Methods Of Manufacture Of 2-Hydrocarbyl-3,3-Bis(Hydroxyaryl)Phthalimidines (SABIC)

CATEGORY: PETROCHEMICALS
Methods Of Manufacture Of 2-Hydrocarbyl-3,3-Bis(Hydroxyaryl)Phthalimidines (SABIC)
United States Patent Application 20160340307
Bhotla; Venkata Ramanarayanan Ganapathy ;   et al.   November 24, 2016
Applicant: SABIC Global Technologies
Abstract
A method for the manufacture of a 2-hydrocarbyl-3,3-bis(hydroxyaryl)phthalimidine composition comprises: reacting a phthalimide of formula (2) with a phenol of formula (3) I (2) I (3) in the presence of a catalyst and optionally a solvent at an elevated temperature to form the 2-hydrocarbyl-3,3-bis(hydroxyaryl)phthalimidine composition, wherein the 2-hydrocarbyl-3,3-bis(hydroxyaryl)phthalimidine composition comprises a 2-hydrocarbyl-3,3-bis(hydroxyaryl)phthalimidine of formula (1) I (1) wherein in formulas (1), (2) and (3), R.sup.1 is hydrogen, C.sub.1-6 alkyl, C.sub.1-6 alkoxy, or phenyl optionally substituted with 1 to 5 C.sub.1-6 alkyls, each occurrence of R.sup.2 and R.sup.3 is independently a C.sub.1-6 alkyl, and p and q are independently 0 to 4. ##STR00001##
BACKGROUND
[0001] This disclosure is directed to a method for the manufacture of 2-hydrocarbyl-3,3-bis(hydroxyaryl)phthalimidines, particularly to the manufacture of N-phenyl phenolphthalein bisphenol and N-methyl phenolphthalein bisphenol. This disclosure is also directed to the manufacture of polycarbonates from the prepared 2-hydrocarbyl-3,3-bis(hydroxyaryl)phthalimidines.
[0002] 2-Hydrocarbyl-3,3-bis(hydroxyaryl)phthalimidines such as N-phenyl phenolphthalein bisphenol (PPPBP) can be used in the manufacture of homopolycarbonates and copolycarbonates. Commercially, PPPBP is synthesized from aniline and phenolphthalein in the presence of hydrogen chloride. The staring material, phenolphthalein, can be manufactured from phthalic anhydride and phenol.
[0003] There are several challenges associated with the commercial process. For example, crude PPPBP obtained via this process typically contains aminophenol impurity, 2-aryl-3-(aminoaryl-3-(hydroxyaryl)phtha dine, which must be removed through several activated carbon treatments. Final purification is conducted by a trituration using a methanol/water solvent system to bring the phenolphthalein within specification limits and to improve the color of the monomer. This multistep purification process uses large amount of activated carbon which is recycled only for few cycles and hence generates waste. In addition, the multistep purification process involves multiple unit operations which lead to yield losses.
[0004] Accordingly, it would be desirable to develop a process for the preparation of 2-hydrocarbyl-3,3-bis(hydroxyaryl)phthalimidine that reduces or avoids formation of aminophenol impurity and waste generation, for example by avoiding the use of activated carbon. It would also be desirable if this process provides 2-hydrocarbyl-3,3-bis(hydroxyaryl)phthalimidine of high yield and purity.
SUMMARY
[0005] Disclosed herein is a method for the manufacture of a 2-hydrocarbyl-3,3-bis(hydroxyaryl)phthalimidine composition. The method comprises reacting a phthalimide of formula (2) with a phenol of formula (3)
##STR00002##
in the presence of a catalyst and optionally a solvent at an elevated temperature to form the 2-hydrocarbyl-3,3-bis(hydroxyaryl)phthalimidine composition, wherein the 2-hydrocarbyl-3,3-bis(hydroxyaryl)phthalimidine composition comprises a 2-hydrocarbyl-3,3-bis(hydroxyaryl)phthalimidine of formula (1)
##STR00003##
wherein in formulas (1), (2) and (3), R.sup.1 is hydrogen, C.sub.1-6 alkyl, C.sub.1-6 alkoxy, or phenyl optionally substituted with 1 to 5 C.sub.1-6 alkyls, each occurrence of R.sup.2 and R.sup.3 is independently a C.sub.1-6 alkyl, and p and q are independently 0 to 4.
[0006] Also disclosed is a method for the manufacture of a polycarbonate comprising:
[0007] reacting a phthalimide of formula (2) with a phenol of formula (3)
##STR00004##
in the presence of a catalyst and optionally a solvent at an elevated temperature to form a 2-hydrocarbyl-3,3-bis(hydroxyaryl)phthalimidine composition comprising a 2-hydrocarbyl-3,3-bis(hydroxyaryl)phthalimidine of formula (1)
##STR00005##
polymerizing the 2-hydrocarbyl-3,3-bis(hydroxyaryl)phthalimidine of formula (1) and optionally a bisphenol different from the 2-hydrocarbyl-3,3-bis(hydroxyaryl)phthalimidine of formula (1) to form the polycarbonate, wherein in formulas (1), (2) and (3), R.sup.1 is hydrogen, C.sub.1-6 alkyl, C.sub.1-6 alkoxy, or phenyl optionally substituted with 1 to 5 C.sub.1-6 alkyls, each occurrence of R.sup.2 and R.sup.3 is independently a C.sub.1-6 alkyl, and p and q are independently 0 to 4.
[0008] A 2-hydrocarbyl-3,3-bis(hydroxyaryl)phthalimidine and a polycarbonate manufactured by the above methods are also provided.
[0009] The above described and other features are exemplified by the following Detailed Description and Examples.
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Selective Hydrogenation of Styrene to Ethylbenzene (ExxonMobil Chemical Patents)

CATEGORY: PETROCHEMICALS: STYRENE TO ETHYLBENZENE
Selective Hydrogenation of Styrene to Ethylbenzene (ExxonMobil Chemical Patents)
United States Patent Application 20160244385
Chen; Tan-Jen ;   et al.   August 25, 2016
Applicant: ExxonMobil Chemical Patents
Abstract
A feedstream comprising paraxylene and styrene is contacted, in the presence of hydrogen, with a catalyst comprising at least one metal, selected from one or more metals selected from Groups 8-10.
FIELD OF THE INVENTION
[0002] The invention relates to the selective hydrogenation of styrene to ethylbenzene and more particularly to the removal of small quantities of styrene present in the product stream of a method of making paraxylene selectively by the alkylation of aromatic species with an alkylating agent over a solid catalyst.
BACKGROUND OF THE INVENTION
[0003] It is well-known to manufacture xylenes by the alkylation of toluene and/or benzene with methanol, and in particular to selectively make paraxylene (PX) product using zeolite catalyst. See, for instance, U.S. Pat. Nos. 4,002,698; 4,356,338; 4,423,266; 5,675,047; 5,804,690; 5,939,597; 6,028,238; 6,046,372; 6,048,816; 6,156,949; 6,423,879; 6,504,072; 6,506,954; 6,538,167; and 6,642,426. See also more recently U.S. application Ser. No. 13/557,605, and references cited therein. Paraxylene selectivity is highly sought after because of the economic importance of paraxylene relative to meta- and orthoxylene. Although each of the xylene isomers have important and well-known end uses, paraxylene is currently the most economically valuable, serving as an intermediate in such important and diverse end uses as bottle plastic and polyester fibers.
[0004] One of the problems with xylenes streams produced by alkylating aromatic species such as benzene and/or toluene with alkylating agents such as methanol and/or dimethyl ether over solid catalysts, such as in the aforementioned processes, is the product stream may contain styrene impurities. This has recently been observed and set forth in Provisional Patent Applications 61/711,341 and 61/681,486 [Attorney Docket Nos. 2012EM298 and 2012EM112, respectively]. Styrene impurities can cause operability problems for downstream process, for example paraxylene recovery by adsorptive separation processes, e.g., Parex.TM. Process or Eluxyl.TM. Process, as well as other processes used to take paraxylene to end products, such as in processes used to make purified terephthalic acid/anhydride and subsequent steps to making fibers or bottle plastic therefrom.
[0005] One method of removing styrene is to convert said species to ethylbenzene by selective hydrogenation. Several characteristics of purifying xylenes containing styrene impurities make selective hydrogenation of styrene challenging. It is highly desirable to minimize the ring saturation reactions since separation of dimethylcyclohexane, ethylcyclohexane, and/or other saturated C8 hydrocarbons from xylenes is difficult. Another potential challenge is that the desired product, paraxylene, is present at higher-than-equilibrium concentration. The catalyst used to hydrogenate styrene must therefore show minimal xylenes isomerization activity.
[0006] It is known to hydrogenate certain aromatic species in paraxylene enriched streams. See, for instance, U.S. Application Ser. Nos. 61/604,926, 61/496,262, 13/303,855, and 13/449,758 [Attorney Docket Nos. 2012EM014, 2011EM150, 2010EM331, 2010EM039, respectively].
[0007] The present inventors have surprisingly discovered a method of selectively hydrogenating styrene impurities present in a xylenes stream nearly stoichiometrically using a catalyst comprising at least one metal selected Groups 8-10 of the Periodic Table, optionally further comprising promoters and/or supports.
SUMMARY OF THE INVENTION
[0008] The invention is directed to a method of hydrogenating styrene impurities present in a xylenes stream using a catalyst comprising M, wherein M is selected from Group 8-10 metals, preferably Pd, Co, Ni, Ru, and mixtures thereof.
[0009] In embodiments, promoters such as Ag, Au, In, K and other alkali metals, Ca and other alkaline earth metals, and mixtures thereof, can be present.
[0010] In embodiments, a support such as Al.sub.2O.sub.3, carbon, SiO.sub.2, TiO.sub.2, and mixtures thereof, may be present.
[0011] It is an object of the invention to eliminate styrene from paraxylene-containing feedstreams prior to processes that would have operability problems with even small quantities of styrene, e.g., catalytic processes, absorption processes, and the like, that are sensitive to the presence of vinyl moiety, while having little or no effect, e.g., ring saturation and/or isomerization, on paraxylene itself.
[0012] These and other objects, features, and advantages will become apparent as reference is made to the following detailed description, preferred embodiments, examples, and appended claims.
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Process for Making Phenol and/or Cyclohexanone (Exxonmobil Chemical Patents)

CATEGORY: PETROCHEMICALS: PHENOL
Process for Making Phenol and/or Cyclohexanone (Exxonmobil Chemical Patents)
United States Patent Application 20160251288
Benitez; Francisco M. ;   et al.   September 1, 2016
Applicant: Exxonmobil Chemical Patents
Abstract
A process for making phenol and/or cyclohexanone, the process comprising: (A) oxidizing a cyclohexylbenzene feed to obtain an oxidation product comprising cyclohexylbenzene, cyclohexylbenzene hydroperoxide and water; (B) removing at least a portion of the water from at least a portion of the oxidation product to obtain a cleavage feed; and (C) contacting at least a portion of the cyclohexylbenzene hydroperoxide in the cleavage feed with an acid catalyst in a cleavage reactor under cleavage conditions to obtain a cleavage product comprising phenol and cyclohexanone. The removing step may also comprises a step of removing a portion of the cyclohexylbenzene contained in the oxidation product. Water removal may be advantageously conducted in a water flashing drum before a cyclohexylbenzene hydroperoxide concentrator.
FIELD
[0002] The present invention relates to a process for making phenol and/or cyclohexanone. In particular, the present invention relates to a process for making phenol and/or cyclohexanone by the cleavage of cyclohexylbenzene hydroperoxide. The present invention is useful, e.g., in making phenol and cyclohexanone via the route of benzene hydroalkylation.
BACKGROUND
[0003] Phenol and cyclohexanone are important materials in the chemical industry and are useful in, for example, the production of phenolic resins, bisphenol A, .epsilon.-caprolactam, adipic acid, and plasticizers.
[0004] Currently, a common route for the production of phenol is the Hock process. This is a three-step process in which the first step involves alkylation of benzene with propylene to produce cumene, followed by oxidation of cumene to the corresponding hydroperoxide, and then cleavage of the hydroperoxide to produce equimolar amounts of phenol and acetone. However, the world demand for phenol is growing more rapidly than that for acetone. In addition, the cost of propylene feed is generally high.
[0005] Thus, a process that uses higher alkenes instead of propylene as feed and coproduces higher ketones, such as cyclohexanone, rather than acetone may be an attractive alternative route to the production of phenols. There is also a growing demand for cyclohexanone.
[0006] It is known from, e.g., U.S. Pat. No. 6,037,513 that cyclohexylbenzene can be produced by contacting benzene with hydrogen in the presence of a bifunctional catalyst comprising a molecular sieve of the MCM-22 type and at least one hydrogenation metal selected from palladium, ruthenium, nickel, cobalt, and mixtures thereof. This reference also discloses that the resultant cyclohexylbenzene can be oxidized to the corresponding hydroperoxide which is then decomposed to the desired phenol and cyclohexanone co-product.
[0007] The oxidation of cyclohexylbenzene to produce cyclohexylbenzene hydroperoxide and the cleavage of cyclohexylbenzene hydroperoxide to produce phenol and cyclohexanone are much more complex than the cumene oxidation and cumene hydroperoxide cleavage in the Hock process. Many process parameters can affect the final yield of phenol and cyclohexanone in the cyclohexylbenzene hydroperoxide cleavage step.
SUMMARY
[0008] It has been found that in the cyclohexylbenzene oxidation product, water is present at a non-negligible amount and the residual cyclohexylbenzene concentration may be high. It has also been found that the presence of water in the cleavage feed can slow the reaction rate of the cyclohexylbenzene hydroperoxide cleavage reaction, and that the presence of cyclohexylbenzene at a high concentration in the cleavage reaction media can reduce the selectivity of phenol and/or cyclohexanone. The method of the present disclosure, by reducing water and/or cyclohexylbenzene concentration(s) in the cleavage feed, increases the overall yield(s) of phenol and/or cyclohexanone.
[0009] The present disclosure relates to a process for making phenol and/or cyclohexanone, the process comprising: [0010] (A) oxidizing a cyclohexylbenzene feed to obtain an oxidation product comprising cyclohexylbenzene, cyclohexylbenzene hydroperoxide and water; [0011] (B) removing at least a portion of the water from at least a portion of the oxidation product to obtain a cleavage feed; and [0012] (C) contacting at least a portion of the cyclohexylbenzene hydroperoxide in the cleavage feed with an acid catalyst in a cleavage reactor under cleavage conditions to obtain a cleavage product comprising phenol and cyclohexanone.
[0013] Step (B) may comprise (B1) flashing the oxidation product at an absolute pressure of at most 50 kPa. Alternatively, step (B) may comprise: (B2) separating at least a portion of the cyclohexylbenzene from the oxidation product. Alternatively, step (B) may comprise both (B1) and (B2) above, and the steps (B1) and (B2) may be conducted in separate vessels or in the same vessel.
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