol A, ortho,ortho-bisphenol A, and / or para,para-bisphenol A of the present invention provides BPA that can be obtained in a more economical and / or environmentally friendly manner. Therefore, the use of this BPA obtained by the process according to the present invention also makes the process for making polycarbonate according to the present invention more economical and / or environmentally friendly.

[0057] Reaction step (ii) is known to those skilled in the art. The polycarbonates can be prepared in known manner from BPA, carbonic acid derivatives, optional chain terminators, and optional branching agents by interphase phosgenation or melt transesterification.

[0058] In interphase phosgenation, the bisphenol and any branching agent are dissolved in an aqueous alkaline solution and reacted with a carbonic acid source, such as phosgene, optionally dissolved in a solvent, in a two-phase mixture containing an aqueous alkaline solution, an organic solvent and a catalyst, preferably an amine compound. The reaction procedure can also be carried out in several stages. Such processes for making polycarbonates are known in principle as interfacial processes, for example in H. Schnell, Chemistry and Physics of Polycarbonates, Polymer Reviews, Vol. 9, Interscience Publishers, New York 1964 page 33 et seq. and Polymer Reviews, Vol. 10, "Condensation Polymers by Interfacial and Solution Methods", Paul W. Morgan, Interscience Publishers, New York 1965, chapter VIII, page 325, so that the basic conditions are well known to those skilled in the art.

[0059] Alternatively, polycarbonates can also be prepared by melt transesterification process.The melt transesterification process is described, for example, in Encyclopedia of Polymer Science, Vol. 10 (1969), Chemistry and Physics of Polycarbonates, Polymer Reviews, H. Schnell, Vol. 9, John Wiley and Sons, Inc. (1964), and in German Patent Application Publication No. 1031512.In the melt transesterification process, the aromatic dihydroxy compounds already described in the interfacial process are transesterified with carbonic acid diesters in the melt with the aid of suitable catalysts and any further additives.

[0060] Preferably, the process for making polycarbonates according to the invention is characterized in that process step (i) further comprises a step of purifying ortho,para-bisphenol A, ortho,ortho-bisphenol A and / or para,para-bisphenol A in order to reduce the amount of at least one compound from the group consisting of 2-methylbenzofuran, impurities formed due to the presence of hydroxyacetone in step (a), 4-cumylphenol and acetophenone. As mentioned above, cheaper raw phenol and / or raw acetone can be used in the process of the invention. However, if these cheaper raw materials contain MBF, hydroxyacetone, AMS and / or acetophenone as impurities, it is believed that further impurities are formed and / or that the impurities themselves remain in the product. These impurities are preferably removed before polymerization. EXAMPLES

[0061] The materials used in the examples are as follows:

[0062] TIFF2024508777000001.tif99170

[0063] The column reactor was equipped with 150 g of phenol wet catalyst (amount of phenol wet catalyst in the reactor: 210 ml-230 ml). The column reactor was heated to 60° C. (catalyst bed temperature during the reaction: 63° C.). A mixture of phenol, acetone (3.9 wt %), and MEPA (160 ppm relative to the total mass of phenol and acetone) was prepared and heated to 60° C. This mixture was pressed into the column reactor at a flow rate of 45 g / h. The column reactor had a sampling point at the bottom. Various samples were taken during the reaction using the opening of the sampling point. The sampling time was 1 hour, and the amount of sample taken every hour was 45 g.

[0064] The first run (standard run) was carried out for 52 hours. Samples were taken and analyzed by GC after 48, 49, 50, and 51 hours.

[0065] A second run (impurity run) was performed for 52 hours. At the beginning of the second run, each impurity was dosed into the reaction (see table for exact amounts). Samples were taken and analyzed by GC after 48, 49, 50, and 51 hours, respectively. A third run (standard run) was then performed for 52 hours using a fresh mixture of acetone, phenol, and MEPA. Samples were taken via syringe and analyzed by GC after 48, 49, 50, and 51 hours, respectively. A fourth run (impurity run) was then performed for 52 hours. At the beginning of the fourth run, each impurity was dosed into the reaction (see table for exact amounts). Samples were taken and analyzed by GC after 48, 49, 50, and 51 hours, respectively. Finally, a fifth run (standard run) was performed for 52 hours. Samples were taken after 48, 49, 50, and 51 hours and analyzed by GC.

[0066] Gas chromatography (GC) of methanol was performed using an Agilent J&W VF-1MS column (100% dimethylpolysiloxane) with dimensions of 50 m x 0.25 mm x 0.25 μm, with a temperature profile of 60° C. for 0.10 min, heating at 12° C. / min to 320° C. and holding at this temperature for 10.00 min, at 300° C. with a 10 / 1 split to inject 1 μl of sample, with a flow rate of 2 ml / min at an initial pressure of 18.3 psi (1.26 bar).

[0067] Gas chromatography (GC) of 2-methylbenzofuran, hydroxyacetone, α-methylstyrene, acetophenone, benzene, cumene, phenol, and para,para-BPA was performed using an Agilent J&W VF-1MS column (100% dimethylpolysiloxane) with dimensions of 50 m × 0.25 mm × 0.25 μm, with a temperature profile of 80 °C for 0.10 min, heating at 12 °C / min to 320 °C and holding at this temperature for 10.00 min, with a 10 / 1 split at 300 °C to inject 1 μl of sample, with a flow rate of 2 ml / min at an initial pressure of 18.3 psi (1.26 bar).

[0068] The standard runs represent the reaction of acetone with phenol to form BPA in the presence of a catalyst and a cocatalyst. From the standard runs, the acetone conversion, including the respective error bars, can be estimated. This conversion represented a baseline for evaluating whether impurities affect the deactivation of the catalyst. The acetone conversion in the third and fifth standard runs was compared with that of the first standard run to determine the effect of each impurity on the catalyst. If the acetone conversion is lower than this conversion, it indicates that this impurity affects the BPA catalyst. To show that this type of evaluation can be used to determine catalyst poisoning, a reference run was performed using methanol as an impurity. Methanol is known from the current state of the art to be a known poison for catalysts in the BPA process, as described, for example, in US Pat. No. 8,143,456. The respective results are shown in Table 1. The values ​​shown in the table are the average values ​​obtained from four samples taken during each run (after 48 hours, 49 hours, 50 hours, and 51 hours).

[0069] TIFF2024508777000002.tif44170

[0070] As can be clearly seen from Table 1, the acetone conversion rate decreased in the first, third and fifth standard runs, which means that the catalyst was poisoned by methanol and could not recover the conversion rate due to the irreversible reaction that reduced the catalytic activity.

[0071] The following table shows the results for the first run (standard run), second run (impurity run), third run (standard run), fourth run (impurity run), and fifth run (standard run) for each impurity. The values ​​shown in the table are the average values ​​obtained from four samples taken during each run (after 48 hours, 49 hours, 50 hours, and 51 hours).

[0072] TIFF2024508777000003.tif85170

[0073] As can be seen from the results in Table 2, the addition of 2-methylbenzofuran in the reaction of phenol with acetone to para,para-BPA causes almost no decrease in the acetone conversion in the first, third and fifth standard runs. This means that MBF is not a poison for the catalyst system used. This effect is seen after each impurity run. Furthermore, it can be seen that during the impurity run, some MBF still leaves the reactor (2-methylbenzofuran OUT can be detected). This means that during the impurity run, not all MBF reacts. The unknown compound(s) were analyzed by GC-MS. Gas chromatography (GC) coupled with mass spectrometry (MS) for the identification of unknown compounds is performed using an Agilent J&W VF-1MS column (100% dimethylpolysiloxane) with dimensions of 30 m x 0.25 mm x 0.25 μm, injecting 0.5 μl of sample with a 10 / 1 split at 250 °C, using a temperature profile of 0.10 min at 60 °C, heating at 12 °C / min to 350 °C and holding at this temperature for 5 min. Here, the flow rate is 1 ml / min with an initial pressure of 24.45 psi (1.685768 bar), and the mass spectrometer scans from mz35 to mz700. At least one unknown compound was found to have a molecular weight of 226 g / mol.

[0074] TIFF2024508777000004.tif85170

[0075] As can be seen from the results in Table 3, the addition of hydroxyacetone in the reaction of phenol with acetone to para,para-BPA does not cause a decrease in the acetone conversion in the first, third and fifth standard runs. This means that hydroxyacetone is not a poison for the catalyst system used. This effect is seen after each impurity run. Moreover, it is seen that during the impurity run, almost all of the hydroxyacetone reacts (hydroxyacetone OUT cannot be detected). The unknown compound(s) were analyzed by GC-MS. Gas chromatography (GC) coupled with mass spectrometry (MS) for identification is performed using an Agilent J&W VF-1MS column (100% dimethylpolysiloxane) with dimensions of 25m x 0.2mm x 0.33μm, with a temperature profile of 80°C held for 0.10 min, heated at 10°C / min to 280°C and held at this temperature for 10.00 min, with a 10 / 1 split injection of 1μl of sample at 250°C. Here, the flow rate is 1 ml / min with an initial pressure of 24.45 psi (1.685768 bar) and the mass spectrometer scans from mz 35 to mz 700. Two compounds were found with molecular weights of 362 g / mol and 434 g / mol.

[0076] TIFF2024508777000005.tif76170

[0077] As can be seen from the results in Table 4, the addition of α-methylstyrene in the reaction of phenol with acetone to para,para-BPA does not cause a decrease in the acetone conversion in the first, third and fifth standard runs. This means that α-methylstyrene is not a poison for the catalyst system used. This effect is seen after each impurity run. Furthermore, it can be seen that during the impurity runs, almost all of the α-methylstyrene reacts (α-methylstyrene OUT cannot be detected). By GC analysis, it was possible to prove that α-methylstyrene was completely reacted to 4-cumylphenol. Since 4-cumylphenol is present in the reaction, it can also be concluded that it is not a poison for the catalyst used, at least in small amounts.

[0078] The stability of 4-cumylphenol during the reaction was also tested using the same set-up as described above for α-methylstyrene, except that 710 ppm of 4-cumylphenol was dosed. Only one run was performed, and the same amount of 4-cumylphenol was detected upon completion.

[0079] Therefore, it can be concluded that the dose of 4-cumylphenol passed completely through the reactor, thus confirming that 4-cumylphenol is a stable molecule in this process.

[0080] TIFF2024508777000006.tif71170

[0081] As can be seen from the results in Table 5, the addition of acetophenone in the reaction of phenol with acetone to form para,para-BPA causes almost no decrease in acetone conversion in the first, third and fifth standard runs. This means that acetophenone is not a poison for the catalyst system used. This effect is seen after each impurity run. Furthermore, it can be seen that acetophenone does not appear to react at all in this system (acetophenone OUT is approximately equal to acetophenone IN).

[0082] TIFF2024508777000007.tif35170

[0083] After the run, no new unknown compounds were detected by GC, so it appears that all of the benzene passed through the reactor and did not react significantly.

[0084] As can be seen from the results in Table 6, the addition of benzene in the reaction of phenol with acetone to para,para-BPA causes almost no decrease in the acetone conversion in the first, third and fifth standard runs. This means that benzene is not a poison for the catalyst system used. This effect is seen after each impurity run. Furthermore, it can be concluded that benzene does not appear to react at all in this system.

[0085] TIFF2024508777000008.tif64170

[0086] As can be seen from the results in Table 7, the addition of cumene in the reaction of phenol with acetone to form para,para-BPA causes almost no decrease in acetone conversion in the first, third and fifth standard runs. This means that cumene is not a poison for the catalyst system used. This effect is seen after each impurity run. Furthermore, it can be seen that cumene does not appear to react at all in this system (cumene OUT is approximately equal to cumene IN).

[0087] Since none of the tested impurities had a substantial effect on the catalyst system, it can be concluded that the combination of at least two of the tested impurities also has a negligible effect on catalyst poisoning.

Claims

1. (a) condensing a feed phenol with a feed acetone in the presence of a catalyst system, the catalyst system comprises an ion exchange resin catalyst and a sulfur-containing cocatalyst, and at least a portion of the sulfur-containing cocatalyst is not covalently or ionically bonded to the ion exchange resin catalyst at the start of process step (a); 1. A process for making ortho,para-bisphenol A, ortho,ortho-bisphenol A, and / or para,para-bisphenol A, comprising: A process characterized in that at least two of the following (A) to (F) apply: (A) the amount of 2-methylbenzofuran present in step (a) is greater than 1 ppm based on the total weight of the feed phenol; and / or (B) the amount of hydroxyacetone present in step (a) is greater than 1 ppm based on the combined weight of the feed phenol and the feed acetone; and / or (C) the amount of α-methylstyrene present in step (a) is greater than 1 ppm, based on the total weight of the feed phenol; and / or (D) the amount of acetophenone present in step (a) is greater than 1 ppm based on the total weight of the feed phenol; and / or (E) the amount of benzene present in step (a) is greater than 1 ppm based on the total weight of the feed acetone; and / or (F) the amount of cumene present in step (a) is greater than 1 ppm based on the total weight of the acetone feedstock.

2. The process according to claim 1, characterized in that at least two of the following (A) to (F) apply: (A) the amount of 2-methylbenzofuran present in step (a) is greater than 1 ppm and less than or equal to 5000 ppm, based on the total weight of the feed phenol; and / or (B) the amount of hydroxyacetone present in step (a) is greater than 1 ppm and less than or equal to 5000 ppm, based on the total weight of the feed phenol and the feed acetone; and / or (C) the amount of α-methylstyrene present in step (a) is greater than 1 ppm and less than or equal to 5000 ppm, based on the total weight of the feed phenol; and / or (D) the amount of acetophenone present in step (a) is greater than 1 ppm and less than or equal to 5000 ppm, based on the total weight of the feed phenol; and / or (E) the amount of benzene present in step (a) is greater than 1 ppm and less than or equal to 5000 ppm, based on the total weight of the feed acetone; and / or (F) The amount of cumene present in step (a) is greater than 1 ppm and not greater than 5000 ppm based on the total weight of the feed acetone.

3. 3. The process according to claim 1 or 2, characterized in that at least one compound from the group consisting of 2-methylbenzofuran, acetophenone, benzene and cumene is present throughout process step (a).

4. (b) separating the mixture obtained after step (a) into a bisphenol A fraction comprising at least one of ortho,para-bisphenol A, ortho,ortho-bisphenol A, or para,para-bisphenol A, and a phenol fraction, 4. The process according to claim 1, further comprising a step, wherein the phenol fraction comprises unreacted phenol and at least two substances selected from the group consisting of 2-methylbenzofuran and / or at least one impurity formed due to the presence of 2-methylbenzofuran in step (a), at least one impurity formed due to the presence of hydroxyacetone in step (a), 4-cumylphenol, acetophenone, benzene and cumene.

5. 5. The process according to claim 4, characterized in that it comprises the additional step of: (c) using at least a portion of the phenolic fraction obtained in step (b) as extract in step (a).

6. 6. The process according to any one of claims 1 to 5, characterized in that the sulfur-containing cocatalyst is selected from the group consisting of mercaptopropionic acid, hydrogen sulfide, alkyl sulfides such as ethyl sulfide, and mixtures thereof.

7. 7. The process of any one of claims 1 to 6, characterized in that each of the 2-methylbenzofuran, the hydroxyacetone, the α-methylstyrene, the acetophenone and / or the cumene present in step (a) when at least one of (A), (B), (C), (D) and / or (F) is satisfied is introduced into the process step (a) as an impurity in the feed phenol.

8. 8. The process according to claim 1, wherein each of the hydroxyacetone, the benzene and / or the cumene present in step (a) when at least one of (B), (E) and / or (F) is satisfied is introduced into the process step (a) as an impurity in the feed acetone.

9. (i) obtaining ortho,para-bisphenol A, ortho,ortho-bisphenol A, and / or para,para-bisphenol A according to the process of any one of claims 1 to 8; (ii) polymerizing the ortho,para-bisphenol A, ortho,ortho-bisphenol A, and / or para,para-bisphenol A obtained in step (i), optionally in the presence of at least one further monomer, to obtain a polycarbonate; A process for making a polycarbonate comprising: