Aromatic feedstock-derived mesophase pitch composition, method of manufacture thereof and use thereof

Abstract

A mesophase pitch composition can be obtained by subjecting an isotropic pitch composition to heat treatment. A method for producing a mesophase pitch composition may include heat treating an isotropic pitch composition containing two or more aromatic classes linked by at least one methylene bridge between each aromatic class at a temperature of about 300°C to about 500°C to produce a mesophase pitch composition having a weight average molecular weight of about 300 g / mol to about 2,000 g / mol, a softening point of about 100°C or higher, a mesophase content of about 0.01 vol% to 100 vol%, based on the total volume of the mesophase pitch composition, and a microresidual carbon content of about 25 wt% or higher, based on the total weight of the mesophase pitch composition; and inducing cyclization between at least two of the two or more aromatic classes, forming one or more five-membered and / or six-membered rings, by the heat treatment.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of and priority to U.S. Provisional Application No. 63 / 167319, filed March 29, 2021, the disclosure of which is incorporated herein by reference. This application is related to concurrently filed provisional patent application USSN 63 / 167,354, entitled "Isotropic Pitch Compositions Derived from Aromatic Feedstocks, Methods for Making Same, and Uses Thereof."

[0002] Field The present disclosure relates to mesophase pitch compositions produced from synthetic isotropic pitch compositions derived from aromatic hydrocarbon feedstocks, methods for their production, and uses thereof. [Background technology]

[0003] The carbon fiber market has grown significantly over the past decade, which can be attributed to increased demand from a wide range of industries, such as, for example, automotive (e.g., body parts such as luggage doors, hoods, front ends, bumpers, doors, chassis, suspension systems such as leaf springs, drive shafts, etc.), aerospace (e.g., aircraft and space systems), high-performance watercraft (e.g., yachts and rowing shells), aircraft, sporting goods (e.g., golf clubs, tennis rackets, skis, snowboards, helmets, rowing boats, or water skiing equipment), construction (non-structural and structural systems), military (e.g., aerial drones, armor, armored vehicles, military aircraft), wind power industry, energy storage applications, fire protection materials, carbon-carbon composites, carbon fibers, and many insulating and sealing materials (e.g., concrete) used in building and road construction, turbine blades, lightweight cylinders and pressure vessels, offshore rope and drilling risers, and medical. Non-limiting properties of carbon fibers make such materials suitable for high performance applications, including high bulk and tensile moduli (depending on the morphology of the carbon fibers), high electrical and thermal conductivity, high specific gravity, etc. However, despite the excellent properties exhibited by such materials, the high cost of carbon fibers limits their applications and widespread use. For these reasons, developing technologies to produce carbon fibers at low cost has become a major challenge for researchers and leading manufacturers. A reliable, low-cost process for producing liquid crystalline or mesophase pitch from heavy oil bottoms suitable for carbon fiber production has been a challenging task in the petrochemical industry, requiring harsh reaction conditions such as high temperature and pressure, long residence times, etc. In addition, non-selective reactions tend to produce a wide range of undesired products, such as gas oil and coke, in addition to pitch. In particular, stringent requirements for product quality and purity for carbon fiber continue to pose challenges. To be suitable for carbon fiber production, mesophase pitch must exhibit trace amounts of sulfur and low solid fines content, both of which are extremely difficult to remove from petroleum bottoms. Highly oriented carbon fibers with excellent mechanical properties derived from pitch precursors have long been a goal of the petrochemical industry. The extremely high tensile modulus of mesophase pitch-based carbon fibers is attributed to the highly oriented aromatic molecules with planar liquid crystalline structure in the parent mesophase pitch. Petroleum by-products containing rich aromatic fractions have commonly been used to produce mesophase pitch. However, such production processes often require toxic and harsh conditions, such as the use of superacids (e.g., HF / BF3 or AlCl3). Furthermore, the severe acidic conditions and the difficulty of producing high-purity pitch materials limit the widespread application of current processes. Furthermore, the mechanical properties of pitch-based carbon fibers depend on the orientation and uniformity of the precursor pitch fibers and the purity of the pitch itself. Factors that determine the suitability of a pitch composition precursor for its intended application (e.g., mesophase pitch production, carbon fiber production, etc.) include, for example, softening point, molecular weight, viscosity, density, melting point, and secondary performance factors that are affected by these parameters. While pitch compositions with a wide range of physical properties may be ideal for use in various types of applications, currently, there are no robust methods for producing high-quality synthetic mesotropic pitch compositions, especially those with the ability to tailor the structural and other physical properties required to meet the specific needs of a given application. Summary of the Invention

[0004] overview In one embodiment, the present disclosure provides a method for producing a mesophase pitch composition, the method comprising: heat treating an isotropic pitch composition containing two or more aromatic classes linked by at least one methylene bridge between each aromatic class at a temperature of about 300°C to about 500°C to produce a mesophase pitch having a weight average molecular weight (Mw) of about 300 g / mol to about 2,000 g / mol, a softening point (T) of about 100°C or greater; sp ), producing a mesophase pitch composition having a mesophase content of about 0.01 vol% to 100 vol%, based on the total volume of the mesophase pitch composition, and a microcarbon residue (MCR) of about 25 wt% or greater, based on the total weight of the mesophase pitch composition; wherein the heat treatment induces cyclization between at least two of the two or more aromatic classes to form one or more five-membered and / or six-membered rings. In some embodiments, the present disclosure provides a mesophase pitch composition having a weight average molecular weight (Mw) of about 300 g / mol to about 2,000 g / mol, a softening point (T) of about 100° C. or greater, and a melting point (Mw) of about 100° C. or greater. sp ), a mesophase content of about 0.01 vol% to 100 vol%, based on the total volume of the mesophase pitch composition, and a microcarbon residue (MCR) of about 25 wt% or greater, based on the total weight of the mesophase pitch composition; wherein the mesophase pitch composition is made from an isotropic pitch composition having two or more aromatic classes linked by at least one methylene bridge between each aromatic class; and the isotropic pitch composition has a weight average molecular weight (Mw) of about 300 g / mol to about 2,000 g / mol, a softening point (T) of 50°C or greater. sp ), and a microcarbon residue (MCR) of about 15 wt. % or greater, based on the total weight of the isotropic pitch composition.

[0005] The following figures are included to illustrate certain aspects of the present disclosure and should not be considered the only structures. The disclosed subject matter is susceptible to possible modifications, variations, combinations, and equivalents in form and function that may occur to one of ordinary skill in the art having the benefit of this disclosure. [Brief explanation of the drawings]

[0006] [Figure 1] FIG. 1 shows a laser desorption / ionization mass spectrometry (LDI-MS) of the isotropic pitch composition of the present disclosure and its predicted structure based on the LDI-MS spectrum. [Figure 2] FIG. 2 is a laser desorption ionization mass spectrometry (LDI-MS) of an isotropic pitch composition corresponding to a mesotropic pitch composition after heat soak treatment. [Figure 3] FIG. 3 is a graph depicting the distribution of oligomers contained in a mesophase pitch composition. [Figure 4A] FIG. 4A depicts the mass spectrum of an isotropic pitch composition corresponding to a mesotropic pitch composition after heat soak treatment. [Figure 4B] FIG. 4B depicts the mass spectrum of an isotropic pitch composition corresponding to a mesotropic pitch composition after heat soak treatment. [Figure 5] FIG. 5 is a mass spectrum depicting the C32 identification of the mesotropic pitch composition after heat soak treatment and its proposed structure based on the LDI-MS spectrum. [Figure 6] FIG. 6 shows the mass spectrum of an isotropic pitch composition corresponding to the mesotropic pitch composition after heat soaking treatment, and its predicted structure based on the LDI-MS spectrum. [Figure 7] FIG. 7 is a polarized light microscope of a mesophase pitch composition of the present disclosure. [Figure 8] FIG. 8 is a laser desorption ionization mass spectrometry (LDI-MS) of a mesophase pitch composition of the present disclosure. [Figure 9] FIG. 9 is a polarized light microscope of a mesophase pitch composition of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0007] Detailed Description of the Invention The present disclosure relates to mesophase pitch compositions produced from synthetic isotropic pitch compositions derived from aromatic hydrocarbon feedstocks, methods for their production, and uses. In particular, the present disclosure relates to the acid-mediated production of said isotropic pitch compositions derived from aromatic hydrocarbon feedstocks, methods for their production, and uses (e.g., conversion to mesophase pitch for carbon fiber production). As noted above, there is an increasing demand in various industries for pitch, particularly high-quality pitch, such as pitch suitable for the production of carbon fibers. Currently, there are no synthetic options available that allow for the production of high-quality mesophase pitch compositions, particularly those that have the ability to tailor the structural, physical, and mechanical properties of the pitch composition to meet the specific needs of a given application. The present disclosure demonstrates that certain abundant products in the chemical and petroleum industries (e.g., aromatic feedstocks) can be suitable precursors for forming high-quality mesophase pitch compositions. More specifically, the present disclosure utilizes aromatics as feedstocks for the production of isotropic pitch compositions containing oligomers (e.g., dimers, trimers, tetramers, pentamers, hexamers, heptamers, etc.), which may be further subjected to heat treatment under mild reaction conditions (e.g., temperatures of about 300°C to about 500°C; atmospheric pressure) to cause cyclization within the individual oligomers in the isotropic pitch composition and form the corresponding mesophase pitch composition. In some instances, the mesophase pitch composition can be dehydrogenated or partially hydrogenated to form a corresponding mesophase pitch composition with higher aromaticity as the reaction product. Surprisingly and advantageously, mesophase pitch compositions with tunable properties and controlled molecular weight distributions (MWDs) may be formed by mild heat treatment (e.g., heat treatment at a temperature range of about 300°C to about 500°C) of well-defined, high-purity isotropic pitch compositions (e.g., about 80% or greater isolated yield, e.g., about 90% or greater isolated yield, e.g., 100% isolated yield). Without being bound by any theory or mechanism, it is believed that narrow MWD materials can produce higher quality mesophase pitches compared to broad MWD materials. Furthermore, mild heat treatment can significantly prevent coke formation, thereby reducing fouling problems. In particular, for isolated oligomers (i.e., well-defined, high-purity isotropic pitch compositions), mild heat treatment can induce cyclization and, in some cases, aromatization of the pitch composition at a temperature range significantly lower than conventional pitch production (e.g., typically about 450°C to about 550°C). Additionally, it is believed that mesophase pitch compositions produced by the mild heat treatment described above may be further processed using solvents (e.g., toluene) having a high Solubility Blending Number (SBN) (e.g., typically 80 or greater, e.g., 100 or greater) to concentrate the mesophase molecules, thereby producing mesophase in higher purity and yield compared to those with a lower SBN (less than 80).

[0008] The present disclosure provides a method for producing an isotropic pitch composition containing two or more aromatic classes linked by at least one methylene bridge between each aromatic class by heat treatment at a temperature of about 300°C to about 500°C, which produces a pitch having a weight average molecular weight (Mw) of about 300 g / mol to about 2,000 g / mol, a softening point (T) of about 100°C or greater, and a melting point (Mw) of about 100°C or greater. sp), producing a mesophase pitch composition having a mesophase content of about 0.01 vol% to 100 vol%, based on the total volume of the mesophase pitch composition, and a microcarbon residue (MCR) of about 25 wt% or greater, based on the total weight of the mesophase pitch composition; the thermal treatment induces cyclization between at least two of the two or more aromatic classes to form one or more five-membered and / or six-membered rings. The cyclization between at least two of the two or more aromatic classes to form one or more six-membered rings may then be followed by dehydrogenative aromatization to produce a highly aromatic mesophase pitch composition. The aromatic class may be unsubstituted and / or substituted aromatics selected from the group consisting of 1-membered aromatic rings (ARC1), 2-membered aromatic rings (ARC2), 3-membered aromatic rings (ARC3), 4-membered aromatic rings (ARC4), 5-membered aromatic rings (ARC5), 6-membered aromatic rings (ARC6), 7-membered aromatic rings (ARC7), 8-membered aromatic rings (ARC8), 9-membered aromatic rings (ARC9), 10-membered or greater aromatic rings (ARC10+), and any combination thereof. The isotropic pitch composition has a weight average molecular weight (Mw) of about 300 g / mol to about 2,000 g / mol, a softening point (T) of 50°C or higher, and sp ), and a micro carbon residue (MCR) of about 15 wt. % or greater, based on the total weight of the isotropic pitch composition.

[0009] Definitions and Test Methods All numerical values in the detailed description and claims herein are modified by "about" or "approximately" with respect to the indicated value and take into account experimental error and variations that can be expected by one of ordinary skill in the art. Unless otherwise specified, ambient (room) temperature is about 25°C. As used in this disclosure and claims, the singular forms "a," "an," and "the" include the plural forms unless the context dictates otherwise. The term "and / or," when used herein in expressions such as "A and / or B," is intended to include "A and B," "A or B," "A," and "B." For purposes of this disclosure and the claims thereto, the following definitions shall be used. Unless otherwise specified, the term "C n " means a hydrocarbon having n carbon atoms per molecule, where n is a positive integer. The term “C n " group or compound refers to a group or compound having a total of n carbon atoms. m -C n " group or compound refers to a group or compound having a total number of carbon atoms ranging from m to n. Thus, C1-C 50 Alkyl refers to alkyl groups having a total number of carbon atoms ranging from 1 to 50. The terms "group," "radical," and "substituent" can be used interchangeably. The terms "hydrocarbyl radical," "hydrocarbyl group," or "hydrocarbyl" are used interchangeably and are defined to mean a group consisting solely of hydrogen and carbon atoms. Preferred hydrocarbyls are C-C 100 A radical, which may be linear, branched, or cyclic, and, if cyclic, may be aromatic or non-aromatic. Examples of such radicals include, but are not limited to, alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isoamyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and the like; and aryl groups such as phenyl, benzylnaphthalenyl, and the like.

[0010] Unless otherwise specified (e.g., in the definition of "substituted hydrocarbyl"), the term "substituted" means that at least one hydrogen atom is replaced with at least one non-hydrogen group, such as a hydrocarbyl group. The term "aryl" or "aryl group" refers to an aromatic ring (typically consisting of 6 carbon atoms) and its substituents, such as phenyl, 2-methylphenyl, xylyl, 4-bromoxyl, and the like. The term "substituted aromatic" means an aromatic group in which one or more hydrogen radicals have been replaced by a hydrocarbyl or substituted hydrocarbyl. The term "ring atom" means an atom that is part of a cyclic ring structure. By this definition, a benzyl group has 6 ring atoms and a tetrahydrofuran has 5 ring atoms. Where isomers of a named alkyl, alkenyl, alkoxide, or aryl group exist (e.g., n-butyl, iso-butyl, sec-butyl, and tert-butyl), a reference to one species of the group (e.g., n-butyl) is intended to specifically disclose the remaining isomers of that group (e.g., iso-butyl, sec-butyl, and tert-butyl). Similarly, a reference to an alkyl, alkenyl, alkoxide, or aryl group without specifying a particular isomer (e.g., butyl) explicitly discloses all isomers (e.g., n-butyl, iso-butyl, sec-butyl, and tert-butyl). The terms "straight chain" or "straight chain hydrocarbon" refer to a hydrocarbon or hydrocarbyl group having a continuous carbon chain without side branching, which may be optionally substituted. The terms "cyclic" or "cyclic hydrocarbon" refer to a hydrocarbon or hydrocarbyl group having a closed carbon ring, which may be optionally substituted. The term "carbocyclic" may refer synonymously to such a hydrocarbon or hydrocarbyl group. The terms "branched" or "branched hydrocarbon" refer to a hydrocarbon or hydrocarbyl group having a linear carbon chain or closed carbon ring from which hydrocarbyl side chains extend. Optional substitution can be present on the linear carbon chain, the closed carbon ring, and / or the hydrocarbyl side chains. The terms "aromatic" or "aromatic hydrocarbon" refer to a hydrocarbon or hydrocarbyl group having a cyclic arrangement of conjugated pi electrons that satisfies Hückel's rule. The term "independently," when referring to the selection of multiple items from a given Markush group, means that the choice selected for the first item does not necessarily affect the choice of any second or subsequent items. That is, the independent selection of multiple items from a given Markush group means that the individual items may be the same or different from each other.

[0011] Examples of saturated hydrocarbyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl (isopentyl), neopentyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, etc., and substituted analogs thereof. Examples of unsaturated hydrocarbyl groups include, but are not limited to, ethenyl, propenyl, allyl, 1,4-butadienyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl, etc., and substituted analogs thereof. Examples of aromatic hydrocarbyl groups include, but are not limited to, phenyl, tolyl, xylyl, naphthyl, etc. Polynuclear aryl groups may include, but are not limited to, naphthalenyl, anthracenyl, indanyl, indenyl, and tetralinyl. Unless otherwise specified, the term "substantially free of" with respect to a particular ingredient means a concentration of that ingredient in the relevant composition of 5 mol % or less (e.g., 3 mol % or less, 1 mol % or less, or about 0%, within the limits of the relevant measurement framework), based on the total amount of the relevant composition. The term "isolated" refers to the condition of a material obtained substantially free of solvents and / or precursors to a given material.

[0012] As used herein, Mw is weight average molecular weight, wt% is weight percent, and mol% is mole percent. Unless otherwise stated, molecular weight units (e.g., Mw) are g / mol. Unless otherwise indicated, the term "room temperature", also referred to as "ambient temperature", is approximately 23°C. The "Micro Carbon Residue Test," also known as the "MCRT," is a standard test method (micromethod) for the determination of carbon residue. Carbon residue values in various petroleum materials serve as an indicator of the material's tendency to form carbonaceous deposits under cracking conditions similar to those used in the test method and can be useful as a guide for the production of a given resource. However, caution should be exercised in interpreting the results. This test method is directed to determining the amount of carbon residue formed after vaporization and pyrolysis of a petroleum material under specified conditions and is intended to provide an indication of the associated coke formation tendency of such materials. MCRT is measured in accordance with ASTM D4530-15 standard test method.

[0013] The term "solvent blending number" (SBN) refers to a parameter related to the compatibility of a material (e.g., oil, pitch, etc.) with different proportions of a model solvent (e.g., toluene) or solvent mixture (e.g., toluene / n-heptane). "Softening point" refers to the temperature or temperature range at which a material softens, where softening point (SP) is measured using a METTLER TOLEDO dropping point apparatus, e.g., a METTLER TOLEDO DP70, according to a procedure similar to ASTM D36. The following abbreviations may be used throughout this disclosure and claims: "MCRT" is Micro Carbon Residue Test, "equiv" is molar equivalent, "ppm" is parts per million, and "T sp " is the softening point temperature.

[0014] Isotropic pitch composition The disclosed method is a non-dehydrogenating synthetic route that provides a route for the production of pitch precursors for the production of advanced carbon products. Furthermore, the disclosed method provides a method for the production of high-quality synthetic isotropic pitch compositions, particularly those with the ability to tailor the structural and other physical properties required to meet the specific needs of a given application. The disclosed isotropic pitch compositions may be used as mesophase pitch precursors for the production of highly oriented carbon fibers with excellent mechanical properties, as well as carbon fibers to improve the production of conventional paraffinic hydrocarbons or thickeners. Embodiments of the present disclosure include isotropic pitch compositions containing two or more aromatic classes linked by at least one methylene bridge between each aromatic class, where the isotropic pitch composition has a weight average molecular weight (Mw) of about 300 g / mol to about 2,000 g / mol, a softening point (T) of 50°C or greater, and sp ), and a microcarbon residue (MCR) of about 15 wt% or greater, based on the total weight of the pitch composition. The isotropic pitch composition of the present disclosure is a methylene-bridged aromatic oligomer produced by reacting an aromatic feedstock with formaldehyde and / or paraformaldehyde in the presence of acetic acid and sulfuric acid. As used herein, aromatic classes may include the following: unsubstituted and / or substituted aromatics selected from the group consisting of 1-membered aromatics (ARC1), 2-membered aromatics (ARC2), 3-membered aromatics (ARC3), 4-membered aromatics (ARC4), 5-membered aromatics (ARC5), 6-membered aromatics (ARC6), 7-membered aromatics (ARC7), 8-membered aromatics (ARC8), 9-membered aromatics (ARC9), 10-membered or higher aromatics (ARC10+), and any combination thereof. Substituted aromatics are unsubstituted and / or substituted aromatics selected from the group consisting of C1-C 20 Hydrocarbyl monosubstituted aromatics, C1-C 20 Hydrocarbyl-disubstituted aromatics, C1-C 20The substituted aromatics may be selected from the group consisting of C1-C5 hydrocarbyl monosubstituted aromatics, C1-C5 hydrocarbyl disubstituted aromatics, C1-C5 hydrocarbyl trisubstituted aromatics, and any combination thereof. In at least one embodiment, the substituted aromatics may be selected from the group consisting of C1-C5 hydrocarbyl monosubstituted aromatics, C1-C5 hydrocarbyl disubstituted aromatics, C1-C5 hydrocarbyl trisubstituted aromatics, and any combination thereof. The isotropic pitch composition can be produced from well-defined, high purity, and cost-effective substituted and / or unsubstituted monocyclic aromatic feedstocks, substituted and / or unsubstituted polycyclic aromatic hydrocarbon (PAH) feedstocks, and any combination thereof. The PAH may comprise a two-ring aromatic feedstock or a multi-ring aromatic feedstock (e.g., a three-ring aromatic feedstock or higher). One or more of the aromatic classes may contain a partially hydrogenated aromatic ring, such as, for example, tetralin (also called "1,2,3,4-tetrahydronaphthalene") or indene.

[0015] The isotropic pitch composition of the present disclosure may be produced by: mixing an aromatic feedstock containing one or more aromatic classes with acetic acid and sulfuric acid at ambient temperature to produce a first mixture; heating the first mixture at a temperature of from about 40°C to about 400°C; adding formaldehyde and / or paraformaldehyde to the first mixture at a temperature of from about 40°C to about 400°C to produce a second mixture containing a reaction product composition, wherein the reaction product composition contains or consists essentially of oligomeric products (e.g., dimers, trimers, tetramers, pentamers, etc.); filtering the second mixture; and isolating the isotropic pitch composition. The isotropic pitch compositions of the present disclosure may be present in a continuous mode, such as in a continuous stirred tank reactor (CSTR) or a tubular reactor, and such reactors may be adapted for continuous production line processing. Other suitable reactors for carrying out the production of isotropic pitch compositions according to the disclosure herein may include a CSTR or a series of CSTRs, a stirred tank reactor (STR) or a series of STRs, a tubular reactor, a staged bubble column reactor, a tubular reactor with cocurrent gas-liquid flow, a tubular reactor with cyclic gas-liquid separation, and the like. The isotropic pitch composition of the present disclosure may be carried out at a temperature ranging from about 40°C to about 400°C, and / or at a residence time ranging from less than 1 minute to about 48 hours, such as 36 hours or less, such as 24 hours or less, such as 12 hours or less, such as 6 hours or less. Another aspect of the present disclosure relates to a method for producing an isotropic pitch composition having: mixing an aromatic feedstock containing one or more aromatic classes with paraformaldehyde in the presence of acetic acid at ambient temperature to produce a first mixture; heating the first mixture at a temperature of about 40°C to about 100°C; and mixing a second mixture containing sulfuric acid and acetic acid with the first mixture at a temperature of about 40°C to about 100°C to form a mixture containing an isotropic pitch composition, wherein the isotropic pitch composition has: one or more aromatic classes linked by at least one methylene bridge between each aromatic class, wherein the isotropic pitch composition has a weight average molecular weight (Mw) of about 300 g / mol to about 2,000 g / mol, a softening point (T) of 50°C or greater, and a melting point (Mw) of 50°C or greater. sp ), and a microcarbon residue (MCR) of about 15 wt. % or greater, based on the total weight of the isotropic pitch composition.

[0016] The reaction conditions of the methods herein are important for the molecular weight distribution and softening point of the isotropic pitch composition. Advantageously, the methods of the present disclosure allow control over both the molecular weight distribution and the softening point by adjusting the molar ratio of acetic acid, sulfuric acid, and / or paraformaldehyde. The softening point of the isotropic pitch composition can be increased based on the amount of sulfuric acid and paraformaldehyde, among others. Acetic acid may be used, at least in part, as a solvent. Furthermore, any residual acid can be easily removed by filtration after washing the residue containing the isotropic pitch composition with water and a dilute base solution (e.g., NaOH or NH4OH), and then the isotropic pitch composition can be obtained as a high-purity material (i.e., quantitatively consumed starting material, and analyzed by mass spectrometry (e.g., Fourier transform ion cyclotron resonance (FTICR)). 1 H NMR, and 13 This facilitates the isolation of the product (as confirmed by C NMR spectroscopy).

[0017] Non-limiting examples of aromatic feedstocks include benzene, toluene, xylenes (e.g., ortho-, meta-, and para-substituted xylenes), naphthalene, 1-methylnaphthalene, 2-methylnaphthalene, 3-methylnaphthalene, 2,6-dimethylnaphthalene, 1-ethylnaphthalene, 2-ethylnaphthalene, 1,7-diisopropylnaphthalene, 2,3-diisopropylnaphthalene, 2,6-diisopropylnaphthalene, 2,7-diisopropylnaphthalene, 1-butylnaphthalene, 2-butylnaphthalene, 1-tert-butylnaphthalene, 2-tert-butylnaphthalene, anthracene, 1-methylanthracene, 2-methylanthracene, 9-methylanthracene, and 1-methylanthracene. tetracene, 9,10-dimethylanthracene, 9,10-diphethylanthracene, phenanthrene, 1-methylphenanthrene, 1-ethylphenanthrene, 2-methylphenanthrene, 1-phenylphenanthrene, 2,7-diphenylphenanthrene, pyrene, 1-propylpyrene, 4-propylpyrene, 1,2,3-trimethylpyrene, benzopyrene, picenecoronene, chrysene, tetracene, pentacene, triphenylene, corannulene, fluorene, benzo[j]fluoranthene, benzo[c]fluorene, perylene, benzo-perylene, ovalene, AROMATIC-200 TM , acenaphthene, and any isomers thereof, and any combinations thereof. Suitable aromatic hydrocarbon compounds may contain 1 to 3 rings and may be substituted with an alkyl group containing 1 to 6 carbon atoms, a phenyl group, or an aralkyl group containing 7 to 9 carbon atoms. In this specification, the aromatic hydrocarbon is advantageously selected from xylene, naphthalene, methylnaphthalene, dimethylnaphthalene, biphenyl, anthracene, phenanthrene, pyrene, and their derivatives substituted with an alkyl group containing 1 to 6 carbon atoms. More preferred are polycyclic aromatic hydrocarbons such as naphthalene, methylnaphthalene, and dimethylnaphthalene, as well as mixtures of these polycyclic aromatic hydrocarbons, such as aromatic oils. When a polycyclic aromatic compound is used as a reactant, the compound may be, for example, an aromatic hydrocarbon oil containing 90 wt% or more of naphthalene, high-purity naphthalene, or an aromatic hydrocarbon oil containing mainly naphthalene. Naphthalene oil fractions, methylnaphthalene oil fractions, and intermediate oil fractions derived from coal tar, as well as intermediate products and residual oils obtained by recovering the main components of these fractions by distillation, extraction, etc., can be used as hydrocarbon oils. The naphthalene- or methylnaphthalene-containing oils are often produced as a mixture of the main component and polycyclic aromatic hydrocarbons with similar boiling points. The aromatic hydrocarbons used in the reaction may also be a mixture, as long as pure raw materials are used. Naphthalene-containing aromatic hydrocarbon oils naturally contain aromatic hydrocarbons as the main component, and may additionally contain aromatic compounds with functional groups containing inert aliphatic hydrocarbons. Aromatic hydrocarbon oils containing 90 wt% or more naphthalene may be refined naphthalene, but a preferred example is 95% grade naphthalene. This particular material contains benzothiophene, methylnaphthalene, etc. in addition to naphthalene. The formaldehyde used in the method of the present disclosure may be formaldehyde itself or a compound capable of producing formaldehyde in the reaction system, and may include formaldehyde, formalin, paraformaldehyde, etc. In some cases, paraformaldehyde may be used under solvent-free conditions or in an alkaline (e.g., NaOH or KOH) solution. Non-limiting examples of acids may include sulfuric acid, hydrochloric acid, nitric acid, acetic acid, phosphoric acid, citric acid, carbonic acid, oxalic acid, aromatic sulfonic acids. The acids of the present disclosure may be used as solvents.

[0018] The isotropic pitch composition of the present disclosure may contain, based on the total weight of the isotropic pitch composition, 0.1 wt% to 100 wt% of ARC1, 0.1 wt% to 100 wt% of ARC2, 0.1 wt% to 100 wt% of ARC3, 0.1 wt% to 100 wt% of ARC4, 0.1 wt% to 100 wt% of ARC5, 0.1 wt% to 100 wt% of ARC6, 0.1 wt% to 100 wt% of ARC7, 0.1 wt% to 100 wt% of ARC8, 0.1 wt% to 100 wt% of ARC9, and 0.1 wt% to 100 wt% of ARC10+. The isotropic pitch composition of the present disclosure may comprise, based on the total weight of the isotropic pitch composition, 0.1 wt% to 100 wt% of ARC1 (0.1 wt% to 95 wt%, or 0.5 wt% to 90 wt%, or 1 wt% to 85 wt%, or 5 wt% to 80 wt%, or 10 wt% to 75 wt%, or 15 wt% to 70 wt%, or 20 wt% to 65 wt%, or 25 wt% to It may contain 60 wt%, or 30 wt% to 55 wt%, or 35 wt% to 50 wt%, or 40 wt% to 45 wt%, or 0.1 wt% to 50 wt%, or 0.5 wt% to 45 wt%, or 1 wt% to 40 wt%, or 1.5 wt% to 35 wt%, or 2 wt% to 30 wt%, or 2.5 wt% to 25 wt%, or 3 wt% to 20 wt%). The isotropic pitch composition of the present disclosure may comprise, based on the total weight of the isotropic pitch composition, 0.1 wt% to 100 wt% of ARC2 (0.1 wt% to 95 wt%, or 0.5 wt% to 90 wt%, or 1 wt% to 85 wt%, or 5 wt% to 80 wt%, or 10 wt% to 75 wt%, or 15 wt% to 70 wt%, or 20 wt% to 65 wt%, or 25 wt% to It may contain 60 wt%, or 30 wt% to 55 wt%, or 35 wt% to 50 wt%, or 40 wt% to 45 wt%, or 0.1 wt% to 50 wt%, or 0.5 wt% to 45 wt%, or 1 wt% to 40 wt%, or 1.5 wt% to 35 wt%, or 2 wt% to 30 wt%, or 2.5 wt% to 25 wt%, or 3 wt% to 20 wt%). The isotropic pitch composition of the present disclosure may comprise, based on the total weight of the isotropic pitch composition, 0.1 wt% to 100 wt% of ARC3 (0.1 wt% to 95 wt%, or 0.5 wt% to 90 wt%, or 1 wt% to 85 wt%, or 5 wt% to 80 wt%, or 10 wt% to 75 wt%, or 15 wt% to 70 wt%, or 20 wt% to 65 wt%, or 25 wt% to It may contain 60 wt%, or 30 wt% to 55 wt%, or 35 wt% to 50 wt%, or 40 wt% to 45 wt%, or 0.1 wt% to 50 wt%, or 0.5 wt% to 45 wt%, or 1 wt% to 40 wt%, or 1.5 wt% to 35 wt%, or 2 wt% to 30 wt%, or 2.5 wt% to 25 wt%, or 3 wt% to 20 wt%). The isotropic pitch composition of the present disclosure may comprise, based on the total weight of the isotropic pitch composition, 0.1 wt% to 100 wt% of ARC4 (0.1 wt% to 95 wt%, or 0.5 wt% to 90 wt%, or 1 wt% to 85 wt%, or 5 wt% to 80 wt%, or 10 wt% to 75 wt%, or 15 wt% to 70 wt%, or 20 wt% to 65 wt%, or 25 wt% to It may contain 60 wt%, or 30 wt% to 55 wt%, or 35 wt% to 50 wt%, or 40 wt% to 45 wt%, or 0.1 wt% to 50 wt%, or 0.5 wt% to 45 wt%, or 1 wt% to 40 wt%, or 1.5 wt% to 35 wt%, or 2 wt% to 30 wt%, or 2.5 wt% to 25 wt%, or 3 wt% to 20 wt%). The isotropic pitch composition of the present disclosure may comprise, based on the total weight of the isotropic pitch composition, 0.1 wt% to 100 wt% of ARC5 (0.1 wt% to 95 wt%, or 0.5 wt% to 90 wt%, or 1 wt% to 85 wt%, or 5 wt% to 80 wt%, or 10 wt% to 75 wt%, or 15 wt% to 70 wt%, or 20 wt% to 65 wt%, or 25 wt% to It may contain 60 wt%, or 30 wt% to 55 wt%, or 35 wt% to 50 wt%, or 40 wt% to 45 wt%, or 0.1 wt% to 50 wt%, or 0.5 wt% to 45 wt%, or 1 wt% to 40 wt%, or 1.5 wt% to 35 wt%, or 2 wt% to 30 wt%, or 2.5 wt% to 25 wt%, or 3 wt% to 20 wt%). The isotropic pitch composition of the present disclosure may comprise, based on the total weight of the isotropic pitch composition, 0.1 wt% to 100 wt% of ARC6 (0.1 wt% to 95 wt%, or 0.5 wt% to 90 wt%, or 1 wt% to 85 wt%, or 5 wt% to 80 wt%, or 10 wt% to 75 wt%, or 15 wt% to 70 wt%, or 20 wt% to 65 wt%, or 25 wt% to It may contain 60 wt%, or 30 wt% to 55 wt%, or 35 wt% to 50 wt%, or 40 wt% to 45 wt%, or 0.1 wt% to 50 wt%, or 0.5 wt% to 45 wt%, or 1 wt% to 40 wt%, or 1.5 wt% to 35 wt%, or 2 wt% to 30 wt%, or 2.5 wt% to 25 wt%, or 3 wt% to 20 wt%). The isotropic pitch composition of the present disclosure may comprise, based on the total weight of the isotropic pitch composition, 0.1 wt% to 100 wt% of ARC7 (0.1 wt% to 95 wt%, or 0.5 wt% to 90 wt%, or 1 wt% to 85 wt%, or 5 wt% to 80 wt%, or 10 wt% to 75 wt%, or 15 wt% to 70 wt%, or 20 wt% to 65 wt%, or 25 wt% to It may contain 60 wt%, or 30 wt% to 55 wt%, or 35 wt% to 50 wt%, or 40 wt% to 45 wt%, or 0.1 wt% to 50 wt%, or 0.5 wt% to 45 wt%, or 1 wt% to 40 wt%, or 1.5 wt% to 35 wt%, or 2 wt% to 30 wt%, or 2.5 wt% to 25 wt%, or 3 wt% to 20 wt%). The isotropic pitch composition of the present disclosure may comprise, based on the total weight of the isotropic pitch composition, 0.1 wt% to 100 wt% of ARC8 (0.1 wt% to 95 wt%, or 0.5 wt% to 90 wt%, or 1 wt% to 85 wt%, or 5 wt% to 80 wt%, or 10 wt% to 75 wt%, or 15 wt% to 70 wt%, or 20 wt% to 65 wt%, or 25 wt% to It may contain 60 wt%, or 30 wt% to 55 wt%, or 35 wt% to 50 wt%, or 40 wt% to 45 wt%, or 0.1 wt% to 50 wt%, or 0.5 wt% to 45 wt%, or 1 wt% to 40 wt%, or 1.5 wt% to 35 wt%, or 2 wt% to 30 wt%, or 2.5 wt% to 25 wt%, or 3 wt% to 20 wt%). The isotropic pitch composition of the present disclosure may comprise 0.1 wt% to 100 wt% of ARC9 (0.1 wt% to 95 wt%, or 0.5 wt% to 90 wt%, or 1 wt% to 85 wt%, or 5 wt% to 80 wt%, or 10 wt% to 75 wt%, or 15 wt% to 70 wt%, or 20 wt% to 65 wt%, or 25 wt% to It may contain 60 wt%, or 30 wt% to 55 wt%, or 35 wt% to 50 wt%, or 40 wt% to 45 wt%, or 0.1 wt% to 50 wt%, or 0.5 wt% to 45 wt%, or 1 wt% to 40 wt%, or 1.5 wt% to 35 wt%, or 2 wt% to 30 wt%, or 2.5 wt% to 25 wt%, or 3 wt% to 20 wt%). The isotropic pitch composition of the present disclosure may contain, based on the total weight of the isotropic pitch composition, 0.1 wt% to 100 wt% of ARC10+ (0.1 wt% to 95 wt%, or 0.5 wt% to 90 wt%, or 1 wt% to 85 wt%, or 5 wt% to 80 wt%, or 10 wt% to 75 wt%, or 15 wt% to 70 wt%, or 20 wt% to 65 wt%, or 25 wt% It may contain 0.1 wt% to 50 wt%, 0.5 wt% to 45 wt%, 1 wt% to 40 wt%, 1.5 wt% to 35 wt%, 2 wt% to 30 wt%, 2.5 wt% to 25 wt%, or 3 wt% to 20 wt%). The isotropic pitch composition of the present disclosure may contain, based on the total weight of the isotropic pitch composition, 0.1 wt% to 100 wt% of ARC1, 0.1 wt% to 100 wt% of ARC2, 0.1 wt% to 80 wt% of ARC3, 0.1 wt% to 50 wt% of ARC4, 0.1 wt% to 50 wt% of ARC5, 0.1 wt% to 25 wt% of ARC6, 0.1 wt% to 25 wt% of ARC7, 0 wt% to 10 wt% of ARC8, 0 wt% to 10 wt% of ARC9, and 0 wt% to 5 wt% of ARC10+.

[0019] Further, the isotropic pitch composition has a T of about 500°C or less (or from about 90°C to about 500°C, or from about 100°C to about 490°C, or from about 110°C to about 480°C, or from about 120°C to about 470°C, or from about 130°C to about 460°C, or from about 140°C to about 450°C, or from about 150°C to about 440°C, or from about 160°C to about 430°C, or from about 170°C to about 420°C, or from about 180°C to about 410°C, or from about 200°C to about 400°C). sp The isotropic pitch composition may have a T of about 100°C or greater. sp may have The isotropic pitch composition may have an MCR of about 40 wt% or less (or 35 wt% or less, or 30 wt% or less, or 25 wt% or less, or 20 wt% or less, or 15 wt% or less), based on the total weight of the isotropic pitch composition. The isotropic pitch composition may have an MCR of about 15 wt% to about 40 wt%, based on the total weight of the isotropic pitch composition. The isotropic pitch composition may have a Mw of about 300 g / mol to about 2,000 g / mol (or about 400 g / mol to about 2,000 g / mol, or about 500 g / mol to about 1,500 g / mol, or about 600 g / mol to about 800 g / mol, or about 300 g / mol to about 1,000 g / mol, or about 300 g / mol to about 500 g / mol). Alternatively, the isotropic pitch composition may have a Mw of about 500 g / mol or less (or from about 100 g / mol to about 500 g / mol, or from about 150 g / mol to about 400 g / mol, or from about 200 g / mol to about 350 g / mol, or from about 250 g / mol to about 300 g / mol, or from about 100 g / mol to about 250 g / mol, or from about 250 g / mol to about 500 g / mol).

[0020] A method for producing the isotropic pitch composition described above may include: mixing an aromatic feedstock containing one or more aromatic classes with paraformaldehyde in the presence of acetic acid at ambient temperature to form a first mixture; heating the first mixture at a temperature of about 40°C to about 100°C; and mixing a second mixture containing sulfuric acid and acetic acid with the first mixture at a temperature of about 40°C to about 100°C to form a mixture containing an isotropic pitch composition, wherein the isotropic pitch composition has one or more aromatic classes linked by at least one methylene bridge between each aromatic class, and wherein the isotropic pitch composition has a weight average molecular weight (Mw) of about 300 g / mol to about 2,000 g / mol, a softening point (T) of 90°C or greater, and a melting point (Mw) of 100°C or greater. sp ), and having a microcarbon residue (MCR) of about 25 wt% or greater, based on the total weight of the isotropic pitch composition. Without being bound by any theory, it is believed that the reaction begins via a Friedel-Crafts acylation reaction, which may be followed by a condensation reaction.

[0021] The blending of the aromatic feedstock and paraformaldehyde can be carried out at a molar ratio of aromatic feedstock to formaldehyde equivalents of from about 10:1 to about 1:10 (or from about 1:1.5 to about 1:9, or from about 1:2 to about 1:8, or from about 1:2.5 to about 1:7, or from about 1:3 to about 1:6, or from about 1:4 to about 1:5). In some cases, the molar ratio of aromatic feedstock to formaldehyde equivalents is 1:3. In other cases, the molar ratio of aromatic feedstock to formaldehyde equivalents is 1:1. Further, the addition of sulfuric acid may be carried out at a molar ratio of aromatic feedstock to sulfuric acid of from about 1:0.001 to about 1:20 (or from about 1:0.01 to about 1:19, or from about 1:0.1 to about 1:18, or from about 1:0.5 to about 1:17, or from about 1:1 to about 1:16, or from about 1:1.5 to about 1:15, or from about 1:2 to about 1:14, or from about 1:2.5 to about 1:13, or from about 1:3 to about 1:12, or from about 1:3.5 to about 1:11, or from about 1:4 to about 1:10). In at least one embodiment, the molar ratio of aromatic feedstock to sulfuric acid is 1:2. The mixing of the second mixture containing sulfuric acid and acetic acid with the first mixture may be carried out at a temperature of about 40°C to about 100°C, for example, about 50°C to about 90°C, for example, about 60°C to about 80°C, for example, about 40°C to about 60°C, for example, about 60°C to about 90°C, for about 5 hours or less (or, for example, about 5 minutes to about 5 hours, or about 10 minutes to about 4 hours, or about 15 minutes to about 3 hours, or about 20 minutes to about 2 hours, or about 25 minutes to about 1 hour, or about 30 minutes), although the conditions may be changed depending on the raw materials and acid used.

[0022] Separation of the isotropic pitch composition from any remaining paraformaldehyde, sulfuric acid, and / or acetic acid can be accomplished by filtering the reaction mixture, using alkali to wash the residue and neutralize the acid. Examples of suitable alkalis include water-soluble alkalis such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, and sodium carbonate. "Water-soluble" means that not only the alkali itself is water-soluble, but also the salt formed by reaction with an acid is water-soluble. Furthermore, "alkali" refers to a substance that can neutralize an acid, examples of which include hydroxides and salts of weak acids, such as carbonates of alkali metals and alkaline earth metals. For example, sodium hydroxide can be used in the filtration process because it is readily available and can dissolve in many acids. The method of the present disclosure may further include: cooling the mixture containing the isotropic pitch composition to ambient temperature; and separating the isotropic pitch composition from any remaining paraformaldehyde, sulfuric acid, and / or acetic acid. In some instances, the mixing of the first mixture with the second mixture containing sulfuric acid and acetic acid may be carried out at ambient pressure.

[0023] Mesophase pitch composition and method for producing same The present disclosure provides a method comprising the steps of: heat treating an isotropic pitch composition (described above) containing two or more aromatic classes linked by at least one methylene bridge between each aromatic class at a temperature of about 300°C to about 500°C to produce a pitch having a weight average molecular weight (Mw) of about 300 g / mol to about 2,000 g / mol, a softening point (T) of 100°C or greater, and a melting point (Mw) of 100°C or greater. sp ), producing a mesophase pitch composition having a mesophase content of about 0.01 vol% to 100 vol%, based on the total volume of the mesophase pitch composition, and a microcarbon residue (MCR) of about 25 wt% or greater, based on the total weight of the mesophase pitch composition; wherein the heat treatment induces cyclization between at least two of the two or more aromatic classes to form one or more five-membered and / or six-membered rings. In some cases, cyclization between at least two of the two or more aromatic classes to form one or more six-membered rings may be followed by dehydrogenative aromatization to produce a highly aromatic mesophase pitch composition. The mesophase pitch may be produced in a batch reactor, preferably a continuous flow reactor. In at least one embodiment, the mesophase pitch is produced in a continuous tubular reactor at a temperature ranging from about 300°C to about 500°C, with a residence time ranging from less than 1 minute to 48 hours (or 36 hours or less, or 24 hours or less, or 20 hours or less, or 15 hours or less, or 10 hours or less, or 5 hours or less, or 2.5 hours or less, or 1 hour or less).

[0024] As noted above, the two or more aromatic classes may be unsubstituted and / or substituted aromatics selected from the group consisting of one-membered aromatics (ARC1), two-membered aromatics (ARC2), three-membered aromatics (ARC3), four-membered aromatics (ARC4), five-membered aromatics (ARC5), six-membered aromatics (ARC6), seven-membered aromatics (ARC7), eight-membered aromatics (ARC8), nine-membered aromatics (ARC9), ten-membered or greater aromatics (ARC10+), and any combination thereof. The mesophase pitch composition may contain, based on the total weight of the isotropic pitch composition, 0.1 wt% to 100 wt% ARC1, 0.1 wt% to 100 wt% ARC2, 0.1 wt% to 100 wt% ARC3, 0.1 wt% to 100 wt% ARC4, 0.1 wt% to 100 wt% ARC5, 0.1 wt% to 100 wt% ARC6, 0.1 wt% to 100 wt% ARC7, 0.1 wt% to 100 wt% ARC8, 0.1 wt% to 100 wt% ARC9, and 0.1 wt% to 100 wt% ARC10+. The isotropic pitch composition of the present disclosure may comprise, based on the total weight of the isotropic pitch composition, 0.1 wt% to 100 wt% of ARC1 (0.1 wt% to 95 wt%, or 0.5 wt% to 90 wt%, or 1 wt% to 85 wt%, or 5 wt% to 80 wt%, or 10 wt% to 75 wt%, or 15 wt% to 70 wt%, or 20 wt% to 65 wt%, or 25 wt% to It may contain 60 wt%, or 30 wt% to 55 wt%, or 35 wt% to 50 wt%, or 40 wt% to 45 wt%, or 0.1 wt% to 50 wt%, or 0.5 wt% to 45 wt%, or 1 wt% to 40 wt%, or 1.5 wt% to 35 wt%, or 2 wt% to 30 wt%, or 2.5 wt% to 25 wt%, or 3 wt% to 20 wt%). The isotropic pitch composition of the present disclosure may comprise, based on the total weight of the isotropic pitch composition, 0.1 wt% to 100 wt% of ARC2 (0.1 wt% to 95 wt%, or 0.5 wt% to 90 wt%, or 1 wt% to 85 wt%, or 5 wt% to 80 wt%, or 10 wt% to 75 wt%, or 15 wt% to 70 wt%, or 20 wt% to 65 wt%, or 25 wt% to It may contain 60 wt%, or 30 wt% to 55 wt%, or 35 wt% to 50 wt%, or 40 wt% to 45 wt%, or 0.1 wt% to 50 wt%, or 0.5 wt% to 45 wt%, or 1 wt% to 40 wt%, or 1.5 wt% to 35 wt%, or 2 wt% to 30 wt%, or 2.5 wt% to 25 wt%, or 3 wt% to 20 wt%). The isotropic pitch composition of the present disclosure may comprise, based on the total weight of the isotropic pitch composition, 0.1 wt% to 100 wt% of ARC3 (0.1 wt% to 95 wt%, or 0.5 wt% to 90 wt%, or 1 wt% to 85 wt%, or 5 wt% to 80 wt%, or 10 wt% to 75 wt%, or 15 wt% to 70 wt%, or 20 wt% to 65 wt%, or 25 wt% to It may contain 60 wt%, or 30 wt% to 55 wt%, or 35 wt% to 50 wt%, or 40 wt% to 45 wt%, or 0.1 wt% to 50 wt%, or 0.5 wt% to 45 wt%, or 1 wt% to 40 wt%, or 1.5 wt% to 35 wt%, or 2 wt% to 30 wt%, or 2.5 wt% to 25 wt%, or 3 wt% to 20 wt%). The isotropic pitch composition of the present disclosure may comprise, based on the total weight of the isotropic pitch composition, 0.1 wt% to 100 wt% of ARC4 (0.1 wt% to 95 wt%, or 0.5 wt% to 90 wt%, or 1 wt% to 85 wt%, or 5 wt% to 80 wt%, or 10 wt% to 75 wt%, or 15 wt% to 70 wt%, or 20 wt% to 65 wt%, or 25 wt% to It may contain 60 wt%, or 30 wt% to 55 wt%, or 35 wt% to 50 wt%, or 40 wt% to 45 wt%, or 0.1 wt% to 50 wt%, or 0.5 wt% to 45 wt%, or 1 wt% to 40 wt%, or 1.5 wt% to 35 wt%, or 2 wt% to 30 wt%, or 2.5 wt% to 25 wt%, or 3 wt% to 20 wt%). The isotropic pitch composition of the present disclosure may comprise, based on the total weight of the isotropic pitch composition, 0.1 wt% to 100 wt% of ARC5 (0.1 wt% to 95 wt%, or 0.5 wt% to 90 wt%, or 1 wt% to 85 wt%, or 5 wt% to 80 wt%, or 10 wt% to 75 wt%, or 15 wt% to 70 wt%, or 20 wt% to 65 wt%, or 25 wt% to It may contain 60 wt%, or 30 wt% to 55 wt%, or 35 wt% to 50 wt%, or 40 wt% to 45 wt%, or 0.1 wt% to 50 wt%, or 0.5 wt% to 45 wt%, or 1 wt% to 40 wt%, or 1.5 wt% to 35 wt%, or 2 wt% to 30 wt%, or 2.5 wt% to 25 wt%, or 3 wt% to 20 wt%). The isotropic pitch composition of the present disclosure may comprise, based on the total weight of the isotropic pitch composition, 0.1 wt% to 100 wt% of ARC6 (0.1 wt% to 95 wt%, or 0.5 wt% to 90 wt%, or 1 wt% to 85 wt%, or 5 wt% to 80 wt%, or 10 wt% to 75 wt%, or 15 wt% to 70 wt%, or 20 wt% to 65 wt%, or 25 wt% to It may contain 60 wt%, or 30 wt% to 55 wt%, or 35 wt% to 50 wt%, or 40 wt% to 45 wt%, or 0.1 wt% to 50 wt%, or 0.5 wt% to 45 wt%, or 1 wt% to 40 wt%, or 1.5 wt% to 35 wt%, or 2 wt% to 30 wt%, or 2.5 wt% to 25 wt%, or 3 wt% to 20 wt%). The isotropic pitch composition of the present disclosure may comprise, based on the total weight of the isotropic pitch composition, 0.1 wt% to 100 wt% of ARC7 (0.1 wt% to 95 wt%, or 0.5 wt% to 90 wt%, or 1 wt% to 85 wt%, or 5 wt% to 80 wt%, or 10 wt% to 75 wt%, or 15 wt% to 70 wt%, or 20 wt% to 65 wt%, or 25 wt% to It may contain 60 wt%, or 30 wt% to 55 wt%, or 35 wt% to 50 wt%, or 40 wt% to 45 wt%, or 0.1 wt% to 50 wt%, or 0.5 wt% to 45 wt%, or 1 wt% to 40 wt%, or 1.5 wt% to 35 wt%, or 2 wt% to 30 wt%, or 2.5 wt% to 25 wt%, or 3 wt% to 20 wt%). The isotropic pitch composition of the present disclosure may comprise, based on the total weight of the isotropic pitch composition, 0.1 wt% to 100 wt% of ARC8 (0.1 wt% to 95 wt%, or 0.5 wt% to 90 wt%, or 1 wt% to 85 wt%, or 5 wt% to 80 wt%, or 10 wt% to 75 wt%, or 15 wt% to 70 wt%, or 20 wt% to 65 wt%, or 25 wt% to It may contain 60 wt%, or 30 wt% to 55 wt%, or 35 wt% to 50 wt%, or 40 wt% to 45 wt%, or 0.1 wt% to 50 wt%, or 0.5 wt% to 45 wt%, or 1 wt% to 40 wt%, or 1.5 wt% to 35 wt%, or 2 wt% to 30 wt%, or 2.5 wt% to 25 wt%, or 3 wt% to 20 wt%). The isotropic pitch composition of the present disclosure may comprise 0.1 wt% to 100 wt% of ARC9 (0.1 wt% to 95 wt%, or 0.5 wt% to 90 wt%, or 1 wt% to 85 wt%, or 5 wt% to 80 wt%, or 10 wt% to 75 wt%, or 15 wt% to 70 wt%, or 20 wt% to 65 wt%, or 25 wt% to It may contain 60 wt%, or 30 wt% to 55 wt%, or 35 wt% to 50 wt%, or 40 wt% to 45 wt%, or 0.1 wt% to 50 wt%, or 0.5 wt% to 45 wt%, or 1 wt% to 40 wt%, or 1.5 wt% to 35 wt%, or 2 wt% to 30 wt%, or 2.5 wt% to 25 wt%, or 3 wt% to 20 wt%). The isotropic pitch composition of the present disclosure may contain, based on the total weight of the isotropic pitch composition, 0.1 wt% to 100 wt% of ARC10+ (0.1 wt% to 95 wt%, or 0.5 wt% to 90 wt%, or 1 wt% to 85 wt%, or 5 wt% to 80 wt%, or 10 wt% to 75 wt%, or 15 wt% to 70 wt%, or 20 wt% to 65 wt%, or 25 wt% It may contain 0.1 wt% to 50 wt%, 0.5 wt% to 45 wt%, 1 wt% to 40 wt%, 1.5 wt% to 35 wt%, 2 wt% to 30 wt%, 2.5 wt% to 25 wt%, or 3 wt% to 20 wt%). The mesophase pitch composition may contain, based on the total weight of the isotropic pitch composition, 0.1 wt% to 100 wt% ARC1, 0.1 wt% to 100 wt% ARC2, 0.1 wt% to 80 wt% ARC3, 0.1 wt% to 50 wt% ARC4, 0.1 wt% to 50 wt% ARC5, 0.1 wt% to 25 wt% ARC6, 0.1 wt% to 25 wt% ARC7, 0 wt% to 10 wt% ARC8, 0 wt% to 10 wt% ARC9, and 0 wt% to 5 wt% ARC10+.

[0025] Herein, the heat treatment may be heat soaking and / or deasphalting. The heat treatment may be carried out at a pressure ranging from atmospheric to 1,000 psi (or, for example, from about 1 psi to about 500 psi, or from about 10 psi to about 450 psi, or from about 50 psi to about 400 psi, or from about 100 psi to about 350 psi, e.g., 300 psi). Deasphalting may be carried out at temperatures ranging from room temperature to 280°C, at pressures ranging from atmospheric to 700 psi, and / or for reaction times ranging from about 1 hour to 3 hours. Non-limiting examples of solvents used for deasphalting may be selected from the group consisting of toluene, heptane, or combinations of the two in various ratios.

[0026] The mesophase pitch compositions of the present disclosure may have a mesophase content ranging from about 40 vol.% to about 100 vol.% (or from about 45 vol.% to about 95 vol.%, or from about 50 vol.% to about 90 vol.%, or from about 55 vol.% to about 85 vol.%, or from about 60 vol.% to about 80 vol.%), based on the total volume of the mesophase pitch composition. The mesophase pitch composition has a softening point (T) of about 100°C or higher (or about 150°C or higher, or about 200°C or higher, or about 250°C or higher, or about 300°C or higher, or about 350°C or higher, or about 400°C or higher). sp The mesophase pitch composition may have a softening point (T) of from about 100°C to about 500°C, e.g., from about 150°C to about 475°C, e.g., from about 200°C to about 450°C. sp ) may be included. The mesophase pitch composition may have a microcarbon residue (MCR) of about 25 wt.% or greater (or from about 25 wt.% to about 95 wt.%, or from about 30 wt.% to about 90 wt.%, or from about 35 wt.% to about 85 wt.%, or from about 40 wt.% to about 80 wt.%), based on the total weight of the mesophase pitch composition. The mesophase pitch compositions of the present disclosure may be used to manufacture one or more fibers, oxidized fibers, carbonized fibers, graphite fibers, fiber webs, oxidized fiber webs, carbonized fiber webs, or graphite fiber webs.

[0027] end use The mesophase pitch compositions of the present disclosure may be used as precursors for the production of highly oriented carbon fibers with excellent mechanical properties, as well as carbon fiber products for improving the production of fibers, oxidized fibers, carbonized fibers, graphite fibers, fiber webs, oxidized fiber webs, carbonized fiber webs, or graphite fiber webs. In one example, the disclosed method comprises heat treating an isotropic pitch composition containing two or more aromatic classes, each aromatic class connected by at least one methylene bridge, at a temperature of about 300°C to about 500°C to produce a mesophase pitch composition suitable for spinning into carbon fiber, wherein the mesophase pitch composition has a weight average molecular weight (Mw) of about 300 g / mol to about 2,000 g / mol, a softening point (T) of about 100°C or greater, and a melting point (Mw) of about 100°C or greater. sp ), a mesophase content of about 0.01 vol% to 100 vol%, based on the total volume of the mesophase pitch composition, and a microcarbon residue (MCR) of about 25 wt% or greater, based on the total weight of the mesophase pitch composition; wherein the heat treatment induces cyclization between at least two of the two or more aromatic classes to form one or more five-membered and / or six-membered rings. Embodiments disclosed herein include the following.

[0028] A. Method for Producing a Mesophase Pitch Composition The method comprises heat treating an isotropic pitch composition containing two or more aromatic classes, each aromatic class being linked by at least one methylene bridge, at a temperature of about 300°C to about 500°C to produce a mesophase pitch having a weight average molecular weight (Mw) of about 300 g / mol to about 2,000 g / mol and a softening point (T) of about 100°C or higher. sp), producing a mesophase pitch composition having a mesophase content of about 0.01 vol% to 100 vol%, based on the total volume of the mesophase pitch composition, and a microcarbon residue (MCR) of about 25 wt% or greater, based on the total weight of the mesophase pitch composition; The heat treatment induces cyclization between at least two of the two or more aromatic classes to form one or more five- and / or six-membered rings. B. Mesophase Pitch Composition. The mesophase pitch composition has a weight average molecular weight (Mw) of about 300 g / mol to about 2,000 g / mol, a softening point (T) of about 100°C or higher, and sp ), having a mesophase content of about 0.01 vol% to 100 vol%, based on the total volume of the mesophase pitch composition, and a microcarbon residue (MCR) of about 25 wt% or greater, based on the total weight of the mesophase pitch composition; The mesophase pitch composition is produced from an isotropic pitch composition having two or more aromatic classes linked by at least one methylene bridge between each aromatic class; The isotropic pitch composition has a weight average molecular weight (Mw) of about 300 g / mol to about 2,000 g / mol and a softening point (T) of 50°C or higher. sp ), and a microcarbon residue (MCR) of about 15 wt. % or greater, based on the total weight of the isotropic pitch composition.

[0029] Embodiments A and B may have one or more of the following elements in any combination. Element 1: Each of the two or more aromatic classes is an unsubstituted aromatic and / or substituted aromatic selected from the group consisting of one-membered aromatic ring (ARC1), two-membered aromatic ring (ARC2), three-membered aromatic ring (ARC3), four-membered aromatic ring (ARC4), five-membered aromatic ring (ARC5), six-membered aromatic ring (ARC6), seven-membered aromatic ring (ARC7), eight-membered aromatic ring (ARC8), nine-membered aromatic ring (ARC9), ten-membered or greater aromatic ring (ARC10+), and any combination thereof. Element 2: Substituted aromatics are C1 to C 20 Hydrocarbyl monosubstituted aromatics, C1-C 20Hydrocarbyl disubstituted aromatics, C1-C 20 Hydrocarbyl trisubstituted aromatics, and any of these combinations thereof. Element 3: Cyclization between at least two of two or more aromatic classes to form one or more six-membered rings, followed by dehydrogenative aromatization to produce a highly aromatic mesophase pitch composition. Element 4: The isotropic pitch composition is produced by: mixing an aromatic feedstock containing one or more aromatic classes with acetic acid and sulfuric acid to form a first mixture; heating the first mixture at a temperature of about 40°C to about 400°C; adding formaldehyde and / or paraformaldehyde to the first mixture at a temperature of about 40°C to about 400°C to produce a second mixture containing a reaction product composition; filtering the second mixture; and Isolating the isotropic pitch composition. Element 5: The isotropic pitch composition has a weight average molecular weight (Mw) of about 300 g / mol to about 2,000 g / mol, a softening point (T) of 50°C or higher, sp ), and a microcarbon residue (MCR) of about 15 wt. % or greater, based on the total weight of the isotropic pitch composition. Element 6: Each of the two or more aromatic classes has a partially hydrogenated aromatic ring. Element 7: Each of two or more aromatic classes includes benzene, toluene, xylene (e.g., ortho-, meta-, para-xylene), naphthalene, 1-methylnaphthalene, 2-methylnaphthalene, anthracene, phenanthrene, pyrene, benzopyrene, picenecoronene, chrysene, tetracene, pentacene, triphenylene, corannulene, benzo[j]fluoranthene, benzo[c]fluorene, perylene, benzo-perylene, ovalene, AROMATIC-200 TM and any combination thereof. Element 8: The molar ratio of aromatic feedstock to formaldehyde equivalents is from about 10:1 to about 1:10. Element 9: The molar ratio of aromatic feedstock to formaldehyde equivalents is 1:3. Element 10: The molar ratio of aromatic feedstock to sulfuric acid is from about 1:0.001 to about 1:20. Element 11: The molar ratio of aromatic feedstock to sulfuric acid is 1:2. Element 12: The isotropic pitch composition contains, based on the total weight of the isotropic pitch composition, 0.1 wt% to 100 wt% of ARC1, 0.1 wt% to 100 wt% of ARC2, 0.1 wt% to 100 wt% of ARC3, 0.1 wt% to 100 wt% of ARC4, 0.1 wt% to 100 wt% of ARC5, 0.1 wt% to 100 wt% of ARC6, 0.1 wt% to 100 wt% of ARC7, 0.1 wt% to 100 wt% of ARC8, 0.1 wt% to 100 wt% of ARC9, and 0.1 wt% to 100 wt% of ARC10+. Element 13: The isotropic pitch composition contains, based on the total weight of the isotropic pitch composition, 0.1 wt% to 100 wt% of ARC1, 0.1 wt% to 100 wt% of ARC2, 0.1 wt% to 80 wt% of ARC3, 0.1 wt% to 50 wt% of ARC4, 0.1 wt% to 50 wt% of ARC5, 0.1 wt% to 25 wt% of ARC6, 0.1 wt% to 25 wt% of ARC7, 0 wt% to 10 wt% of ARC8, 0 wt% to 10 wt% of ARC9, and 0 wt% to 5 wt% of ARC10+. Element 14: The heat treatment is heat soaking and / or deasphalting. Element 15: Deasphalting is carried out at temperatures ranging from room temperature to 280°C, pressures ranging from atmospheric to 700 psi, and / or reaction times ranging from about 1 hour to 3 hours. Element 16: The solvent used for deasphalting is selected from the group consisting of toluene, heptane, or a combination of the two in various ratios. Element 17: The heat treatment is carried out at pressures ranging from atmospheric to 1,000 psi. Element 18: The mesophase pitch composition has a mesophase content ranging from about 40 vol% to about 100%, based on the total volume of the mesophase pitch composition. Element 19: A fiber, oxidized fiber, carbonized fiber, graphite fiber, fiber web, oxidized fiber web, carbonized fiber web, or graphite fiber web prepared using the mesophase pitch composition of any of the preceding elements.

[0030] By way of non-limiting example, exemplary combinations that may be applied to A include, but are not limited to, the following: 1 or 2 and 3; 1 or 2 and 4; 1 or 2 and 5; 1 or 2 and 6; 1 or 2 and 7; 1 or 2 and 8; 1 or 2 and 9; 1 or 2 and 10; 1 or 2 and 11; 1 or 2 and 12; 1 or 2 and 13; 1 or 2 and 14; 1 or 2 and 15; 1 or 2 and 16; 1 or 2 and 17; 1 or 2 and 18; 1 or 2 and 19; 1 or 2 and 6 and 7; 1 or 2 and 13 and 14; 15 and 16. By way of non-limiting example, exemplary combinations that may be applied to B include, but are not limited to, the following: 1 or 2 and 3; 1 or 2 and 4; 1 or 2 and 5; 1 or 2 and 6; 1 or 2 and 7; 1 or 2 and 8; 1 or 2 and 9; 1 or 2 and 10; 1 or 2 and 11; 1 or 2 and 12; 1 or 2 and 13; 1 or 2 and 14; 1 or 2 and 15; 1 or 2 and 16; 1 or 2 and 17; 1 or 2 and 18; 1 or 2 and 19; 1 or 2 and 6 and 7; 1 or 2 and 13 and 14; 15 and 16; 1 or 2 and 18 and 19. To facilitate a better understanding of the embodiments of the present disclosure, the following preferred or representative examples are provided, which should not be construed in any way as limiting or defining the scope of the invention. [Example]

[0031] AROMATIC-200 TM All solvents and reagents, except for the fluids, were purchased from Sigma-Aldrich or Fisher Scientific and used as received without further purification. Unless otherwise stated, all reactions were carried out under a standard N2 atmosphere. TM Fluid ("Naphthalene-free" grade) is AR-200 TM (e.g., SOLVESSOTM 200 Fluid), was obtained from ExxonMobil Chemical Company and used as received.

[0032] General procedure for the synthesis of isotropic pitch compositions: To a three-neck round-bottom flask was added aromatic molecules (1 molar equivalent), 18 M sulfuric acid (2 molar equivalents), and acetic acid (adjusted to a total volume of 200 mL). A dropping funnel containing formaldehyde solution (3 molar equivalents, 35 wt% aqueous solution, or paraformaldehyde pre-dissolved in dilute NaOH) was attached to the three-neck round-bottom flask. With rapid stirring (either a large stir bar or mechanical stirrer, depending on the reaction scale), the mixture was heated to 100°C. Once the temperature reached 60°C, the formaldehyde solution was added dropwise very slowly over a period of 2.5–3 h, while the reaction mixture continued to heat and maintain the temperature between 90–100°C. After the dropwise addition was complete, the mixture was heated at 100°C for an additional 1–3 h, after which the temperature was allowed to cool to room temperature. Water was added, the slurry mixture was filtered, and the solid was washed thoroughly with dilute ammonia or sodium hydroxide and finally with water to give either a gel-like or powdery residue (depending on the reaction conditions and aromatic starting material used).

[0033] Table 1 shows the reaction conditions and physical properties of the isotropic pitch compositions. In Example 1, paraformaldehyde was used and a ratio of naphthalene to sulfuric acid to formaldehyde of 1:10:3 was used. In Example 2, a 35% formaldehyde solution was used and a ratio of naphthalene to sulfuric acid to formaldehyde of 1:2:3 was used. In Example 3, a formaldehyde solution prepared from paraformaldehyde in a dilute solution of NaOH was used and a ratio of naphthalene to sulfuric acid to formaldehyde of 1:2:3 was used.

[0034] [Table 1]

[0035] Figure 1 shows a laser desorption / ionization mass spectrometry (LDI-MS) of an isotropic pitch composition (Example 2) showing the presence of five oligomers, including dimer, trimer, tetramer, pentamer, and hexamer. Mass spectrometry analysis of an isotropic pitch composition (Example 2) formed from naphthalene showed a distribution of oligomers ranging from dimer to hexamer (MW 200 g / mol-900 g / mol), with the major component being in the trimer to pentamer range (MW 400 g / mol-700 g / mol).

[0036] The synthesized isotropic pitch compositions (Examples 1-8) were subjected to mild heat treatment to form the corresponding mesophase pitch compositions. The heat treatment was carried out at a temperature sufficient to induce dehydrogenative cyclization between the oligomers in the isotropic pitch composition, but not too high to prevent thermal decomposition. The reaction conditions and physical properties of the pitch compositions are shown in Table 2. Each methylene bridge between aromatic molecules served as a cyclization means. Heat treatment (e.g., heat soaking) was carried out at temperatures ranging from 300°C to 420°C, which is significantly lower than conventional thermal conversion processes for pitch production (i.e., typically ranging from 420°C to 550°C). Table 2 shows the results of mesophase pitch compositions (Examples 9-11) obtained by heat treating an isotropic pitch composition containing naphthalene-based oligomers (Example 2) at temperatures ranging from 300°C to 350°C. The MCR values of the mesophase pitch compositions (Examples 9-11) were higher than the MCR value of the isotropic pitch composition (Example 2). The T of the mesophase pitch compositions (Examples 9-11) sp The value is the T of the isotropic pitch composition (Example 2) sp value, and as the heat treatment temperature increases, the T of the mesophase pitch composition sp Note the decrease in . Examples 9-11 did not contain any mesophase. The results from Examples 9-11 highlight the minimum temperature requirement for mesophase formation.

[0037] [Table 2] Table 2 (continued). TIFF0007724306000003.tif34153

[0038] Figure 2 shows the laser desorption / ionization mass spectrometry (LDI-MS) of Example 2 and its corresponding mesotropic pitch compositions (Examples 9-11) after the heat soak treatment. Significantly condensed molecules were observed in Examples 9 and 10. Figure 3 is a graph depicting the distribution of oligomers contained in mesophase pitch compositions (Examples 9-11). Figure 3 shows that tetramer was the major product after heat soaking in Example 2. Mass spectrometry analysis revealed that the heat-treated isotropic pitch compositions underwent dehydrogenative cyclization reactions, resulting in new molecules with very little change in carbon number and mild to severe hydrogen deficiency. Figures 4A and 4B depict mass spectrometry analyses of the isotropic pitch composition (Example 2) and its corresponding mesotropic pitch compositions (Examples 9-11) after heat soak treatment. Broadband spectra revealed the extent of condensation with increasing heat treatment temperature. Condensed molecules were observed with increasing heat (see Figure 4B). For species with the same carbon number, a loss of up to eight hydrogen atoms was observed in the treated samples, indicating not only cyclization but also evidence of extensive aromatization. The resulting species are believed to be highly conjugated aromatic species, ideal molecules for high-quality pitch. FIG. 5 is a mass spectrum depicting the C32 identification of the mesotropic pitch composition (Example 10) after heat soak treatment. FIG. 6 shows mass spectra of an isotropic pitch composition (Example 2) and its corresponding mesotropic pitch composition (Example 10) after heat soak treatment, illustrating the reaction mechanism for mesophase formation and carbon number redistribution.

[0039] Table 3 shows the AROMATIC-200 TM The conditions and results obtained after heat treatment of the base isotropic pitch composition (mesophase pitch composition, Examples 12-13) are shown. Heat treatment was carried out in an autoclave at 420°C and 300 psi for 3 hours according to the following: AROMATIC-200TM was first introduced into a scintillation vial, which was then inserted, open, into an autoclave preloaded with silica sand. The overall setup simulated an "open" thermal treatment under pressure, where gaseous substances were released from the vial during the reaction but were not necessarily collected in the vial at the end of the reaction. FIG. 7 is a polarized light microscope of Example 12 depicting large mesophase domains, thus demonstrating that the resulting solid residue (20% isolated recovery) exhibits large mesophase domains (i.e., the white domains shown in FIG. 7). FIG. 8 is a laser desorption ionization mass spectrometry (LDI-MS) of Example 12, a mesophase pitch composition.

[0040] [Table 3] Table 3 (continued). TIFF0007724306000005.tif28153

[0041] Table 4 shows the conditions and results obtained after heat treatment of a 1-methylnaphthalene-formaldehyde-based isotropic pitch composition. Example 14 was carried out in a reactor (conventional autoclave) at 300 psi, where light molecules were condensed back into the product residue after the reaction. The recovered residue had a low melting point of approximately 50°C and was free of mesophase. The recovered residue was further deasphalted using a heptane / toluene mixed solvent (70:30, v / v) at a solvent-to-sample ratio of 10, which resulted in the formation of mesophase (60% mesophase). Figure 9 is a polarized light microscope image of Example 15 depicting large mesophase domains (i.e., the white domains shown in Figure 9).

[0042] [Table 4] Table 4 (continued) TIFF0007724306000007.tif28153

[0043] All documents described herein are incorporated by reference herein for purposes of all jurisdictions where such practice is permitted, including any priority documents and / or testing procedures to the extent consistent with this text. While a form of the disclosure has been illustrated and disclosed, various modifications can be made without departing from the spirit and scope of the disclosure, as is apparent from the foregoing general description and specific embodiments. Accordingly, the disclosure is not intended to be limited thereby. For example, the compositions described herein may not have any component or composition not specifically listed or disclosed herein. Any method may lack any step not listed or disclosed herein. Similarly, the term "comprising" is considered synonymous with the term "comprise." Whenever a method, composition, element, or group of elements is preceded by the transitional phrase "comprising," it is understood that the same composition or group of components is also contemplated, as are the transitional phrases "consisting essentially of," "consisting of," "selected from the group consisting of," or "is," preceding a composition, single element, or multiple element listing, and vice versa. One or more illustrative embodiments incorporating one or more elements of the invention are presented herein. For clarity, not all features of a natural implementation are described or shown in this application. It is understood that in developing a natural implementation incorporating one or more elements of the invention, numerous objective-specific decisions must be made to achieve the developer's goals, including compliance with system-related, business-related, government-related, and other constraints that vary from implementation to implementation and from time to time. While the developer's efforts may require significant time, such efforts would nevertheless be routine for one of ordinary skill in the art and would have the benefit of this disclosure. Unless otherwise expressly indicated, all numbers expressing quantities of factors, properties, such as molecular weight, reaction conditions, and the like, and otherwise used in this specification and the pertinent claims should be understood as being modified in all instances by the term "about." Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and appended claims are approximations that may vary depending upon the desired properties to be obtained by embodiments of the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of significant reported digits and by applying ordinary rounding techniques. Whenever a numerical range with a lower and upper limit is disclosed, any number and any included range falling within that range is specifically disclosed and includes the lower and upper limits. In particular, each value range disclosed herein (in the form of "from about a to about b," or equivalently, "from approximately a to b," or equivalently, "approximately a b") is understood to specify each number and range encompassed within the broader value range. Furthermore, the terms in the claims are to be given their plain and ordinary meaning unless expressly and unambiguously defined by the patentee. Moreover, the open-ended articles "a" or "an," as used in the claims, are defined herein to mean one or more of the elements they refer to.

[0044] Thus, the present disclosure is well adapted to achieve the objects and advantages mentioned and its inherent purposes. The particular embodiments disclosed above are illustrative only, as the disclosure may be modified and practiced in equivalent manners that are different but apparent to those of ordinary skill in the art and having the benefit of the teachings herein. Furthermore, no limitations are intended to the details of construction or design herein shown, other than as described in the claims that follow. It is therefore evident that the specific exemplary embodiments disclosed above may be changed, combined, or modified, and all such variations are considered within the scope and spirit of the present disclosure. The embodiments illustratively disclosed herein may suitably be practiced in the absence of any element not specifically disclosed herein and / or any optional element disclosed herein. Another aspect of the present invention may be as follows. [1] An isotropic pitch composition containing two or more aromatic classes, each aromatic class being linked by at least one methylene bridge, is heat-treated at a temperature of about 300°C to about 500°C to produce a pitch having a weight average molecular weight (Mw) of about 300 g / mol to about 2,000 g / mol and a softening point (T) of about 100°C or higher. sp ), to produce a mesophase pitch composition having a mesophase content of about 0.01 vol.% to 100 vol.%, based on the total volume of the mesophase pitch composition, and a microcarbon residue (MCR) of about 25 wt.% or greater, based on the total weight of the mesophase pitch composition; A method wherein the heat treatment induces cyclization between at least two of the two or more aromatic classes to form one or more five- and / or six-membered rings. [2] The method according to [1], wherein each of the two or more aromatic classes is an unsubstituted aromatic and / or substituted aromatic selected from the group consisting of one-membered aromatic ring (ARC1), two-membered aromatic ring (ARC2), three-membered aromatic ring (ARC3), four-membered aromatic ring (ARC4), five-membered aromatic ring (ARC5), six-membered aromatic ring (ARC6), seven-membered aromatic ring (ARC7), eight-membered aromatic ring (ARC8), nine-membered aromatic ring (ARC9), ten-membered or more-membered aromatic ring (ARC10+), and any combination thereof. [3] The substituted aromatic is C 1 ~C 20 Hydrocarbyl monosubstituted aromatic, C 1 ~C 20 Hydrocarbyl disubstituted aromatic, C 1 ~C 20 The method according to [2] above, wherein the aromatic hydrocarbon group is selected from the group consisting of: a hydrocarbyl tri-substituted aromatic hydrocarbon group; a hydrocarbyl tri-substituted aromatic hydrocarbon group; and any combination thereof. [4] The method according to [1], wherein at least two of the two or more aromatic classes are cyclized to form one or more six-membered rings, followed by dehydrogenative aromatization to produce a highly aromatic mesophase pitch composition. [5] The method according to [1], wherein an isotropic pitch composition is produced by: mixing an aromatic feedstock containing one or more aromatic classes with acetic acid and sulfuric acid to form a first mixture; heating the first mixture at a temperature of about 40°C to about 400°C; adding formaldehyde and / or paraformaldehyde to the first mixture at a temperature of about 40°C to about 400°C to produce a second mixture containing the reaction product composition. ; filtering the second mixture; and Isolating the isotropic pitch composition. [6] The isotropic pitch composition has a weight average molecular weight (Mw) of about 300 g / mol to about 2,000 g / mol, a softening point (T) of 50°C or higher, sp ), and a micro carbon residue (MCR) of about 15 wt% or more based on the total weight of the isotropic pitch composition. [7] The method according to [1], wherein each of the two or more aromatic classes has a partially hydrogenated aromatic ring. [8] Each of two or more aromatic classes is selected from the group consisting of benzene, toluene, xylene (e.g., ortho-, meta-, and para-xylene), naphthalene, 1-methylnaphthalene, 2-methylnaphthalene, anthracene, phenanthrene, pyrene, benzopyrene, picenecoronene, chrysene, tetracene, pentacene, triphenylene, corannulene, benzo[j]fluoranthene, benzo[c]fluorene, perylene, benzo-perylene, ovalene, and AROMATIC-200. TM and any combination thereof. [9] The method according to [5] above, wherein the molar ratio of aromatic feedstock to formaldehyde equivalents is from about 10:1 to about 1:10.

[10] The method according to [5] above, wherein the molar ratio of aromatic raw material to formaldehyde equivalent is 1:3.

[11] The method according to [5], wherein the molar ratio of aromatic feedstock to sulfuric acid is from about 1:0.001 to about 1:20.

[12] The method according to [5] above, wherein the molar ratio of aromatic raw material to sulfuric acid is 1:2.

[13] The method according to [1], wherein the isotropic pitch composition contains, based on the total weight of the isotropic pitch composition, 0.1 wt% to 100 wt% of ARC1, 0.1 wt% to 100 wt% of ARC2, 0.1 wt% to 100 wt% of ARC3, 0.1 wt% to 100 wt% of ARC4, 0.1 wt% to 100 wt% of ARC5, 0.1 wt% to 100 wt% of ARC6, 0.1 wt% to 100 wt% of ARC7, 0.1 wt% to 100 wt% of ARC8, 0.1 wt% to 100 wt% of ARC9, and 0.1 wt% to 100 wt% of ARC10+.

[14] The method according to [1], wherein the isotropic pitch composition contains, based on the total weight of the isotropic pitch composition, 0.1 wt% to 100 wt% of ARC1, 0.1 wt% to 100 wt% of ARC2, 0.1 wt% to 80 wt% of ARC3, 0.1 wt% to 50 wt% of ARC4, 0.1 wt% to 50 wt% of ARC5, 0.1 wt% to 25 wt% of ARC6, 0.1 wt% to 25 wt% of ARC7, 0 wt% to 10 wt% of ARC8, 0 wt% to 10 wt% of ARC9, and 0 wt% to 5 wt% of ARC10+.

[15] The method according to [1] above, wherein the heat treatment is heat soaking and / or deasphalting.

[16] The method according to

[15] , wherein the deasphalting is carried out at a temperature ranging from room temperature to 280°C, at a pressure ranging from atmospheric pressure to 700 psi, and / or for a reaction time ranging from about 1 hour to 3 hours.

[17] The method according to

[15] or

[16] , wherein the solvent used for deasphalting is selected from the group consisting of toluene, heptane, or a combination of these two in various ratios.

[18] The method according to [1], wherein the heat treatment is carried out at a pressure ranging from atmospheric pressure to 1,000 psi.

[19] The method according to any one of

[12] to

[18] , wherein the mesophase pitch composition has a mesophase content ranging from about 40 vol% to about 100% based on the total volume of the mesophase pitch composition.

[20] A fiber, oxidized fiber, carbonized fiber, graphite fiber, fiber web, oxidized fiber web, carbonized fiber web, or graphite fiber web prepared using the mesophase pitch composition according to any one of [1] to

[19] above.

[21] Weight average molecular weight (Mw) of approximately 300g / mol to approximately 2,000g / mol, softening point (T sp ), a mesophase content of about 0.01 vol% to 100 vol%, based on the total volume of the mesophase pitch composition, and a microcarbon residue (MCR) of about 25 wt% or greater, based on the total weight of the mesophase pitch composition; The mesophase pitch composition is produced from an isotropic pitch composition having two or more aromatic classes linked by at least one methylene bridge between each aromatic class; The isotropic pitch composition has a weight average molecular weight (Mw) of about 300 g / mol to about 2,000 g / mol and a softening point (T) of 50°C or higher. sp ), and a microcarbon residue (MCR) of about 15 wt. % or greater, based on the total weight of the isotropic pitch composition.

[22] The mesophase pitch composition according to

[21] , wherein each of the two or more aromatic classes is an unsubstituted aromatic and / or substituted aromatic selected from the group consisting of one-membered aromatic ring (ARC1), two-membered aromatic ring (ARC2), three-membered aromatic ring (ARC3), four-membered aromatic ring (ARC4), five-membered aromatic ring (ARC5), six-membered aromatic ring (ARC6), seven-membered aromatic ring (ARC7), eight-membered aromatic ring (ARC8), nine-membered aromatic ring (ARC9), ten-membered or higher-membered aromatic ring (ARC10+), and any combination thereof.

[23] The mesophase pitch composition according to

[21] , wherein the isotropic pitch composition contains, based on the total weight of the isotropic pitch composition, 0.1 wt% to 100 wt% of ARC1, 0.1 wt% to 100 wt% of ARC2, 0.1 wt% to 80 wt% of ARC3, 0.1 wt% to 50 wt% of ARC4, 0.1 wt% to 50 wt% of ARC5, 0.1 wt% to 25 wt% of ARC6, 0.1 wt% to 25 wt% of ARC7, 0 wt% to 10 wt% of ARC8, 0 wt% to 10 wt% of ARC9, and 0 wt% to 5 wt% of ARC10+.

Claims

1. An isotropic pitch composition containing two or more aromatic groups, each aromatic group being connected by at least one methylene bridge, is heat treated at a temperature of 300°C to 500°C to produce a pitch having a weight average molecular weight (Mw) of 300 g / mol to 2,000 g / mol and a softening point (T) of 100°C or higher. sp ), producing a mesophase pitch composition having a mesophase content of 0.01 vol.% to 100 vol.%, based on the total volume of the mesophase pitch composition, and a microcarbon residue (MCR) of 25 wt.% or greater, based on the total weight of the mesophase pitch composition; heat treatment induces cyclization between at least two of the two or more aromatic groups to form one or more five- and / or six-membered rings; combining an aromatic feedstock containing one or more aromatic groups with acetic acid and sulfuric acid to form a first mixture; heating the first mixture at a temperature of from 40°C to 400°C; adding formaldehyde and / or paraformaldehyde to the first mixture at a temperature of 40°C to 400°C to produce a second mixture containing the reaction product composition; filtering the second mixture; and A method for producing an isotropic pitch composition by isolating an isotropic pitch composition.

2. Each of the two or more aromatic groups is an unsubstituted aromatic and / or substituted aromatic selected from the group consisting of a 5-membered aromatic ring (ARC5), a 6-membered aromatic ring (ARC6), a 7-membered aromatic ring (ARC7), and any combination thereof, and the substituted aromatic is selected from the group consisting of C 1 ~C 20 Hydrocarbyl monosubstituted aromatic, C 1 ~C 20 Hydrocarbyl disubstituted aromatics, C 1 ~C 20 10. The method of claim 1, wherein the two or more aromatic groups are selected from the group consisting of hydrocarbyl tri-substituted aromatics, and any combination thereof, and cyclization is performed between at least two of the two or more aromatic groups to form one or more six-membered rings, followed by dehydrogenative aromatization to produce a highly aromatic mesophase pitch composition.

3. A method for producing a process for the production of ... a molar ratio of aromatic feedstock to sulfuric acid of from 1:0.001 to 1:20, or a molar ratio of aromatic feedstock to sulfuric acid of 1:2; 10. The method of claim 1, wherein the mesophase pitch composition has a mesophase content ranging from 40 vol.% to 100 vol.%, based on the total volume of the mesophase pitch composition.

4. The isotropic pitch composition has a weight average molecular weight (Mw) of 300 g / mol to 2,000 g / mol and a softening point (T sp ), and a microcarbon residue (MCR) of 15 wt. % or greater, based on the total weight of the isotropic pitch composition, and wherein each of the two or more aromatic groups has a partially hydrogenated aromatic ring.

5. 2. The method of claim 1, wherein each of the two or more aromatic groups is selected from the group consisting of benzene, toluene, xylene (e.g., ortho-, meta-, para-xylene), naphthalene, 1-methylnaphthalene, 2-methylnaphthalene, anthracene, phenanthrene, pyrene, benzopyrene, picene, coronene, chrysene, tetracene, pentacene, triphenylene, corannulene, benzo[j]fluoranthene, benzo[c]fluorene, perylene, benzo-perylene, ovalene, and any combination thereof.

6. 2. The method of claim 1, wherein the isotropic pitch composition contains 0.1 wt % to 100 wt % ARC5, 0.1 wt % to 100 wt % ARC6, or 0.1 wt % to 100 wt % ARC7, based on the total weight of the isotropic pitch composition; or 0.1 wt % to 50 wt % ARC5, 0.1 wt % to 25 wt % ARC6, or 0.1 wt % to 25 wt % ARC7, based on the total weight of the isotropic pitch composition.

7. 2. The method of claim 1, wherein the heat treatment is heat soaking and / or deasphalting, and the deasphalting is carried out at a temperature ranging from room temperature to 280°C, at a pressure ranging from atmospheric pressure to 700 psi, and / or for a reaction time ranging from 1 hour to 3 hours, and the solvent used for deasphalting is selected from the group consisting of toluene, heptane, or a combination of the two in various ratios, and the heat treatment is carried out at a pressure ranging from atmospheric pressure to 1,000 psi.

8. A fiber prepared using the mesophase pitch composition of any one of claims 1 to 7.

9. Weight average molecular weight (Mw) of 300g / mol to 2,000g / mol, softening point (T sp ), a mesophase pitch composition having a mesophase content of 0.01 vol.% to 100 vol.%, based on the total volume of the mesophase pitch composition, and a microcarbon residue (MCR) of 25 wt.% or greater, based on the total weight of the mesophase pitch composition; The mesophase pitch composition is produced from an isotropic pitch composition having two or more aromatic groups connected by at least one methylene bridge between each aromatic group; The isotropic pitch composition has a weight average molecular weight (Mw) of 300 g / mol to 2,000 g / mol and a softening point (T) of 50°C or higher. sp ), and a micro carbon residue (MCR) of 15 wt. % or more based on the total weight of the isotropic pitch composition; combining an aromatic feedstock containing one or more aromatic groups with acetic acid and sulfuric acid to form a first mixture; heating the first mixture at a temperature of from 40°C to 400°C; adding formaldehyde and / or paraformaldehyde to the first mixture at a temperature of 40°C to 400°C to produce a second mixture containing the reaction product composition; filtering the second mixture; and A mesophase pitch composition, wherein the isotropic pitch composition is produced by isolating the isotropic pitch composition.

10. 10. The mesophase pitch composition of claim 9, wherein each of the two or more aromatic groups is an unsubstituted aromatic and / or substituted aromatic selected from the group consisting of a five-membered aromatic ring (ARC5), a six-membered aromatic ring (ARC6), a seven-membered aromatic ring (ARC7), and any combination thereof, and the isotropic pitch composition contains 0.1 wt. % to 50 wt. % ARC5, 0.1 wt. % to 25 wt. % ARC6, or 0.1 wt. % to 25 wt. % ARC7, based on the total weight of the isotropic pitch composition.

Images