Biohydroxybenzoic acid for use in the formation of bioliquid crystal polymers

Abstract

A technology for forming bio-based hydroxybenzoic acid monomers (e.g., "bioHBA") derived from bionaphtha, and a bio-liquid crystal polymer ("bioLCP") formed from the monomer are provided.

Description

[Technical Field]

[0001] Related applications

[0001] This application claims priority to U.S. Provisional Patent Application No. 63 / 495,157, filed on 10 April 2023, which is incorporated herein by reference. [Background technology]

[0002]

[0002] Liquid crystal polymers are commonly used in a wide variety of high-performance applications, such as high-voltage connectors, medical products, and camera modules. Such polymers are typically produced by reacting one or more aromatic hydroxycarboxylic acids (e.g., 4-hydroxybenzoic acid ("HBA") or 2-hydroxy-6-naphthoic acid ("HNA")) and / or one or more dicarboxylic acids (e.g., terephthalic acid ("TA"), isophthalic acid ("IA"), and 2,6-naphthylenedicarboxylic acid ("NDA")) with one or more aromatic diols (e.g., hydroquinone ("HQ"), 4,4'-biphenol ("BP"), etc.) to form ester repeating units. HBA accounts for the majority of aromatic carboxylic acids used in most commercial liquid crystal polymers. Traditionally, hydroxybenzoic acid (HBA) has been produced from crude oil through catalytic cracking processes. However, in recent years, there has been a growing need for a more carbon-neutral approach. To become carbon neutral, companies must remove the same amount of carbon dioxide they emit into the atmosphere, achieving net-zero carbon emissions. Carbon-negative companies, on the other hand, remove more carbon from the atmosphere than they emit. In light of the remarkable efforts of companies worldwide to become carbon neutral or carbon-negative, there is a need for methods to produce hydroxybenzoic acid and liquid crystal polymers in a more sustainable way without significantly altering the properties of such polymers. [Overview of the Initiative]

[0003]

[0003] According to one embodiment of the present invention, a method for forming a biohydroxybenzoic acid monomer for use in liquid crystal polymers is disclosed. The method includes the steps of providing a biophenol derived from bionaphtha, treating the biophenol with an alkali metal hydroxide to form an alkali metal phenolate, and heating the alkali metal phenolate in the presence of carbon dioxide to form a biohydroxybenzoic acid monomer.

[0004]

[0004] According to another embodiment of the present invention, a bioliquid crystal polymer is disclosed comprising repeating units derived from one or more aromatic hydroxycarboxylic acids, optional repeating units derived from one or more dicarboxylic acids, and optional repeating units derived from one or more aromatic diols. The one or more aromatic hydroxycarboxylic acids include bio-4-hydroxybenzoic acid derived from bionaphtha.

[0005]

[0005] Other features and aspects of the present invention are described in more detail below. [Modes for carrying out the invention]

[0006]

[0006] It will be understood by those skilled in the art that this discussion is merely a description of exemplary embodiments and is not intended to limit broader aspects of the present invention.

[0007] Generally, this disclosure relates to technologies for forming bio-based hydroxybenzoic acid monomers derived from bio-naphtha, and bio-liquid crystal polymers ("Bio-LCPs") formed from these monomers. Ultimately, Bio-LCPs and compositions formed from such polymers may be certified under the ISCC+ standards defined by the International Sustainability Carbon Certification ("ISCC") scheme. ISCC is a globally applicable sustainability certification scheme that encompasses all sustainable raw materials, including agricultural and forest biomass, circular and bio-based materials, and renewable materials. ISCC follows a mass balance approach that allows for verification of the renewable material content of polymers. In mass balance, renewable raw materials are attributed to selected products according to individual formulations that take into account all yields and losses. In mass balance, only raw materials used as raw materials in production (but not for energy) are considered. Key criteria used in applying the mass balance approach include raw material qualification, control chain, and product claims. The mass balance approach makes it possible to track the quantity and sustainability characteristics of reused and / or bio-based raw materials throughout the value chain and attribute them to the final product in a verifiable manner. In one embodiment, the liquid crystal polymer described herein may be prepared from carbon-negative or carbon-neutral components under a mass balance approach.

[0007]

[0008] Next, various embodiments of the present invention will be described in more detail. I. Biohydroxybenzoic acid

[0009] As stated above, the biohydroxybenzoic acid of this disclosure is derived from "bio-naphtha." The term "bio-naphtha" generally refers to naphtha produced from renewable sources. Bio-naphtha is a hydrocarbon composition primarily containing paraffins that can be converted into bio-aromatic compounds (e.g., biobenzene). The hydrocarbon content typically has 8 to 24 carbon atoms, and in some cases 10 to 18 carbon atoms. To form bio-naphtha, bio-distillate raw materials are typically provided, including complex mixtures of naturally occurring fats and / or oils, such as plant-based fats and oils (e.g., cotton, coconut, corn, palm, peanut, flaxseed, rice, rapeseed, olive, soybean, sunflower, linola, tallow, tall, castor, etc.) and animal-based fats and oils (e.g., butter or milk fat). Raw materials may be provided in an unused (virgin) state and / or may be obtained from waste such as cooking oils, non-edible highly saturated oils, waste cooking oils, by-products of vegetable oil refining, and mixtures thereof. Natural fats and oils mainly contain triglycerides and to some extent free fatty acids (FFAs). Many different types of triglycerides are produced naturally and are of either plant or animal origin. Fatty acids in fats and oils are found esterified to glycerol (triacylglycerol). Acyl groups are long chains with carboxyl groups at the end (C 12 ~C 22) are hydrocarbons, and the carboxyl group is generally esterified with glycerol. Fats and oils are characterized by the chemical composition and structure of their fatty acid portion. The fatty acid portion may be saturated or may contain one or more double bonds. The aforementioned sources of fats and / or oils may contain fatty acids, such as saturated fatty acids (e.g., caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, etc.) and / or unsaturated fatty acids (e.g., myristoleic acid, palmitoleic acid, heptadecenoic acid, oleic acid, linoleic acid, linolenic acid, gadelic acid, ricinoleic acid (riconoleic), rosinic acid, etc.). Tall oils include, for example, myristic acid, stearic acid, arachidic acid, oleic acid, linoleic acid, and gadelic acid.

[0008]

[0010] Biodistillate raw materials may be classified as follows based on their free fatty acid (FFA) content: refined oils such as soy or refined canola oil (FFA < 1.5%); low free fatty acid yellow grease and animal fats (FFA < 4%); and high free fatty acid grease and animal fats (FFA > 20%). In certain cases, it may be desirable to subject the raw materials to refining processes (e.g., physical refining, chemical refining, etc.) to remove most of the non-triglyceride and non-fatty acid components. For example, in physical refining, steam stripping can remove FFAs, unsaponifiable matter, and other impurities, thereby eliminating soap stock formation and minimizing the loss of neutral oil. However, degumming pretreatment of crude fats and oils may be required to remove impurities that would darken the product when heated to the temperature required for steam distillation, or otherwise cause a substandard product. The degumming process may involve treating the crude oil with water, a saline solution, enzymes, caustic soda, or a diluting acid such as phosphoric acid, citric acid, or maleic acid to remove phosphatides, waxes, oxidation accelerators, and other impurities. The degumming process converts phosphatides into hydrated gums, which are insoluble in oil and readily separated as sludge by sedimentation, filtration, or centrifugation.

[0009]

[0011] The optionally refined oil may contain an unsaturated or substantially unsaturated, liquid or substantially liquid triglyceride portion (phase L) and a saturated or substantially saturated, solid or substantially solid triglyceride portion (phase S). The solid phase S may then be converted to linear or substantially linear paraffin as a “bio-naphtha”. More specifically, the refined oil can be fractionated into phases L and S by fractional crystallization, which involves controlled cooling, during which the triglycerides of the composite mixture having substantially saturated acyl moieties crystallize and precipitate from the mixture to form phase S, while the triglycerides having substantially unsaturated acyl moieties remain liquid to form phase L, and the two phases are then separated by simple filtration or decantation or centrifugation. In one embodiment, the fractionation may be “dry fractionation” or “dry winterization,” which is the removal of solids by controlled crystallization and separation techniques involving the use of solvents or dry treatments (sometimes called dewaxing). The fractionation process mainly consists of two stages. The first is the crystallization stage. As the temperature of the molten fat and oil or its solution is lowered, crystals grow, and their solubility at the final or separation temperature determines the triglyceride composition of the crystals formed and their mother liquor. The separation process is the second step of fractionation. Several options can be used, such as vacuum filters, centrifuges, conical screen scroll centrifuges, hydraulic presses, membrane filter presses, or decanters. Fractionation may also be carried out in the presence of a solvent such as paraffin, alkyl acetate, ether, ketone, alcohol, or chlorinated hydrocarbon.

[0010]

[0012] Once obtained, phase S may be converted to linear or substantially linear paraffins as bionaphtha by known processes, such as thermal decarboxylation (e.g., using soap raw materials obtained by chemically refining fats and oils), catalytic decarboxylation (e.g., using fatty acid raw materials obtained by physically refining oils and fats), and catalytic hydrogenation (using triglycerides and / or fatty acid raw materials). Hydrogenation is often utilized and involves ultimately removing oxygen atoms from fats and oils. Hydrogenation is preferably carried out in a continuous fixed-bed reactor, a continuous stirred-tank reactor, or a slurry-type reactor, which includes a solid catalyst. The catalyst may include, for example, Ni, Mo, Co, or mixtures of NiW, NiMo, CoMo, NiCoW, NiCoMo, NiMoW, and CoMoW oxides or sulfides supported on high-surface-area carbon, alumina, silica, titania, or zirconia as the catalytic active phase, or a mixture of Group 10 (Ni, Pt, or Pd) or Group 11 (Cu or Ag) metals or alloys supported on high-surface-area carbon, magnesia, zinc oxide, spinel (Mg2Al2O4, ZnAl2O4), perovskite (BaTiO3, ZnTiO3), calcium silicate (e.g., xonotlite), alumina, silica, or a mixture of the latter as the catalytic active phase. The support of the catalytic active phase preferably exhibits low acidity, preferably neutral or basic, in order to avoid branched paraffins and hydroisomerization reactions that lead to decomposition. Hydrogen deoxygenation may be carried out at a temperature of about 200°C to about 500°C, and in some embodiments, about 280°C to about 400°C, under a pressure of about 1 MPa to about 10 MPa, and with a hydrogen-to-refined oil ratio of about 100 to about 2000, and in some embodiments, about 350 to about 1500.

[0011]

[0013] Regardless of the method by which bionaphtha is formed, the resulting raw material containing bionaphtha can be subjected to a steam cracking process to obtain bioaromatic compounds (e.g., biobenzene). A steam cracking apparatus is a complex industrial facility that can be divided into three main zones, each containing several types of equipment with very specialized functions: (i) a high-temperature zone including a pyrolysis or cracking furnace, quench exchanger and quench ring, and columns for a high-temperature separation train; (ii) a compression zone including a cracking gas compressor, purification and separation columns, and a dryer; and (iii) a low-temperature zone including a cold box, a demethane tower, fractionation columns for a low-temperature separation train, C2 and C3 converters, and a gasoline hydro-stabilizing reactor. Hydrocarbon cracking may be carried out in a tubular reactor within a direct-fired heater (furnace). Various tube sizes and configurations can be used, such as coiled tubes, U-tubes, or straight-tube arrangements. Each furnace consists of a convection zone where waste heat is recovered and a radiation zone where pyrolysis takes place. The feedstock-steam mixture is preheated to approximately 530-650°C in the convection zone, or the feedstock is preheated in the convection section, then mixed with diluted steam, and then flows into the radiation zone where pyrolysis takes place at temperatures varying between 750-950°C. The steam / feedstock (steam / [hydrocarbon feedstock]) weight ratio may be approximately 0.2-1.0 kg / kg. In the case of a steam cracking furnace, the severity can be controlled by temperature, residence time, total pressure, and partial pressure of hydrocarbons. Evaporates from the pyrolysis furnace include unreacted feedstock, olefins (mainly ethylene and propylene), hydrogen, methane, C4 mixtures (mainly isobutylene and butadiene), aromatics in the C6-C8 range, ethane, propane, diolefins (acetylene, methylacetylene, propadiene), and heavy hydrocarbons that boil in the fuel oil temperature range. This decomposition gas is rapidly quenched to 338-510°C to stop the thermal decomposition reaction, minimize continuous reaction, and recover sensible heat from the gas by generating high-pressure steam in a parallel transfer line heat exchanger (TLE).

[0012]

[0014] The resulting mixed hydrocarbon feed may then be fed to a “de-aromatizing unit,” which is a purification unit for separating aromatic hydrocarbons (e.g., biobenzene). Such de-aromatizing processes are described in Folkins (2000) Benzene, Ullmann's Encyclopedia of Industrial Chemistry. One particular method for separating aromatic hydrocarbons from a mixture of aromatic and aliphatic hydrocarbons is solvent extraction, as described in WO2012 / 135111, which is incorporated herein by reference. Preferred solvents used for aromatic solvent extraction are sulfolane, tetraethylene glycol, and N-methylpyrrolidone, which are commonly used solvents in commercial aromatic extraction processes. These species are often used in combination with water and / or other solvents or other chemicals (sometimes called co-solvents), such as alcohol. Non-nitrogen-containing solvents such as sulfolane are particularly preferred. Solvent extraction of heavy aromatics is described in the Art; see, for example, U.S. Patent No. 5,880,325, which is incorporated herein by reference in its entirety. Alternatively, known methods other than solvent extraction, such as molecular sieving separation or boiling point-based separation, can be applied to the separation of heavy aromatics in the dearomatic process.

[0013]

[0015] Once obtained, the resulting biobenzene can be converted to biophenol, a reactant used in the production of biohydroxybenzoic acid. In this regard, the biobenzene may first be converted to biocumene (isopropylbenzene). For example, one preferred process involves an alkylation reaction using propylene and biobenzene starting materials. A typical propylene starting material may be a nearly pure polymer-grade material or may contain a significant amount of propane, as is typically found in purified-grade propylene. A typical biobenzene starting material may contain benzene (minimum 99.9 wt%) and toluene (minimum 0.05 wt%). The alkylation reactor may be operated in gas phase, liquid phase, or mixed phase. At lower temperatures in liquid-phase operation, xylene impurities are not produced, and a cumene product of good quality is produced. The temperature is typically about 100°C to about 310°C, and the pressure is typically about 8 to 50 bar. The alkylation reactor may contain an effective amount of alkylation catalyst, such as a solid acid catalyst (e.g., solid oxide zeolite). Examples include zeolite beta, zeolite X, zeolite Y, mordenite, faujasite, zeolite omega, UZM-8, MCM-22, MCM-36, MCM-49, and MCM-56.

[0014]

[0016] In the alkylation reactor, biobenzene is alkylated with propylene to form biocumene (isopropylbenzene). However, several polyisopropylbenzenes, mainly disubstituted and trisubstituted propylbenzenes, are also formed. To minimize the formation of dialkylation products of benzene, it is generally desirable to maintain a molar excess of benzene throughout the reaction zone, with a benzene to propylene ratio of approximately 4:1 to approximately 16:1, more preferably approximately 8:1. A transalkylation reactor can also be used to transalkylate the polyisopropylbenzene produced in the alkylation reactor to further form cumene. Preferred conditions and catalysts may be the same as those described for the alkylation reactor. The effluents from the alkylation and transalkylation reactors are subjected to separation operations to separate the benzene, cumene product, polyisopropylbenzene, and byproduct streams using a distillation column such as the one described in U.S. Patent Publication 2008 / 0293986, which is incorporated herein by reference. For example, a first distillation column may be used to recover excess benzene from the reactor effluent. The overhead of the benzene column, which is mostly benzene, is typically reused in the alkylation and transalkylation reactors. A second distillation column may be used to recover the cumene product from the bottom of the benzene column. The cumene product is typically the net overhead from the cumene column. A third distillation column, which is a polyisopropylbenzene column, may also be used to recover a polyisopropylbenzene reuse stream from the bottom of the cumene column. The polyisopropylbenzene is recovered as overhead from the polyisopropylbenzene column and is typically reused in the transalkylation reactor.

[0015]

[0017] Once formed, biocumene can then be reacted to form biophenols using a process known as the "cumene process." More specifically, biocumene can be first oxidized to obtain cumene hydroperoxide radicals. This may be done by oxidation of cumene in an alkaline medium in which the hydroperoxide product is stable. Biocumene may be emulsified in an alkaline aqueous solution such as sodium carbonate at pH 8.5–10.5 using an emulsifier such as sodium stearate. Oxidation with air or oxygen may be carried out at a slowly rising temperature of about 70°C–130°C. Subsequently, the cumene hydroperoxide undergoes cleavage, during which an acid catalyst is added, and the hydroperoxide is decomposed into biophenols, acetone, and other by-products. The acid catalyst used may be any acidic material such as phosphoric acid, sulfuric acid, and SO2. For example, cumene hydroperoxide can be treated with dilute sulfuric acid (5–25 percent concentration) at a temperature of about 50°C–70°C. After cleavage is complete, the reaction mixture can be separated, and the oil layer can be distilled to obtain biophenol, acetone, unreacted cumene, alpha-methylstyrene, acetophenone, and tar.

[0016]

[0018] Biophenols can then be converted to biohydroxybenzoic acid using the Kolbe-Schmitt reaction, as described, for example, in U.S. Publication No. 2006 / 0052632 and U.S. Patent No. 5,072,036, which are incorporated herein by reference. More specifically, the Kolbe-Schmitt reaction is a carboxylation reaction that proceeds by treating biophenols with an alkali metal hydroxide (e.g., potassium hydroxide) to form an alkali metal phenolate (e.g., potassium phenolate), heating the alkali metal phenolate in the presence of carbon dioxide (under pressure or at atmospheric pressure), and then optionally treating the product with sulfuric acid. When potassium phenolate is used, 4-hydroxybenzoic acid is preferably obtained. The temperature at which the alkali metal phenolate is heated is typically in the range of about 230°C to about 450°C, and the pressure of carbon dioxide is typically from atmospheric pressure to about 6 kg / cm².2 The range is as follows.Optionally, carbon dioxide may be diluted or mixed with a gas inert to the starting materials and products under the reaction conditions specified herein.For example, carbon dioxide may be introduced together with nitrogen, hydrogen, helium, argon, carbon monoxide, hydrocarbons, etc.Alkali metal phenolates may optionally be reacted with carbon dioxide in the presence of substituted phenolates, such as monosubstituted phenolates (e.g., potassium cresolate and potassium phenyl phenolate), disubstituted phenolates (e.g., potassium 2,3-, 2,4-, 2,5-, 2,6-, 3,4- and 3,5-xylenolates, dipotassium salts of dihydroxybenzene), or trisubstituted phenolates (e.g., potassium 2,4,6-, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5- and 3,4,5-trimethylphenolates). When used, the amount of substituted phenolates in the reaction system may range from about 0.2 to about 30 equivalents, calculated in relation to the equivalent amount of potassium oxy radicals in these compounds based on the equivalent amount of the starting potassium phenolate. The process may be carried out in an inert reaction medium or without any reaction medium. When the process is carried out in an inert reaction medium, examples of such mediums include aromatic hydrocarbons, aromatic ethers, aromatic alkanes, aromatic alkenes, aromatic ketones and their hydrogenation products, aliphatic petroleum hydrocarbons, aprotic polar solvents, and higher alcohols.

[0017] II. Bio-liquid crystal polymer ("Bio-LCP")

[0019] As described above, the resulting biohydroxybenzoic acid (e.g., bio-4-hydroxybenzoic acid) may be particularly suitable for use in the formation of bio-based liquid crystal polymers ("bioLCPs"). BioLCPs generally contain aromatic repeating units derived from the biohydroxybenzoic acid described above. Examples of such acids include, for example, bio-4-hydroxybenzoic acid, bio-4'-hydroxyphenyl-4-benzoic acid, bio-3'-hydroxyphenyl-4-benzoic acid, bio-4'-hydroxyphenyl-3-benzoic acid, and their alkyl, alkoxy, aryl, and halogen substituents. Particularly preferred is bio-4-hydroxybenzoic acid ("HBA"). Preferably, all hydroxybenzoic acids used in liquid crystal polymers are biohydroxybenzoic acids derived from bionaphtha. However, this is by no means essential, and some of such acids may also be derived from conventional fossil fuel sources (e.g., petroleum), as is known in the art. Nevertheless, repeating units derived from hydroxybenzoic acid (e.g., biohydroxybenzoic acid) typically constitute about 20 mol.% to about 85 mol.% of the polymer, about 30 mol.% to about 80 mol.% in some embodiments, and about 40 mol.% to about 75 mol.% in some embodiments. In one particular embodiment, for example, the liquid crystal polymer may contain repeating units derived from bioHBA in amounts of 40 mol.% to about 85 mol.%, about 45 mol.% to about 82 mol.% in some embodiments, and about 50 mol.% to about 80 mol.% in some embodiments.

[0020] BioLCPs may also contain aromatic repeating units derived from other types of hydrocarboxylic acids, such as hydroxynaphthoic acid. Examples of such acids include, for example, 2-hydroxy-6-naphthoic acid ("HNA"); 2-hydroxy-5-naphthoic acid; 3-hydroxy-2-naphthoic acid; 2-hydroxy-3-naphthoic acid, as well as their alkyl, alkoxy, aryl, and halogen substituents, and combinations thereof. When utilized, repeating units derived from hydroxynaphthoic acid may constitute about 1 mol.% to about 50 mol.% of the polymer, about 2 mol.% to about 40 mol.% in some embodiments, and about 5 mol.% to about 30 mol.% in some embodiments. Aromatic dicarboxylic acid repeating units derived from aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4'-dicarboxybiphenyl, bis(4-carboxyphenyl) ether, bis(4-carboxyphenyl)butane, bis(4-carboxyphenyl)ethane, bis(3-carboxyphenyl) ether, bis(3-carboxyphenyl)ethane, and alkyl, alkoxy, aryl, and halogen-substituted derivatives thereof, as well as combinations thereof, may also be used. Particularly preferred aromatic dicarboxylic acids include, for example, terephthalic acid ("TA"), isophthalic acid ("IA"), and 2,6-naphthalenedicarboxylic acid ("NDA"). When used, repeating units derived from aromatic dicarboxylic acids (e.g., IA, TA, and / or NDA) typically constitute about 1 mol.% to about 50 mol.% of the polymer, about 5 mol.% to about 40 mol.% in some embodiments, and about 10 mol.% to about 35 mol.% in some embodiments.

[0018]

[0021] Other repeating units can also be used. For example, in certain embodiments, repeating units derived from aromatic diols such as hydroquinone, resorcinol, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 4,4'-dihydroxybiphenyl (or 4,4'-biphenol), 3,3'-dihydroxybiphenyl, 3,4'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl ether, bis(4-hydroxyphenyl)ethane, and their alkyl, alkoxy, aryl, and halogen-substituted derivatives, as well as combinations thereof, may be used. Particularly preferred aromatic diols include, for example, hydroquinone ("HQ") and 4,4'-biphenol ("BP"). When used, repeating units derived from aromatic diols (e.g., HQ and / or BP) typically constitute about 1 mol.% to about 50 mol.% of the polymer, about 5 mol.% to about 40 mol.% in some embodiments, and about 10 mol.% to about 35 mol.% in some embodiments. Furthermore, repeating units such as those derived from aromatic amides (e.g., acetaminophen ("APAP")) and / or aromatic amines (e.g., 4-aminophenol ("AP"), 3-aminophenol, 1,4-phenylenediamine, 1,3-phenylenediamine, etc.) may be used. If used, repeating units derived from aromatic amides (e.g., APAP) and / or aromatic amines (e.g., AP) typically constitute about 0.1 mol.% to about 20 mol.% of the polymer, about 0.5 mol.% to about 15 mol.% in some embodiments, and about 1 mol.% to about 10% in some embodiments. It should also be understood that various other monomer repeating units may be incorporated into the polymer. For example, in certain embodiments, the polymer may contain one or more repeating units derived from non-aromatic monomers such as aliphatic or alicyclic hydroxycarboxylic acids, dicarboxylic acids, diols, amides, and amines. Naturally, in other embodiments, the polymer may be "totally aromatic" in that it does not contain repeating units derived from non-aromatic (e.g., aliphatic or alicyclic) monomers.

[0019]

[0022] Regardless of the specific components and properties of the polymer, bio-LCP can be prepared by first introducing an aromatic monomer used in the formation of an ester repeating unit (e.g., aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, etc.) and / or other repeating units (e.g., aromatic diol, aromatic amide, aromatic amine, etc.) into a reaction vessel to initiate a polycondensation reaction. Specific conditions and steps utilized in such reactions are well known and may be described in more detail in U.S. Patent No. 4,161,470 to Calundann, U.S. Patent No. 5,616,680 to Linstid, III et al., U.S. Patent No. 6,114,492 to Linstid, III et al., U.S. Patent No. 6,514,611 to Shepherd, and WO2004 / 058851 to Waggoner. The vessel utilized in the reaction is not particularly limited, but it is generally desired to utilize those typically used for reactions of highly viscous fluids. Examples of such reaction vessels include a stirred tank type apparatus having a stirrer with various shaped stirring blades such as an anchor type, multi-stage type, helical ribbon type, screw shaft type, etc., or modified shapes thereof. Further examples of such reaction vessels include mixing apparatuses commonly used for resin kneading such as a kneader, roll mill, Banbury mixer, etc.

[0020]

[0023] If desired, the reaction can proceed by acetylation of the monomers known in the art. This can be achieved by adding an acetylating agent (e.g., acetic anhydride) to the monomers. Acetylation is generally initiated at a temperature of about 90 °C. In the initial stage of acetylation, reflux may be utilized to maintain a gas phase temperature below the point at which acetic acid by-products and anhydrides begin to distill. The temperature during acetylation typically ranges from 90 °C to 150 °C, and in some embodiments from about 110 °C to about 150 °C. When reflux is used, the gas phase temperature typically exceeds the boiling point of acetic acid but remains low enough to retain the remaining acetic anhydride. For example, acetic anhydride vaporizes at a temperature of about 140 °C. Thus, it is particularly desirable to provide a gas phase reflux to the reactor at a temperature of about 110 °C to about 130 °C. To ensure a substantially complete reaction, an excess amount of acetic anhydride can be utilized. The amount of excess anhydride varies depending on the specific acetylation conditions utilized, including the presence or absence of reflux. It is not uncommon to use an excess of acetic anhydride of about 1 to about 10 mole percent based on the total number of moles of reactant hydroxyl groups present.

[0021]

[0024] Acetylation may be carried out in a separate reaction vessel or in situ within the polymerization reaction vessel. If a separate reaction vessel is utilized, one or more of the monomers can be introduced into the acetylation reactor and then transferred to the polymerization reactor. Similarly, one or more of the monomers may be introduced directly into the reaction vessel without prior acetylation.

[0022]

[0025] In addition to monomers and optional acetylating agents, other components that help promote polymerization may also be included in the reaction mixture. For example, catalysts such as metal salt catalysts (e.g., magnesium acetate, tin(I) acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, etc.) and organic compound catalysts (e.g., N-methylimidazole) can be optionally used. Such catalysts are typically used in amounts of about 50 to about 500 million parts relative to the total weight of the repeating unit precursor. When separate reactors are used, it is typically desirable, but not necessarily, to apply the catalyst to the acetylation reactor rather than the polymerization reactor.

[0023]

[0026] The reaction mixture is generally heated to a high temperature in a polymerization reactor vessel to initiate melt polycondensation of the reactants. Polycondensation may take place in a temperature range, for example, about 200°C to about 400°C. For example, one preferred technique for forming aromatic polyesters may involve introducing precursor monomers and acetic anhydride into a reactor, heating the mixture to a temperature of about 90°C to about 150°C to acetylate the hydroxyl groups of the monomers (e.g., forming acetoxy), and then raising the temperature to about 200°C to about 400°C to carry out melt polycondensation. As the final polymerization temperature approaches, volatile by-products of the reaction (e.g., acetic acid) can also be removed, thereby easily achieving the desired molecular weight. The reaction mixture is generally stirred during polymerization to ensure good heat transfer and mass transfer, and consequently, good material homogeneity. The rotational speed of the stirrer may vary during the reaction, but is typically in the range of about 10 to about 100 revolutions per minute ("rpm"), and in some embodiments, about 20 to about 80 rpm. To increase the molecular weight of the molten material, the polymerization reaction can also be carried out under vacuum, which facilitates the removal of volatile substances formed in the final stage of polycondensation. Vacuum can be created by applying suction pressure ranging from 0.35 kg to 2.10 kg per square centimeter (approximately 5 to 30 pounds per square inch) ("psi"), and in some embodiments, from 0.70 kg to 1.40 kg per square centimeter (approximately 10 to 20 psi).

[0024]

[0027] After melt polymerization, the molten polymer may be discharged from the reactor through an extrusion orifice typically equipped with a die of the desired shape, cooled, and recovered. Generally, the molten material is discharged through a perforated die to form strands, which are then taken into a water bath, pelletized, and dried. In some embodiments, the melt-polymerized polymer may also be subjected to a subsequent solid polymerization method to further increase its molecular weight. Solid polymerization can be carried out in the presence of a gas (e.g., air, an inert gas, etc.). Suitable inert gases include, for example, nitrogen, helium, argon, neon, krypton, xenon, and combinations thereof. The solid polymerization reaction vessel may be of substantially any design that allows the polymer to be maintained at a desired solid polymerization temperature for a desired residence time. Examples of such vessels may have a fixed bed, a stationary bed, a moving bed, a fluidized bed, etc. The temperature at which solid polymerization is carried out may vary, but is typically in the range of about 200°C to about 400°C. The polymerization time naturally varies based on the temperature and the target molecular weight. However, in most cases, the solid polymerization time is about 2 to 12 hours, and in some embodiments, about 4 to 10 hours.

[0025]

[0028] Once formed, the resulting bio-LCP may have a "bio-content" of approximately 1 wt.% to 100 wt.% of the total weight of monomers (repeating units) used in the polymer, approximately 2 wt.% to 90 wt.% in some embodiments, approximately 5 wt.% to 70 wt.% in some embodiments, and approximately 10 wt.% to 60 wt.% in some embodiments. As used herein, the term "bio-content" generally refers to the weight percentage of monomers (repeating units) derived from bio-naphtha. Therefore, it should be understood that this weight percentage may include biohydroxybenzoic acid (e.g., bio-4-hydroxybenzoic acid) as described herein, as well as other monomer components that may also be derived from bionaphtha, such as bioterephthalic acid ("bioTA"), bioisophthalic acid ("bioIA"), bio-4,4'-biphenol ("bioBP"), biohydroquinone ("bioHQ"), bio-2-hydroxy-6-naphthoic acid ("bioHNA"), bio-2,6-naphthalenedicarboxylic acid ("bioNDA"), bio-4-aminophenol ("bioAP"), bioacetaminophen ("bioAPAP"), etc. Despite such a high bio content, the resulting bioLCP can still exhibit properties similar to those of liquid crystal polymers formed from conventional fossil fuel sources. That is, bioLCP is still considered "thermotropic" as long as it has a rod-like structure and can exhibit crystalline behavior in its molten state (e.g., thermotropic nematic state). Bio-LCPs also have high melting temperatures, typically around 280°C to 400°C, about 290°C to 380°C in some embodiments, and about 300°C to 350°C in some embodiments. The melting temperature can be determined using differential scanning calorimetry ("DSC"), as is well known in the art, such as by ISO 11357-3:2018.

[0026] III. Polymer Compositions

[0029] Bio-LCP can be used in neat form (i.e., a composition containing 100 wt.% bio-LCP) or blended with other components to form a polymer composition. In such embodiments, bio-LCP typically constitutes about 10 wt.% to about 90 wt.%, about 20 wt.% to about 80 wt.%, about 25 wt.% to about 70 wt.%, and about 30 wt.% to about 60 wt.% of the polymer composition. In such embodiments, other additives similarly constitute about 10 wt.% to about 90 wt.%, about 20 wt.% to about 80 wt.%, about 30 wt.% to about 75 wt.%, and about 40 wt.% to about 70 wt.% of the polymer composition. If desired, other additives may also be derived from sustainable sources such as recycled materials, renewable materials, and bio-based materials. For example, the total “sustainable content” of a polymer composition is typically about 5 wt.% to 100 wt.% of the total weight of the composition, about 10 wt.% to 90 wt.% in some embodiments, and about 20 wt.% to 80 wt.% in some embodiments. The term “sustainable content” generally refers to the weight percentage of components derived from sustainable sources. For example, in the case of a composition containing only bio-LCP, the “sustainable content” is the same as the “bio-content” (weight percentage of monomers derived from bio-naphtha). In the case of a composition containing bio-LCP, other sustainable materials (e.g., recycled materials), and non-sustainable materials (e.g., fossil fuel-based materials, virgin materials, etc.), the “sustainable content” can be determined as follows:

[0027]

number

[0028]

[0030] The following are various examples of other additives that can be used in polymer compositions. A. Mineral filler

[0031] The polymer composition may optionally contain one or more mineral fillers. When used, such mineral fillers typically constitute about 1 wt.% to about 50 wt.%, about 2 wt.% to about 45 wt.%, and about 5 wt.% to about 40 wt.%, of the polymer composition. The properties of the mineral fillers used in the polymer composition may vary, including mineral particles, mineral fibers (or "whiskers"), and blends thereof. Typically, the mineral fillers used in the polymer composition have a certain hardness value to help improve the mechanical strength, adhesive strength, and surface properties of the composition. For example, the hardness value may be about 2.0 or higher, about 2.5 or higher, about 3.0 or higher, about 3.0 to about 11.0, about 3.5 to about 11.0, and about 4.5 to about 6.5, based on the Mohs hardness scale.

[0029]

[0032] Any of a variety of different types of mineral particles, for example, natural and / or synthetic silicate minerals such as talc, mica, silica (e.g., amorphous silica), alumina, halloysite, kaolinite, illite, montmorillonite, vermiculite, palygorskite, pyrophyllite, calcium silicate, aluminum silicate, wollastonite, etc.; sulfates; carbonates; phosphates; fluorides, borates, etc. may generally be used in the polymer composition. Particularly suitable particles are talc, calcium carbonate (CaCO3), copper hydroxycarbonate (Cu2CO3(OH)2); calcium fluoride (CaFl2); calcium pyrophosphate ((Ca2P2O7), anhydrous calcium hydrogen phosphate (CaHPO4), hydrated aluminum phosphate (AlPO4·2H2O); silica (SiO2), potassium aluminum silicate (KAlSi3O8), copper silicate (CuSiO3·H2O); calcium borosilicate hydroxide (Ca2B5SiO9(OH)5); alumina (AlO2); calcium sulfate (CaSO4), barium sulfate (BaSO4), talc, mica, etc., and particles including combinations thereof. Talc, mica, calcium carbonate, and barium sulfate are particularly suitable. Any form of mica can generally be used, for example, muscovite (KAl2(AlSi3)O 10 (OH)2), biotite (K(Mg,Fe)3(AlSi3)O 10 (OH)2), phlogopite (KMg3(AlSi3)O 10 (OH)2), lepidolite (K(Li,Al) 2-3 (AlSi3)O 10 (OH)2), glauconite (K,Na)(Al,Mg,Fe)2(Si,Al)4O 10 (OH)2), etc. are included.

[0030]

[0033] In certain embodiments, mineral particles such as barium sulfate and / or calcium sulfate particles may generally have a granular or nodular shape. In such embodiments, the particles may have a median diameter (e.g., diameter) of about 0.5 to about 20 micrometers, about 1 to about 15 micrometers in some embodiments, about 1.5 to about 10 micrometers in some embodiments, and about 2 to about 8 micrometers in some embodiments, determined using laser diffraction techniques (e.g., using a Horiba LA-960 particle size distribution analyzer) in accordance with ISO 13320:2009. In other embodiments, it may be desirable to utilize flake-like mineral particles such as mica particles having relatively high aspect ratios (e.g., average diameter divided by average thickness) of about 4 or more, about 8 or more in some embodiments, and about 10 to about 500 in some embodiments. In such embodiments, the average diameter of the particles may be in the range of, for example, about 5 to about 200 micrometers, about 8 to about 150 micrometers in some embodiments, and about 10 to about 100 micrometers in some embodiments. The average thickness may be less than or equal to about 2 micrometers, determined similarly using laser diffraction techniques in accordance with ISO 13320:2009 (e.g., using a Horiba LA-960 particle size distribution analyzer), about 5 nanometers to about 1 micrometer in some embodiments, and about 20 nanometers to about 500 nanometers in some embodiments. The mineral particles may also have a narrow size distribution; that is, at least about 70 volume percent of the particles, at least about 80 volume percent of the particles, and at least about 90 volume percent of the particles may have a size within the above range.

[0031]

[0034] Suitable mineral fibers include, similarly, silicates such as neosilicate, sorosilicate, inosilicate (e.g., calcium inosilicate such as wollastonite; calcium magnesium inosilicate such as tremolite; calcium magnesium iron inosilicate such as yoncite; magnesium iron inosilicate such as orthopole), phyllosilicate (e.g., aluminum phyllosilicate such as palygorskite), tectosilicate, etc.; sulfates such as calcium sulfate (e.g., dehydrated or anhydrous gypsum); mineral wool (e.g., rock wool or slag wool); and others. Particularly preferred are fibers having a desired hardness value, including fibers derived from inosilicate such as wollastonite (Mohs hardness 4.5-5.0) which is commercially available from Nyco Minerals under the trade name Nyglos® (e.g., Nyglos® 4W or Nyglos® 8). Mineral fibers are approximately 1 to 35 micrometers in size. In some embodiments, the median width (e.g., diameter) can be about 2 to about 20 micrometers, in some embodiments about 3 to about 15 micrometers, and in some embodiments about 7 to about 12 micrometers. Mineral fibers can also have a narrow size distribution; that is, at least about 60 volume percent of the fibers, in some embodiments at least about 70 volume percent of the fibers, and in some embodiments at least about 80 volume percent of the fibers may have sizes within the above ranges. In addition to having the above size characteristics, mineral fibers can also have relatively high aspect ratios (average length divided by median width) to help further improve the mechanical properties and surface quality of the resulting polymer composition. For example, mineral fibers can have aspect ratios of about 2 to about 100, in some embodiments about 2 to about 50, in some embodiments about 3 to about 20, and in some embodiments about 4 to about 15. The volume-average length of such mineral fibers may range, for example, from about 1 to about 200 micrometers, from about 2 to about 150 micrometers in some embodiments, from about 5 to about 100 micrometers in some embodiments, and from about 10 to about 50 micrometers in some embodiments.

[0032] B. Fibrous fillers

[0035] Fibrous fillers may also be used in polymer compositions. Fibrous fillers typically consist of fibers having high tensile strength relative to their mass. For example, the ultimate tensile strength of the fibers (determined according to ASTM D2101) is typically about 1,000 to about 15,000 megapascals ("MPa"), about 2,000 to about 10,000 MPa in some embodiments, and about 3,000 to about 6,000 MPa in some embodiments. To help maintain desired properties, such high-strength fibers may be formed from materials that are generally intrinsically insulating, such as glass, ceramics (e.g., alumina or silica), aramid (e.g., Kevlar®, sold by EIdu Pont de Nemours, Wilmington, Del.), polyolefins, and polyesters. Glass fibers such as E-glass, A-glass, C-glass, D-glass, AR-glass, R-glass, S1-glass, and S2-glass are particularly preferred. If desired, all or part of such fibers may be recycled.

[0033]

[0036] The fibers used in the fibrous filler may have a variety of different sizes, but fibers with specific aspect ratios can help improve the mechanical properties of the resulting polymer composition. Specifically, fibers with aspect ratios (average length divided by nominal diameter) of about 5 to about 50, about 6 to about 40 in some embodiments, and about 8 to about 25 in some embodiments are particularly beneficial. Such fibers may have, for example, a weight-average length of about 100 to about 800 micrometers, about 120 to about 500 micrometers in some embodiments, about 150 to about 350 micrometers in some embodiments, and about 200 to about 300 micrometers in some embodiments. The fibers may also have a nominal diameter of about 6 to about 35 micrometers, and about 9 to about 18 micrometers in some embodiments. The relative amount of the fibrous filler can also be selectively controlled to help achieve the desired mechanical and thermal properties. For example, the fibrous filler may constitute about 1 wt.% to about 40 wt.% of the polymer composition, about 3 wt.% to about 30 wt.% in some embodiments, and about 5 wt.% to about 20 wt.% in some embodiments.

[0034] C. Impact modifier

[0037] Impact modifiers may also be used in polymer compositions. For example, the impact modifier may be a polymer containing olefin monomer units derived from one or more α-olefins. Examples of such monomers include, for example, linear and / or branched α-olefins having 2 to 20 carbon atoms, typically 2 to 8 carbon atoms. Specific examples include ethylene, propylene, 1-butene; 3-methyl-1-butene; 3,3-dimethyl-1-butene; 1-pentene; 1-pentene with one or more methyl, ethyl, or propyl substituents; 1-hexene with one or more methyl, ethyl, or propyl substituents; 1-heptene with one or more methyl, ethyl, or propyl substituents; 1-octene with one or more methyl, ethyl, or propyl substituents; 1-nonene with one or more methyl, ethyl, or propyl substituents; ethyl, methyl, or dimethyl substituted 1-decene; 1-dodecene; and styrene. Particularly desired α-olefin monomers are ethylene and propylene. The olefin polymer may be in the form of a copolymer containing other monomer units, as is known in the art. For example, other suitable monomers include "(meth)acrylic" monomers, which include acrylic and methacrylic monomers, as well as their salts or esters, such as acrylate and methacrylate monomers.Examples of such (meth)acrylic monomers include methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, s-butyl acrylate, i-butyl acrylate, t-butyl acrylate, n-amyl acrylate, i-amyl acrylate, isobornyl acrylate, n-hexyl acrylate, 2-ethylbutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-decyl acrylate, methylcyclohexyl acrylate, cyclopentyl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate Examples include methyl methacrylate, 2-hydroxyethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, i-propyl methacrylate, i-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, i-amyl methacrylate, s-butyl methacrylate, t-butyl methacrylate, 2-ethylbutyl methacrylate, methylcyclohexyl methacrylate, cinnamyl methacrylate, clotyl methacrylate, cyclohexyl methacrylate, cyclopentyl methacrylate, 2-ethoxyethyl methacrylate, isobornyl methacrylate, and combinations thereof. In one embodiment, for example, the impact modifier may be ethylene methacrylate copolymer ("EMAC"). When used, the relative parts of the monomer components can be selectively controlled. α-olefin monomers may constitute, for example, about 55 wt.% to about 95 wt.% of the copolymer, about 60 wt.% to about 90 wt.% in some embodiments, and about 65 wt.% to about 85 wt.% in some embodiments. Other monomer components (e.g., (meth)acrylic monomers) may constitute about 5 wt.% to about 35 wt.% of the copolymer, about 10 wt.% to about 32 wt.% in some embodiments, and about 15 wt.% to about 30 wt.% in some embodiments.

[0035]

[0038] Other suitable olefin copolymers may be “epoxy-functionalized” in that they contain an average of two or more epoxy functional groups per molecule. Copolymers may also contain epoxy-functional monomer units. One example of such units is an epoxy-functional (meth)acrylic monomer component. For example, suitable epoxy-functional (meth)acrylic monomers include, but are not limited to, those containing 1,2-epoxy groups, such as glycidyl acrylate and glycidyl methacrylate. Other suitable epoxy-functional monomers include allyl glycidyl ether, glycidyl ethyl acrylate, and glycidyl itoconate. Other suitable monomers may also be utilized to help achieve the desired molecular weight. In one particular embodiment, for example, the copolymer may be a terpolymer formed from an epoxy-functional (meth)acrylic monomer component, an α-olefin monomer component, and a non-epoxy-functional (meth)acrylic monomer component. The copolymer may be, for example, poly(ethylene-co-butyl acrylate-co-glycidyl methacrylate). When used, epoxy-functionalized (meth)acrylic monomers typically constitute about 1 wt.% to about 20 wt.% of the copolymer, about 2 wt.% to about 15 wt.% in some embodiments, and about 3 wt.% to about 10 wt.% in some embodiments.

[0036]

[0039] When used, the impact modifier typically constitutes about 0.5 to about 60 parts by weight, about 1 to about 50 parts by weight, and about 2 to about 30 parts by weight, per 100 parts by weight of the liquid crystal polymer used in the composition. For example, the impact modifier may constitute about 0.1 wt.% to about 30 wt.% of the polymer composition, about 0.5 wt.% to about 25 wt.% in some embodiments, and about 1 wt.% to about 20 wt.% in some embodiments.

[0037] D. Laser-activatable additives

[0040] While not strictly necessary, polymer compositions may be “laser-activatable” in the sense that they contain additives that can be activated by a laser direct structuring ("LDS") process. In such a process, the additives are exposed to a laser that causes metal emission. The laser then traces a pattern of conductive elements onto the surface, leaving a rough surface embedded with metal particles. These particles act as nuclei for crystal growth during subsequent plating processes (e.g., copper plating, gold plating, nickel plating, silver plating, zinc plating, tin plating, etc.). Laser-activatable additives generally contain oxide crystals, which can contain two or more metal oxide cluster configurations within a definable crystal formation. For example, the overall crystal formation can be expressed by the following formula: AB2O4 or ABO2 (In the formula, A is a metal cation having two or more valencies, such as cadmium, chromium, manganese, nickel, zinc, copper, cobalt, iron, magnesium, tin, titanium, and combinations thereof; B is a metal cation with a valency of 3 or higher, such as antimony, chromium, iron, aluminum, nickel, manganese, tin, etc., and combinations thereof. It can have.

[0038]

[0041] Typically, in the above formula, A provides the main cation component of the first metal oxide cluster, and B provides the main cation component of the second metal oxide cluster. These oxide clusters may have the same or different structures. In one embodiment, for example, the first metal oxide cluster has a tetrahedral structure, and the second metal oxide cluster has an octahedral cluster. Nevertheless, the clusters together may provide a single, recognizable crystalline structure with enhanced sensitivity to electromagnetic radiation. Examples of suitable oxide crystals include, for example, MgAl2O4, ZnAl2O4, FeAl2O4, CuFe2O4, CuCr2O4, MnFe2O4, NiFe2O4, TiFe2O4, FeCr2O4, MgCr2O4, tin / antimony oxides (e.g., (Sb / Sn)O2) and combinations thereof. Copper chromium oxide (CuCr2O4) is particularly suitable for use in the present invention and is available from Shepherd Color Co. under the name "Shepherd Black 1GM". In some cases, laser-activatable additives may also have a core-shell configuration, such as those described in WO2018 / 130972. In such additives, the shell component of the additive is typically laser-activatable, while the core may be any common compound, such as an inorganic compound (e.g., titanium dioxide, mica, talc, etc.).

[0039]

[0042] When used, the laser-activatable additive typically constitutes about 0.1 wt.% to about 30 wt.% of the polymer composition, about 0.5 wt.% to about 20 wt.% in some embodiments, and about 1 wt.% to about 10 wt.% in some embodiments. Naturally, the polymer composition may also not contain such laser-activatable additives, such as spinel crystals (i.e., 0 wt.%), or such additives may be present only in small concentrations, such as about 1 wt.% or less, about 0.5 wt.% or less in some embodiments, and about 0.001 wt.% to about 0.2 wt.% in some embodiments.

[0040] E. Other optional additives

[0043] A wide variety of other additional additives may also be included in the polymer composition, such as lubricants, thermally conductive fillers, pigments (e.g., carbon black), antioxidants, stabilizers, surfactants, waxes, flame retardants, anti-sagging additives, nucleating agents (e.g., boron nitride), tribological agents (e.g., fluoropolymers), antistatic fillers (e.g., carbon nanotubes, carbon fibers, ionic liquids, carbon black, etc.), dielectric fillers, flow modifiers (e.g., aluminum trihydrate), and other materials added to improve properties and processability. For example, lubricants that can withstand the processing conditions of liquid crystal polymers without substantially decomposing can be used in the polymer composition. Examples of such lubricants include fatty acid esters, their salts, esters, fatty acid amides, organophosphate esters, and hydrocarbon waxes of the type commonly used as lubricants in the processing of engineering plastic materials, including mixtures thereof. Suitable fatty acids typically have a carbon chain skeleton of about 12 to about 60 carbon atoms, such as myristic acid, palmitic acid, stearic acid, arachidic acid, montanic acid, octadecanoic acid, and parinric acid. Suitable esters include fatty acid esters, fatty alcohol esters, wax esters, glycerol esters, glycol esters, and complex esters. Fatty acid amides include primary fatty acid amides, secondary fatty acid amides, methylene and ethylenebisamides, and alkanolamides, such as palmitic acid amide, stearic acid amide, oleic acid amide, and N,N'-ethylenebisstearamide. Also suitable are metal salts of fatty acids such as calcium stearate, zinc stearate, and magnesium stearate; hydrocarbon waxes including paraffin wax, polyolefin and oxidized polyolefin wax; and microcrystalline waxes. Particularly suitable lubricants are acids, salts, or amides of stearic acid, such as pentaerythritol tetrastearate, calcium stearate, or N,N'-ethylenebisstearamide.When used, the lubricant typically constitutes about 0.05 wt.% to about 1.5 wt.% (by weight) of the polymer composition, and in some embodiments, about 0.1 wt.% to about 0.5 wt.% (by weight).

[0041]

[0044] The components used to form the polymer composition may be combined using any of the various different techniques known in the art. In a particular embodiment, for example, bioLCP and any other additives may be melted as a mixture in an extruder to form the polymer composition. The mixture may be melt-kneaded in a single-screw or multi-screw extruder at a temperature of about 250°C to about 450°C. In one embodiment, the mixture may be melted in an extruder having multiple temperature zones. The temperature of each zone is typically set in the range of about -60°C to about 25°C relative to the melt temperature of the liquid crystal polymer. As an example, the mixture can be melted using a twin-screw extruder such as a Leistritz 18mm co-rotating fully meshed twin-screw extruder. The mixture can be melted using a general-purpose screw design. In one embodiment, the mixture containing all the components may be fed by a positive displacement feeder into a feed port in a first barrel. In another embodiment, different components may be added at different addition points in the extruder, as known. For example, a liquid crystal polymer may be applied at a feed port, and a specific additive (e.g., a dielectric filler) may be supplied in the same or a different temperature zone located downstream from there. Nevertheless, the resulting mixture can be melted, mixed, and then extruded through a die. The extruded polymer composition can then be quenched and solidified in a water bath, granulated in a pelletizer, and then dried.

[0042]

[0045] Despite containing bio-LCP, the polymer composition can nevertheless exhibit a variety of properties similar to those formed from conventional types of liquid crystal polymers. For example, the polymer composition may exhibit excellent melt processability. For instance, the polymer composition can be processed at a shear rate of 1,000 seconds according to ISO 11443:2021. -1The polymer composition may have an ultra-low melt viscosity, such as about 0.1 to about 100 Pa·s, about 0.2 to about 75 Pa·s in some embodiments, about 0.5 to about 65 Pa·s in some embodiments, about 0.1 to about 50 Pa·s in some embodiments, about 0.2 to about 45 Pa·s in some embodiments, about 0.5 to about 40 Pa·s in some embodiments, and about 1 to about 35 Pa·s in some embodiments, determined at a temperature about 15°C higher than the melt temperature of the polymer composition. The polymer composition may also have excellent thermal properties. The melt temperature of the composition may be, for example, about 280°C to about 400°C, about 290°C to about 380°C in some embodiments, and about 300°C to about 350°C in some embodiments. Even at such melt temperatures, the ratio of the temperature of deflection under load ("DTUL"), a measure of short-term heat resistance, to the melt temperature may still remain relatively high. For example, the ratio may range from about 0.5 to about 1.00, in some embodiments from about 0.6 to about 0.95, and in some embodiments from about 0.65 to about 0.85. Specific DTUL values ​​may be, for example, about 200°C or higher, in some embodiments from about 220°C or higher, in some embodiments from about 230°C to about 300°C, and in some embodiments from about 240°C to about 280°C. Such high DTUL values ​​can, in particular, enable the use of fast and reliable surface mounting processes for mating the structure with other parts.

[0046] The polymer composition may also have high impact strength, which is useful when forming thin layers. The composition is determined, for example, to be about 0.5 kJ / m² at a temperature of 23°C according to ISO test No. ISO179-1:2010. 2 In some embodiments described above, the load is approximately 1 to approximately 60 kJ / m³. 2 In some embodiments, the load is approximately 2 to 50 kJ / m³. 2 In some embodiments, approximately 5 to approximately 45 kJ / m³ 2It may have a Charpy notch impact strength. The tensile and flexural mechanical properties of the composition may also be good. For example, the polymer composition may have a tensile strength of about 20 to about 500 MPa, about 50 to about 400 MPa in some embodiments, and about 70 to about 350 MPa in some embodiments; a tensile fracture strain of about 0.4% or more, about 0.5% to about 10% in some embodiments, and about 0.6% to about 3.5% in some embodiments; and / or a tensile modulus of about 5,000 MPa to about 20,000 MPa, about 8,000 MPa to about 20,000 MPa in some embodiments, and about 10,000 MPa to about 20,000 MPa in some embodiments. The tensile properties may be determined at a temperature of 23°C according to ISO Test No. 527:2019. The polymer composition may also exhibit a flexural strength of about 20 to about 500 MPa, about 50 to about 400 MPa in some embodiments, and about 100 to about 350 MPa in some embodiments; a flexural elongation of about 0.4% or more, about 0.5% to about 10% in some embodiments, and about 0.6% to about 3.5% in some embodiments; and / or a flexural modulus of about 5,000 MPa to about 20,000 MPa, about 8,000 MPa to about 20,000 MPa in some embodiments, and about 10,000 MPa to about 15,000 MPa in some embodiments. The flexural properties may be determined at a temperature of 23°C according to 178:2019.

[0043]

[0047] Once formed, the polymer composition may be molded into any of a variety of different molded parts using techniques known in the art. For example, the molded parts may be molded using a one-component injection molding process in which dried and preheated plastic granules are injected into a mold. Regardless of the molding technique used, the polymer composition is suitable for forming electronic parts with small dimensional tolerances. Such parts include at least one micro-sized dimension (e.g., thickness, width, height, etc.), such as generally about 500 micrometers or less, about 50 to about 450 micrometers in some embodiments, and about 100 to about 400 micrometers in some embodiments.

[0044]

[0048] One such component is a fine-pitch electrical connector. More specifically, such electrical connectors are often used to detachably mount a central processing unit ("CPU") to a printed circuit board. The connector may include insertion passages configured to receive contact pins. These passages are defined by opposing walls, which may be formed from a thermoplastic resin. To help achieve desired electrical performance, the pitch of these pins is generally small to accommodate the large number of contact pins required within a given space. This, in turn, necessitates a small pitch for the pin insertion passages and the width of the opposing walls separating those passages. For example, the walls may have a width of about 500 micrometers or less, about 50 to about 450 micrometers in some embodiments, and about 100 to about 400 micrometers in some embodiments. The polymer compositions of the present invention are particularly suitable for forming the walls of a fine-pitch connector. It should also be understood that, in addition to, or instead of, the walls, any other parts of the connector housing may also be formed from the polymer composition. For example, the connector may also include a shield surrounding the housing. Part or all of the shield may be formed from the polymer composition. For example, the housing and shield may each be a one-piece structure integrally molded from a polymer composition. Similarly, the shield may be a two-piece structure comprising a first shell and a second shell, each of which may be formed from a polymer composition.

[0045]

[0049] Naturally, polymer compositions can also be used in a wide variety of other components. For example, polymer compositions may be molded onto planar substrates for use in electronic components. The substrates may be thin, having a thickness of about 500 micrometers or less, about 50 to about 450 micrometers in some embodiments, and about 100 to about 400 micrometers in some embodiments. In one embodiment, for example, one or more conductive elements can be applied to the planar substrate using various known techniques (e.g., laser direct structuring, electroplating, etc.). The conductive elements can serve a variety of different purposes. In one embodiment, for example, the conductive elements form an integrated circuit, such as one used in a SIM card. In another embodiment, the conductive elements form various different types of antennas, such as antennas with resonant elements formed from patch antenna structures, inverted F antenna structures, closed and open slot antenna structures, loop antenna structures, monopoles, dipoles, planar inverted F antenna structures, and hybrids of these designs. The resulting antenna structures can be incorporated into housings of relatively compact portable electronic components, such as those described above, where the available internal space is relatively small.

[0046]

[0050] Planar substrates formed from the polymer compositions described above may be used for other applications. For example, in one embodiment, the planar substrate may be used to form the base of a compact camera module ("CCM") commonly used in wireless communication devices (e.g., mobile phones). The compact camera module may include a lens assembly that overlaps the base. The base, in turn, overlaps an optional main substrate. Due to their relatively thin nature, the base and / or main substrate are particularly well suited to being formed from the polymer compositions described above. The lens assembly may have any of the various configurations known in the art and may include fixed-focus lenses and / or autofocus lenses. In one embodiment, for example, the lens assembly may be in the form of a hollow lens barrel housing the lens, which is positioned on the main substrate and communicates with an image sensor controlled by a circuit. The lens barrel may have any of various shapes, such as rectangular or cylindrical. In certain embodiments, the lens barrel may also be formed from the polymer composition and have wall thicknesses within the range described above. It should be understood that other parts of the camera module may also be formed from the polymer composition. For example, a polymer film (e.g., a polyester film) and / or a thermal insulating cap may cover the lens assembly. In some embodiments, the film and / or cap may also be formed from a polymer composition.

[0047]

[0051] Other possible electronic components that can utilize polymer compositions include, for example, mobile phones, laptop computers, small portable computers (e.g., ultraportable computers, netbooks, and tablet computers), wristwatch devices, pendant devices, headphones and earphone devices, media players with wireless communication capabilities, handheld computers (sometimes called personal digital assistants), remote controllers, global positioning system (GPS) devices, handheld game devices, battery covers, speakers, camera modules, integrated circuits (e.g., SIM cards), housings for electronic devices, electrical control devices, circuit breakers, switches, power electronics, and printer parts.

[0048]

[0052] The following test methods can be used to determine one or more of the characteristics identified above.

[0053] Melt viscosity: Melt viscosity (Pa·s) was measured using a Dynisco LCR7001 capillary rheometer at a shear rate of 400 s⁻¹. -1 or 1,000s -1 The temperature may be determined according to ISO 11443:2021 at a temperature 15°C higher than the melting temperature (e.g., approximately 325°C). The rheometer orifice (die) may have a diameter of 1 mm, a length of 20 mm, an L / D ratio of 20.1, and an inlet angle of 180°. The barrel diameter may be 9.55 mm + 0.005 mm, and the rod length may be 233.4 mm.

[0049]

[0054] Melting temperature: The melting temperature ("Tm") can be determined by differential scanning calorimetry ("DSC"), as is well known in the art. The melting temperature is the differential scanning calorimetry (DSC) peak melting temperature as determined by ISO 11357-3:2018. In the DSC procedure, the sample was heated and cooled at 20°C per minute using DSC measurements performed on a TA Q2000 Instrument, as described in ISO standard 10350.

[0050]

[0055] Temperature of deflection under load ("DTUL"): The temperature of deflection under load can be determined according to ISO 75-2:2013 (technically equivalent to ASTM D648). More specifically, a test specimen having a length of 80 mm, a thickness of 10 mm, and a width of 4 mm may be subjected to an edgewise three-point bending test with a specified load (maximum outer fiber stress) of 1.8 megapascals. The specimen may be lowered in a silicone oil bath with a temperature increase of 2°C per minute until it deflects by 0.25 mm (0.32 mm in ISO test No. 75-2:2013).

[0051]

[0056] Tensile modulus, tensile stress, and tensile elongation: Tensile properties can be tested according to ISO 527:2019 (technically equivalent to ASTM D638). Measurements of modulus and strength may be performed on identical test specimens having a length of 80 mm, a thickness of 10 mm, and a width of 4 mm. The test temperature may be 23°C, and the test speed may be 1 or 5 mm / min.

[0052]

[0057] Bending modulus, bending stress, and bending elongation: Bending properties can be tested according to ISO 178:2019 (technically equivalent to ASTM D790). This test can be carried out with a support span of 64 mm. The test may be performed on the central portion of an uncut ISO 3167 multipurpose bar. The test temperature may be 23°C and the test speed may be 2 mm / min.

[0053]

[0058] Charpy impact strength: Charpy impact strength can be tested according to ISO 179-1:2010 (technically equivalent to ASTM D256-10, Method B). This test can be performed using a Type 1 specimen size (length 80 mm, width 10 mm, and thickness 4 mm). When testing impact strength with a notch, the notch may be a Type A notch (bottom radius 0.25 mm). The specimen can be cut from the center of a multipurpose bar using a single-tooth milling machine. The test temperature may be 23°C.

[0054]

[0059] These and other modifications and variations of the present invention may be practiced by those skilled in the art without departing from the spirit and scope of the invention. In addition, it should be understood that the various embodiments are interchangeable, either in whole or in part. Furthermore, those skilled in the art will understand that the foregoing description is for illustrative purposes only and is not intended to limit the invention to what is further described in such appended claims.

Claims

1. A method for forming a biohydroxybenzoic acid monomer for use in liquid crystal polymers, A step of providing biophenols derived from bionaphtha, The steps include treating the biophenol with an alkali metal hydroxide to form an alkali metal phenolate, and The step of heating the alkali metal phenolate in the presence of carbon dioxide to form the biohydroxybenzoic acid monomer. Methods that include...

2. The method according to claim 1, wherein the alkali metal hydroxide comprises potassium hydroxide and the alkali metal phenolate comprises potassium phenolate.

3. The method according to claim 1, wherein the heating is performed at a temperature of approximately 230°C to approximately 450°C.

4. The method according to claim 1, wherein the carbon dioxide is under atmospheric pressure.

5. The method according to claim 1, wherein the carbon dioxide is under pressure.

6. The method according to claim 1, wherein the biophenol is formed by oxidizing biocumene to form a hydroperoxide radical, and then cleaving the cumene hydroperoxide radical in the presence of an acid catalyst to form the biophenol, and the biocumene is derived from the bionaphtha.

7. The method according to claim 6, wherein the biocumene is formed by alkylating biobenzene, and the biobenzene is derived from bionaphtha.

8. The method according to claim 7, wherein the bionaphtha is subjected to a steam decomposition process to form the biobenzene.

9. The method according to claim 1, wherein the bionaphtha is formed from a biodistillate raw material comprising a naturally occurring complex mixture of fats and / or oils.

10. The method according to claim 9, wherein the biodistillate raw materials include fats and / or oils derived from cotton, coconut, corn, palm, peanut, flaxseed, rice, rapeseed, olive, soybean, sunflower, linola, animal fat, tall, castor, butter, milk, or a combination thereof.

11. The method according to claim 9, wherein the bionaphtha is formed by a method comprising fractionating the biodistillate raw material into a substantially liquid triglyceride phase L and a saturated or substantially saturated solid or substantially solid triglyceride phase S, and the bionaphtha is derived from phase S.

12. The method according to claim 1, wherein the biohydroxybenzoic acid monomer is bio-4-hydroxybenzoic acid.

13. Biohydroxybenzoic acid formed by the method according to claim 1.

14. A bioliquid crystal polymer comprising repeating units derived from biohydroxybenzoic acid as described in claim 13.

15. A bioliquid crystal polymer comprising repeating units derived from one or more aromatic hydroxycarboxylic acids, optional repeating units derived from one or more dicarboxylic acids, and optional repeating units derived from one or more aromatic diols, wherein the one or more aromatic hydroxycarboxylic acids include bio-4-hydroxybenzoic acid derived from bionaphtha.

16. The bio-liquid crystal polymer according to claim 14, comprising repeating units derived from bio-4-hydroxybenzoic acid in an amount of 40 mol.% to about 85 mol.%.

17. The bioliquid crystal polymer according to claim 14, further comprising repeating units derived from 2-hydroxy-6-naphthoic acid, terephthalic acid, isophthalic acid, 2,6-naphthylenedicarboxylic acid, hydroquinone, 4,4'-biphenol, 4-aminophenol, acetaminophen, or a combination thereof.

18. The bioliquid crystal polymer according to claim 14, wherein the thermotropic liquid crystal polymer is fully aromatic.

19. The bioliquid crystal polymer according to claim 14, wherein the polymer composition has a melting temperature of about 280°C to about 400°C.

20. The bio-liquid crystal polymer according to claim 14, having a bio-content of about 5 wt.% to 70 wt.% relative to the total weight of monomers used in the polymer.

21. The polymer composition according to claim 14, comprising the bio-liquid crystal polymer and one or more optionally selected additives.

22. The polymer composition according to claim 21, wherein the polymer composition has a sustained content of about 10 wt.% to 90 wt.% based on the total weight of the composition.

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