Biobiphenols for use in the formation of bioliquid crystal polymers

Abstract

A technology is provided for forming bio-based biphenol monomers derived from bionaphtha (e.g., "bio-BP") and bio-liquid crystal polymers ("bio-LCP") formed therefrom.

Description

[Technical Field]

[0001] Related applications

[0001] This application is based on U.S. Provisional Patent Application No. 63 / 495,160, filed on 10 April 2023, which is incorporated herein by reference, and claims priority therefrom. [Background technology]

[0002] Background of the Invention

[0002] Liquid crystal polymers are commonly used in a 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. BP constitutes a significant portion of the aromatic diols employed in many commercial liquid crystal polymers. Convention Historically, BP has produced its products from crude oil through catalytic cracking processes. However, in recent years, there has been a growing need for a more carbon-neutral approach. To be carbon-neutral, companies must remove the same amount of carbon dioxide they release into the atmosphere to achieve net-zero carbon emissions. Carbon-negative companies, on the other hand, remove more carbon from the atmosphere than they release. Given the considerable efforts of companies worldwide to become carbon-neutral or carbon-negative, there is a need for processes to produce biphenol and liquid crystal polymers in a more sustainable way without significantly altering the properties of such polymers. [Overview of the project]

[0003]

[0003] According to one embodiment of the present invention, a method for forming biobiphenol monomers for use in liquid crystal polymers is disclosed. The method includes providing a biodialkylphenol derived from bionaphtha; oxidatively coupling the biodialkylphenol to form an alkylated biphenol; and dealkylating the alkylated phenol to form a biobiphenol.

[0004]

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

[0005]

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

[0006]

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

[0007] Generally speaking, this disclosure is directed to technologies for forming bio-based biphenol monomers derived from bionaphtha and bio-liquid crystal polymers ("bio-LCPs") formed therefrom. Ultimately, bio-LCPs and compositions formed from such polymers can be certified under the ISCC+ criteria specified by the International Sustainability and Carbon Certification ("ISCC") system. ISCC is a globally applicable sustainability certification system that covers all sustainable raw materials, including agricultural and forest biomass, circular and bio-based materials, and renewable energy sources. ISCC follows a mass balance approach in which the renewable amount of polymers can be verified. In mass balance, renewable raw materials are allocated to selected products according to their individual formulations, taking into account all yields and losses. Only raw materials used as raw materials for production (not for energy) are considered for mass balance. Key criteria used to apply the mass balance approach include feedstock qualification, chain of custody, and product claim. The mass balance approach allows for tracking the quantity and sustainability characteristics of recycled and / or bio-based raw materials throughout the value chain and attributing them to the final product in a verifiable manner. In one embodiment, the liquid crystal polymers described herein can be produced from carbon-negative or carbon-neutral components under the mass balance approach.

[0007]

[0008] Herein, various embodiments of the present invention will be described in more detail. I. Biobiphenol

[0009] As stated above, the biobiphenols of this disclosure are derived from "bio-naphtha." The term "bio-naphtha" generally refers to naphtha produced from renewable sources. Bio-naphtha is a hydrocarbon composition and mainly contains 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 provided, typically comprising complex mixtures of naturally occurring fats and / or oils, e.g., vegetable fats and oils (e.g., cotton, coconut, corn, palm, peanut, linseed, rice, rapeseed, olive, soybean, sunflower, linola, animal fat, tall, castor, etc.), as well as animal fats and oils (e.g., butter or milk fat). Raw materials may be supplied in an unused (unprocessed) state and / or may be obtained from waste such as edible oils, highly saturated oils unsuitable for consumption, waste cooking oils, by-products of vegetable oil refining, and mixtures thereof. Natural fats and oils mainly contain triglycerides and some free fatty acids (FFAs). Many different types of triglycerides are produced naturally, either from plants or animals. Fatty acids in fats and oils have been found to be esterified to glycerol (triacylglycerol). The acyl group is a long chain (C) with a carboxyl group at the end. 12 ~C 22) are hydrocarbons, and generally the carboxyl group is 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. Sources of the aforementioned fats and / or oils include, for example, saturated fatty acids (e.g., caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, arachidin, behenic acid, lignoceric acid, etc.) and / or unsaturated fatty acids (e.g., myristoleic acid, palmitoleic acid, heptadecenoic acid, oleic acid, linoleic acid, linolenic acid, gadolenic acid, ricinoleic acid, rosin, etc.). Tall oils, for example, contain myristic acid, stearic acid, arachidic acid, oleic acid, linoleic acid, and gadolenic acid.

[0008]

[0010] Biodistillate raw materials can be classified as follows based on their free fatty acid (FFA) content: refined oils, e.g., soybean oil or refined canola oil (FFA < 1.5%); yellow grease and animal fats with low free fatty acid content (FFA < 4%); and grease and animal fats with high free fatty acid content (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 components other than triglycerides and fatty acids. Physical refining, for example, by steam stripping, can remove FFAs as well as unsaponifiable matter and other impurities, thus eliminating the formation of soap stock and minimizing the loss of neutral oil. However, degumming pretreatment of crude fats and oils may be necessary to remove impurities that may cause discoloration or result in a low-quality product when heated to the temperature required for steam distillation. The degumming process may involve treating crude oil with water, a saline solution, enzymes, caustic soda, or a dilute acid such as phosphoric acid, citric acid, or maleic acid to remove phospholipids, waxes, oxidation promoters, and other impurities. The degumming process converts phospholipids 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 can then be converted to linear or substantially linear paraffin as "bio-naphtha". More specifically, the refined oil can be separated into phase L and phase S by a fractional crystallization method, which includes a controlled cooldown during which the triglycerides of the composite mixture having substantially saturated acyl portions crystallize and precipitate from the mixture constituting phase S, while the triglycerides having substantially unsaturated acyl portions remain liquid and form phase L, and then both phases are separated by simple filtration or decantation or centrifugation. In one embodiment, fractionation may be "dry fractionation" or "dry winterization," which is the removal of solids by controlled crystallization and separation techniques involving the use of a solvent or dry treatment (sometimes also called dewaxing). The fractionation process has two main stages, the first of which is the crystallization stage. Crystals grow as the temperature of the molten fats and oils or their solutions decreases, and their solubility at the final temperature or separation temperature determines the triglyceride composition of the formed crystals and their mother liquor. The separation process is the second fractionation step. Several options may be employed, such as vacuum filters, centrifugal separators, 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 can be converted to linear or substantially linear paraffins as bionaphtha via known processes, for example, 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 employed and ultimately involves the removal of oxygen atoms from fats and oils. Hydrogenation is preferentially carried out in continuous fixed-bed reactors, continuous stirred tank reactors, or slurry-type reactors containing solid catalysts. The catalyst may contain, as the catalytically active phase, Ni, Mo, Co, or mixtures of these, such as NiW, NiMo, CoMo, NiCoW, NiCoMo, NiMoW, and CoMoW oxides or sulfides, preferably supported by high-surface-area carbon, alumina, silica, titania, or zirconia, or a mixture of Group 10 (Ni, Pt, or Pd) or Group 11 (Cu or Ag) metals or alloys, supported by high-surface-area carbon, magnesia, zinc oxide, spinel (Mg2Al2O4, ZnAl2O4), perovskite (BaTiO3, ZnTiO3), calcium silicate (e.g., xonotlite), alumina, silica, or mixtures thereof. The support for the catalytically active phase preferably exhibits low acidity, preferably neutral or basic, in order to avoid branched paraffin and hydrogen isomerization reactions that can lead to cracking. Hydrogen deoxygenation may be carried out at a temperature of approximately 200°C to approximately 500°C, or in some embodiments, at a temperature of approximately 280°C to approximately 400°C, under a pressure of approximately 1 MPa to approximately 10 MPa, with a hydrogen-to-refined oil ratio of approximately 100 to approximately 2000, or in some embodiments, approximately 350 to approximately 1500.

[0011]

[0013] The resulting bionaphtha-containing raw material, regardless of the method of its formation, may be subjected to a steam cracking process to obtain bioaromatic compounds (e.g., biobenzene). A steam cracker is a complex industrial facility that can be divided into three main zones, each of which has several types of equipment with very specific functions: (i) the high-temperature zone includes a high-temperature decomposition or cracking furnace, a quench heat exchanger and quench ring, and columns for a high-temperature separation train; (ii) the compression zone includes a compressor for the cracked gas, purification and separation columns, and a dryer; and (iii) the low-temperature zone includes a cold box, a de-methanizer, fractionation columns for a low-temperature separation train, C2 and C3 converters, and a gasoline hydrostabilization reactor. Hydrocarbon cracking may be carried out in a tubular reactor in a direct-combustion heater (furnace). Various tube sizes and arrangements can be used, for example, coiled tubes, U-tubes, or straight tube layouts can be used. Each furnace consists of a convection zone where waste heat is recovered and a radiation zone where high-temperature decomposition occurs. The raw material-steam mixture is preheated to approximately 530-650°C in the convection zone, or the raw material is preheated in the convection section, then mixed with diluted steam, and then flows over the radiation zone where high-temperature decomposition occurs at temperatures ranging from 750 to 950°C. The steam / raw material (steam / [hydrocarbon raw material]) weight ratio can be approximately 0.2 to approximately 1.0 kg / kg. With respect to steam cracking furnaces, their severity can be adjusted by temperature, residence time, total pressure, and partial pressure of hydrocarbons. Effluent from the high-temperature cracking reactor contains unreacted raw materials, olefins (mainly ethylene and propylene), hydrogen, methane, a mixture of C4 compounds (mainly isobutylene and butadiene), aromatic compounds in the C6-C8 range, ethane, propane, diolefins (acetylene, methylacetylene, propadiene), and heavy hydrocarbons that boil within the fuel oil temperature range.The cracked gas is rapidly quenched to 338-510°C to stop the high-temperature decomposition reaction, minimize the 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 specific method for separating aromatic hydrocarbons from a mixture of aromatic and aliphatic hydrocarbons is solvent extraction, described, for example, in WO2012 / 135111, which is incorporated herein by reference. Preferred solvents used in aromatic solvent extraction are sulfolane, tetraethylene glycol, and N-methylpyrrolidone, which are commonly used solvents in commercial aromatic compound extraction processes. These chemical species are often used in combination with other solvents or other chemicals such as water and / or alcohols (sometimes called co-solvents). Nitrogen-free solvents, such as sulfolane, are particularly preferred. Solvent extraction of heavy aromatic compounds is described in the art; see, for example, U.S. Patent No. 880,325, which is incorporated herein by reference in its entirety. Alternatively, other known methods besides solvent extraction, such as molecular sieving or boiling point-based separation, can be applied to the separation of heavy aromatic compounds in the dearomatic process.

[0013]

[0015] Once biobenzene is obtained, it can then be converted to biophenol, which is the reactant employed in the production of biobiphenol. In this regard, biobenzene can 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 can 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 zeolite oxide). 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, some polyisopropylbenzene is also formed, and such polyisopropylbenzene is mainly disubstituted and trisubstituted propylbenzene. To minimize the production of dialkylation products of benzene, it is generally desirable to maintain an excess molar concentration of benzene across the reaction zone in a benzene-to-propylene ratio of about 4:1 to about 16:1, more preferably about 8:1. A transalkylation reactor may be used to transalkylate the polyisopropylbenzene produced in the alkylation reactor to form additional cumene. Preferred conditions and catalysts may be the same as those described for the alkylation reactor. The alkylation and transalkylation effluents are subjected to separation operations using a distillation column, as described in U.S. Patent Publication 2008 / 0293986, etc., incorporated herein by reference, to separate the benzene, cumene product, polyisopropylbenzene, and byproduct streams. For example, a first distillation column may be employed to recover excess benzene from the reactor effluent. The overhead of the benzene column is mostly benzene, which is typically recycled for alkylation and transalkylation. A second distillation column may be employed 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 may also be employed, which is a polyisopropylbenzene column used to recover a polyisopropylbenzene recycling stream from the bottom of the cumene column. The polyisopropylbenzene is recovered as overhead from the polyisopropylbenzene column and is typically recycled for transalkylation.

[0015]

[0017] Biocumene, once formed, then reacts using a process known as the "cumene process" to form biophenols. More specifically, biocumene is first oxidized to produce cumene hydroperoxide radicals. This can occur via the oxidation of cumene in an alkaline medium where the hydroperoxide product is stable. Biocumene may be emulsified with an emulsifier such as sodium stearate in an aqueous alkaline solution such as sodium carbonate at a pH of 8.5–10.5. Oxidation in air or oxygen may be carried out at a moderately high 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 byproducts. The acid catalyst employed may be any acidic material, such as phosphoric acid, sulfuric acid, and SO2. For example, cumene hydroperoxide may be treated with dilute sulfuric acid (5–25 percent concentration) at a temperature of about 50°C–70°C. After the cutting 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] Subsequently, the biophenol may be converted to a biobiphenol. For example, the biophenol may first be alkylated in the presence of a solid alkylation catalyst (e.g., aluminum phenoxide) via Friedel-Crafts alkylation of a hydrocarbon (e.g., isobutene). Such a process is well known in the art and is described, for example, in U.S. Patent No. 2,684,389, which is incorporated herein by reference. This reaction can form biodialkylphenols, such as bio-2,4-di-tert-butylphenol and / or bio-2,6-di-tert-butylphenol, according to the following reaction scheme: C6H5OH+2CH2=C(CH3)2→((CH3)3C)2C6H3OH

[0019] Dialkylphenols (at least one of which is a biodialkylphenol) are, once formed, oxidatively coupled to form biobiphenols. Such oxidative coupling reactions are described, for example, in U.S. Patent Publication 2003 / 0050515, which is incorporated herein by reference. In one embodiment, for example, bio-2,4-dialkylphenol and / or bio-2,6-dialkylphenol are oxidatively coupled together, either alone or in combination, in the presence of a catalyst (e.g., a copper-amino complex) to produce a bioalkylated biphenol (e.g., bio-2,2',6,6'-tetraalkyl-4,4'-biphenol). In some cases, a one-step reaction scheme may be employed. Alternatively, a multi-step reaction scheme in which 2,4-dialkylphenol and / or 2,6-dialkylphenol are reacted in a stepwise manner may also be employed. For example, the first step may involve the synthesis of an alkylated diphenoquinone (e.g., 3,3',5,5'-tetraalkyl-4,4'-diphenoquinone) using oxygen as an oxidizing agent for coupling 2,6-dialkylphenol. The second step may involve the synthesis of an alkylated biphenol (e.g., 2,2',6,6'-tetraalkyl-4,4'-biphenol) using 3,3',5,5'-tetraalkyl-4,4'-diphenoquinone as an oxidizing agent for coupling 2,6-dialkylphenol.

[0017]

[0020] If necessary, the dialkylphenol (e.g., 2,6-dialkylphenol) may first be dissolved in a solvent (e.g., methanol, ethanol, isopropanol, butanol, etc.). Typically, an excess of phenol is used in the reaction. The reaction temperature may easily and typically be in the range of about 30°C to about 50°C. Typically, after approximately 35-40% of the initial 2,6-dialkylphenol has been converted to the corresponding 3,3',5,5'-tetraalkyl-4,4'-diphenoquinone, the addition of oxygen may be stopped and the reaction may proceed in the absence of oxygen. At this stage, the solvent may be removed by distillation for reuse, and then the water produced as a byproduct of the reaction is removed by distillation at a higher temperature. For the second step of the reaction, the temperature may be raised typically to about 130°C to about 160°C to maintain the reaction mixture in liquid form. The presence of the catalyst allows the intermediate 3,3',5,5'-tetraalkyl-4,4'-diphenoquinone to function as an oxidizing agent for the subsequent coupling of 2,6-dialkylphenol. After the consumption of 3,3',5,5'-tetraalkyl-4,4'-diphenoquinone, the reaction mixture generally contains about 70-80% 2,2',6,6'-tetraalkyl-4,4'-biphenol and 20-30% 2,6-dialkylphenol. The reaction mixture is then cooled to approximately 60°C, and the solvent is added back to the reaction mixture. The 2,2',6,6'-tetraalkyl-4,4'-biphenol can be completely precipitated within a few minutes and removed by filtration or centrifugation, while the 2,6-dialkylphenol and the active catalyst remain in the filtrate. After the addition of fresh 2,6-dialkylphenol and an optional fresh catalyst, these mother liquors can be reused to initiate another cycle of 2,2',6,6'-tetraalkyl-4,4'-biphenol production.

[0018]

[0021] Thereafter, biobisphenol (e.g., bio-4,4'-bisphenol) can be produced from alkylated bisphenol (e.g., 2,2',6,6'-tetra-t-butyl-4,4'-bisphenol) via dealkylation. The dealkylation method may include contacting the alkylated bisphenol with an acid (or an optional mixture containing an acid and a solvent). The dealkylation reaction is usually carried out at a temperature of about 130 to about 170 °C. Examples of suitable solvents that can be employed in the reaction mixture include, for example, hydrocarbons having 7 to 9 carbons, and halogenated hydrocarbons having a boiling point of about 80 to about 130 °C. Examples of suitable acids that can be used in dealkylation include, for example, sulfonic acids such as methanesulfonic acid, sulfuric acid, toluenesulfonic acid, aluminum phenoxide, and the like.

[0019] II. Bio-liquid crystal polymer ("Bio-LCP")

[0022] As described above, the resulting biobiphenols may be particularly suitable for use in forming bio-based liquid crystal polymers ("bio-LCPs"). Bio-LCPs generally contain aromatic repeating units derived from the biobiphenols described above. Examples of such biphenols include, for example, 4,4'-biphenol, 3,3'-dihydroxybiphenyl, 3,4'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl ether, bis(4-hydroxyphenyl)ethane, and their alkyl, alkoxy, aryl, and halogen substituents, as well as combinations thereof. Particularly preferred is bio-4,4'-biphenol ("bio-BP"). Preferably, all biphenols used in the liquid crystal polymer are biobiphenols derived from bionaphtha. However, this is by no means required, and some of such biphenols may also be derived from conventional fossil fuel sources (e.g., petroleum), as is known in the art. In any case, the repeating units derived from biphenols (e.g., biobiphenols) typically constitute about 1 mol.% to about 50 mol.% of the polymer, in some embodiments about 5 mol.% to about 40 mol.% and in some embodiments about 10 mol.% to about 35 mol.%. In one particular embodiment, for example, a liquid crystal polymer may contain repeating units derived from bio-BP in amounts of 6 mol.% to about 30 mol.%, in some embodiments about 8 mol.% to about 28 mol.% and in some embodiments about 10 mol.% to about 25 mol.%.

[0020]

[0023] Bio-LCP may also contain aromatic repeating units derived from other types of aromatic diols, and such aromatic repeating units include, for example, hydroxyphenols, naphthenic diols, etc., such as hydroquinone, resorcinol, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, etc. In addition, their alkyl, alkoxy, aryl and halogen substituents, as well as combinations thereof are included. Particularly preferred other aromatic diols include, for example, hydroquinone (“HQ”). When employed, repeating units (e.g., HQ) derived from such other aromatic diols typically constitute from about 1 mol.% to about 50 mol.% of the polymer, in some embodiments from about 5 mol.% to about 40 mol.%, and in some embodiments from about 10 mol.% to about 35 mol.%.

[0021]

[0024] Aromatic hydroxycarboxylic acids may also be used, and examples of such aromatic hydroxycarboxylic acids include hydroxybenzoic acids (e.g., 4-hydroxybenzoic acid, 4'-hydroxyphenyl-4-benzoic acid, 3'-hydroxyphenyl-4-benzoic acid, 4'-hydroxyphenyl-3-benzoic acid, etc.); hydroxynaphthenic acids (e.g., 2-hydroxy-6-naphthoic acid ("HNA"), 2-hydroxy-5-naphthoic acid, 3-hydroxy-2-naphthoic acid, 2-hydroxy-3-naphthoic acid, etc.), as well as their alkyl, alkoxy, aryl, and halogen substituents. Particularly preferred are bio-4-hydroxybenzoic acid ("HBA") and 2-hydroxy-6-naphthoic acid. When adopted, repeating units derived from hydroxybenzoic acid typically constitute about 20 mol.% to about 85 mol.% of the polymer, in some embodiments about 30 mol.% to about 80 mol.% and in some embodiments about 40 mol.% to about 75 mol.%; and repeating units derived from hydroxynaphthenic acid typically constitute about 1 mol.% to about 50 mol.% of the polymer, in some embodiments about 2 mol.% to about 40 mol.% and in some embodiments about 5 mol.% to 30 mol.%. In one particular embodiment, for example, a liquid crystal polymer may contain repeating units derived from HBA in amounts of 40 mol.% to about 85 mol.%, in some embodiments about 45 mol.% to about 82 mol.% and in some embodiments about 50 mol.% to about 80 mol.%.

[0022]

[0025] Aromatic dicarboxylic acid repeating units derived from aromatic dicarboxylic acids may also be used, 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 their alkyl, alkoxy, aryl, and halogen substituents, as well as combinations thereof. Particularly preferred aromatic dicarboxylic acids include, for example, terephthalic acid ("TA"), isophthalic acid ("IA"), and 2,6-naphthalenedicarboxylic acid ("NDA"). Repeating units derived from aromatic dicarboxylic acids (e.g., IA, TA, and / or NDA), when employed, 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. Repeating units such as those derived from aromatic amides (e.g., acetaminophen ("APAP")) and / or those derived from aromatic amines (e.g., 4-aminophenol ("AP"), 3-aminophenol, 1,4-phenylenediamine, 1,3-phenylenediamine, etc.) may also be employed. Repeating units derived from aromatic amides (e.g., APAP) and / or those derived from aromatic amines (e.g., AP), when employed, 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 mol.% in some embodiments. It will 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, amines, etc.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.

[0023]

[0026] Regardless of the specific components and properties of the polymer, bio-LCPs can be prepared by first introducing aromatic monomers used to form repeating units (e.g., aromatic hydroxycarboxylic acids, aromatic dicarboxylic acids, etc.) and / or other repeating units (e.g., aromatic diols, aromatic amides, aromatic amines, etc.) into a reactor vessel to initiate a polycondensation reaction. Specific conditions and steps employed in such reactions are well known. Calundann U.S. Patent No. 4,161,470; Linstid, III et al. U.S. Patent No. 5,616,680; Linstid, III et al. U.S. Patent No. 6,114,492; Shepherd et al. U.S. Patent No. 6,514,611; and Waggoner Further details may be found in WO2004 / 058851. The vessel used in the reaction is not particularly limited, but it is generally preferable to use one that is commonly used in reactions of high-viscosity fluids. Examples of such reaction vessels include agitated tank-type devices with stirrers having variable-shaped stirring blades, such as anchor-type, multi-stage-type, spiral ribbon-type, screw shaft-type, or modified shapes thereof. Further examples of such reaction vessels include mixing devices commonly used for kneading resins, such as kneaders, roll mills, and Banbury mixers.

[0024]

[0027] If necessary, the reaction may proceed via monomer acetylation known in the art. This can be achieved by adding an acetylating agent (e.g., acetic anhydride) to the monomer. Acetylation is generally initiated at a temperature of about 90°C. During the initial stages of acetylation, reflux may be employed to maintain the vapor phase temperature below the point at which the acetic acid byproduct and anhydride begin to distill. The temperature during acetylation is typically in the range of 90°C to 150°C, and in some embodiments, in the range of about 110°C to about 150°C. When reflux is used, the vapor phase temperature is typically above the boiling point of acetic acid but remains low enough to retain any residual acetic anhydride. For example, acetic anhydride evaporates at a temperature of about 140°C. Therefore, it is particularly desirable to provide the reactor with a vapor phase reflux at a temperature of about 110°C to about 130°C. To ensure a substantially complete reaction, an excess of acetic anhydride may be employed. The amount of excess anhydride is expected to vary depending on the specific acetylation conditions employed, such as the presence or absence of reflux. The use of an excess of approximately 1 to 10 mole percent of acetic anhydride, based on the total moles of hydroxyl groups in the reactants, is not uncommon.

[0025]

[0028] Acetylation may be carried out in a separate reactor vessel or in situ within the polymerization reactor vessel. If a separate reactor vessel is used, one or more monomers may be introduced into the acetylation reactor and then transferred to the polymerization reactor. Similarly, one or more monomers may be introduced directly into the reactor vessel without prior acetylation.

[0026]

[0029] In addition to monomers and optional acetylating agents, other components may be included in the reaction mixture to facilitate polymerization. For example, catalysts may be optionally employed, 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). Such catalysts are typically used in amounts of about 50 to about 500 ppm (parts per million), based on the total weight of the repeating unit precursors. If a separate reactor is employed, it is typically preferable, but not necessarily, that the catalyst be applied to the acetylation reactor rather than the polymerization reactor.

[0027]

[0030] To initiate the melt polycondensation of the reactants, the reaction mixture is generally heated to a high temperature in a polymerization reactor vessel. The polycondensation may take place in a temperature range of, for example, about 200°C to about 400°C. For example, one preferred technique for forming an aromatic polyester may involve placing a precursor monomer 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., to form acetoxy), and then increasing the temperature to about 200°C to about 400°C to carry out melt polycondensation. Once the final polymerization temperature is reached, volatile by-products of the reaction (e.g., acetic acid) may be removed so that the desired molecular weight can be easily achieved. The reaction mixture is generally subjected to stirring during polymerization to ensure good heat and mass transfer, followed by good material homogeneity. The rotation speed of the stirrer may be changed during the course of the reaction, but is typically in the range of about 10 to about 100 rpm ("revolutions per minute"), and in some embodiments, about 20 to about 80 rpm. To increase the molecular weight of the molten material, the polymerization reaction may be carried out in a vacuum, which facilitates the removal of volatile substances formed during the final stage of polycondensation. A vacuum can be created by applying a suction pressure, for example, in the range of about 5 to about 30 psi ("pounds per square inch"), and in some embodiments, in the range of about 10 to about 20 psi.

[0028]

[0031] After melt polymerization, the molten polymer can be released from the reactor through an extrusion orifice typically equipped with a die having a desired configuration, cooled, and recovered. Generally, the molten material is released 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-phase polymerization method to further increase its molecular weight. Solid-phase polymerization may be carried out in the presence of a gas (e.g., air, an inert gas). Suitable inert gases include, for example, nitrogen, helium, argon, neon, krypton, xenon, and combinations thereof. The solid-phase polymerization reactor vessel may have substantially any design as long as it can maintain the polymer at the desired solid-phase polymerization temperature for a desired residence time. Examples of such vessels may have a fixed bed, a static bed, a moving bed, a fluidized bed, etc. The temperature at which solid-phase polymerization is carried out can be varied, but is typically in the range of about 200°C to about 400°C. Polymerization time is naturally expected to vary depending on temperature and target molecular weight. However, in most cases, solid-phase polymerization time is expected to be about 2 to 12 hours, and in some embodiments, about 4 to 10 hours.

[0029]

[0032] The resulting bio-LCP, once formed, may have a "bio-content" of approximately 1 wt.% to 100 wt.% based on the total weight of monomers (repeating units) employed in the polymer, and in some embodiments, it may have a "bio-content" of approximately 2 wt.% to 90 wt.%, in some embodiments, approximately 5 wt.% to 70 wt.%, and in some embodiments, approximately 10 wt.% to 60 wt.%. As used herein, the term "bio-content" generally refers to the weight percentage of monomers (repeating units) derived from bionaphtha. Therefore, it should be understood that this weight percentage may include biobiphenols described herein (e.g., bio-4,4'-biphenol), as well as other monomeric components that can be derived from bionaphtha, such as bio-4-hydroxybenzoic acid ("bio-HBA"), bio-terephthalic acid ("bio-TA"), bio-isophthalic acid ("bio-IA"), bio-hydroquinone ("bio-HQ"), bio-2-hydroxy-6-naphthoic acid ("bio-HNA"), bio-2,6-naphthalenedicarboxylic acid ("bio-NDA"), bio-4-aminophenol ("bio-AP"), bio-acetaminophen ("bio-APAP"), and the like. Despite containing such a high bio-content, the resulting bio-LCP can still exhibit properties similar to those of liquid crystal polymers formed from conventional fossil fuel sources. In other words, bio-LCP is still considered "thermotropic" to the extent that it possesses a rod-like structure and can exhibit crystalline behavior (e.g., a thermotropic nematic state) in its molten state. Bio-LCP also typically has a high melting temperature, for example, about 280°C to about 400°C, in some embodiments about 290°C to about 380°C, and in some embodiments about 300°C to about 350°C. The melting temperature can be determined using differential scanning calorimetry ("DSC"), as is well known in the art, for example, according to ISO 11357-3:2018.

[0030] III. Polymer composition

[0033] Bio-LCP may be used in its pure form (i.e., in 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.%, in some embodiments about 20 wt.% to about 80 wt.%, in some embodiments about 25 wt.% to about 70 wt.%, and in some embodiments 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.%, in some embodiments about 20 wt.% to about 80 wt.%, in some embodiments about 30 wt.% to about 75 wt.%, and in some embodiments about 40 wt.% to about 70 wt.% of the polymer composition. Optionally, other additives may also be derived from sustainable sources, such as recycled materials, renewable materials, or bio-based materials. For example, the total “sustainable content” of a polymer composition is typically about 5 wt.% to 100 wt.%, about 10 wt.% to 90 wt.%, and about 20 wt.% to 80 wt.%, based on the total weight of the composition. The term “sustainable content” generally refers to the weight percentage of components derived from sustainable sources. For a composition containing only bio-LCP, for example, the “sustainable content” is the same as the “bio-content” (weight percentage of monomers derived from bio-naphtha). For a composition containing bio-LCP, other sustainable materials (e.g., recycled materials), and non-sustainable materials (e.g., fossil fuel-based materials, unused materials, etc.), the “sustainable content” can be determined as follows:

[0031]

number

[0034] Various other examples of additives that can be used in polymer compositions are listed below.

[0032] A. Inorganic fillers

[0035] The polymer composition may optionally contain one or more inorganic fillers. If used, such inorganic fillers typically constitute about 1 wt.% to about 50 wt.%, in some embodiments about 2 wt.% to about 45 wt.%, and in some embodiments about 5 wt.% to about 40 wt.% of the polymer composition. The properties of the inorganic fillers used in the polymer composition may vary, and may include, for example, inorganic particles, mineral fibers (or "whiskers"), or blends thereof. Typically, the inorganic fillers used in the polymer composition have a specific hardness value that helps improve the mechanical strength, adhesive strength, and surface properties of the composition. For example, the hardness value may be about 2.0 or higher, based on the Mohs hardness scale, in some embodiments it may be about 2.5 or higher, in some embodiments it may be about 3.0 or higher, in some embodiments it may be about 3.0 to about 11.0, in some embodiments it may be about 3.5 to about 11.0, and in some embodiments it may be about 4.5 to about 6.5.

[0033]

[0036] Various types of inorganic particles can generally be used in polymer compositions, 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. Particularly preferred are particles containing talc, calcium carbonate (CaCO3), copper carbonate hydroxide (Cu2CO3(OH)2); calcium fluoride (CaFl2); calcium pyrophosphate ((Ca2P2O7)), anhydrous dicalcium 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, and combinations thereof. Talc, mica, calcium carbonate, and barium sulfate are particularly preferred. All forms 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), lithia mica (K(Li,Al) 2~3 (AlSi3)O 10 (OH)2), glauconite (K,Na)(Al,Mg,Fe)2(Si,Al)4O 10 Examples include (OH)2).

[0034]

[0037] In certain embodiments, inorganic particles, such as barium sulfate and / or calcium sulfate particles, may actually have a granular or spherical shape in general. In such embodiments, the particles may have a median diameter (e.g., diameter) of about 0.5 to about 20 micrometers, and in some embodiments, a median diameter (e.g., diameter) of about 1 to about 15 micrometers, in some embodiments, about 1.5 to about 10 micrometers, and in some embodiments, about 2 to about 8 micrometers, which are measured using laser diffraction techniques, for example, in accordance with ISO 13320:2009 (e.g., using a Horiba LA-960 particle size distribution analyzer). In other embodiments, it may be desirable to employ flake-type inorganic particles, such as mica particles, having a relatively high aspect ratio (e.g., average diameter divided by average thickness) of about 4 or higher, in some embodiments about 8 or higher, and in some embodiments about 10 to about 500. In such embodiments, the average diameter of the particles may be, for example, in the range of about 5 micrometers to about 200 micrometers, in some embodiments, about 8 micrometers to about 150 micrometers, in some embodiments, about 10 micrometers to about 100 micrometers. The average thickness may similarly be about 2 micrometers or less, in some embodiments, about 5 nanometers to about 1 micrometer, in some embodiments, about 20 nanometers to about 500 nanometers, which is determined, for example, in accordance with ISO 13320:2009 (e.g., using a LA-960 particle size distribution analyzer from Horiba, Ltd.). The inorganic particles may also have a narrow particle size distribution; that is, at least about 70% by volume of the particles, in some embodiments, at least about 80% by volume of the particles, and in some embodiments, at least about 90% by volume of the particles may have a size within the above range.

[0035]

[0038] Other suitable mineral fibers include silicates, such as neosilicates, solosilicates, inosilicates (for example, calcium inosilicate such as wollastonite; calcium magnesium inosilicate such as tremolite; calcium magnesium iron inosilicate such as actinolite; magnesium iron inosilicate such as anthophylite), layered silicates (for example, aluminum layered silicates such as palygorskite), tectosilicates, etc.; sulfates, such as calcium sulfate (for example, dehydrated or anhydrous gypsum); and mineral wool (for example, rock or slag wool). Particularly preferred are fibers having a desired hardness value, examples of which include inosilicates, such as fibers derived from wollastonite (Mohs hardness of 4.5 to 5.0), which are commercially available from Nyco Minerals under the trade name Nyglos® (e.g., Nyglos® 4W or Nyglos® 8). The mineral fibers may have a median diameter (e.g., diameter) of about 1 to about 35 micrometers, and in some embodiments, a median diameter of 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. The mineral fibers may also have a narrow grain size distribution; that is, at least about 60 volume percent of the fiber, in some embodiments, at least about 70 volume percent of the fiber, and in some embodiments, at least about 80 volume percent of the fiber may have a size within the above range. In addition to having the size characteristics described above, the mineral fibers may also have a relatively high aspect ratio (average length divided by median diameter) to help further improve the mechanical properties and surface quality of the resulting polymer composition.For example, the mineral fibers may 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, in some embodiments about 2 to about 150 micrometers, in some embodiments about 5 to about 100 micrometers, and in some embodiments about 10 to about 50 micrometers.

[0036] B. Fibrous filler

[0039] Fibrous fillers may be used in polymer compositions. Typical fibrous fillers include fibers that have 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"), in some embodiments about 2,000 to about 10,000 MPa, and in some embodiments about 3,000 to about 6,000 MPa. To help maintain desirable properties, such high-strength fibers may be formed from materials that are inherently insulating, such as glass, ceramics (e.g., alumina or silica), aramid (e.g., Kevlar®, sold by EI du Pont de Nemours, Wilmington, Delaware), polyolefins, polyesters, etc. Glass fibers are particularly preferred, including, for example, E-glass, A-glass, C-glass, D-glass, AR-glass, R-glass, S1-glass, S2-glass, etc. If necessary, all or part of these fibers may be recycled.

[0037]

[0040] The fibers used in the fibrous filler may have various 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, in some embodiments about 6 to about 40, and in some embodiments about 8 to about 25 are particularly beneficial. Such fibers may have, for example, a weight-average length of about 100 to about 800 micrometers, in some embodiments about 120 to about 500 micrometers, in some embodiments about 150 to about 350 micrometers, and in some embodiments about 200 to about 300 micrometers. The fibers may also have a nominal diameter of about 6 to about 35 micrometers, and in some embodiments about 9 to about 18 micrometers. 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, in some embodiments about 3 wt.% to about 30 wt.%, and in some embodiments about 5 wt.% to about 20 wt.%.

[0038] C. Impact modifier

[0041] Impact modifiers may also be employed in the polymer composition. 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; 1-decene substituted with ethyl, methyl, or dimethyl; 1-dodecene; and styrene. Particularly preferred α-olefin monomers are ethylene and propylene. Olefin polymers may be copolymers containing other monomer units known in the art. For example, other suitable monomers include "(meth)acrylic" monomers, such as 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 of methacrylates include 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 ratio of monomer components can be selectively controlled. The α-olefin monomer may constitute, for example, about 55 wt.% to about 95 wt.%, in some embodiments about 60 wt.% to about 90 wt.%, and in some embodiments about 65 wt.% to about 85 wt.%, of the copolymer. Other monomer components (e.g., (meth)acrylic monomers) may constitute about 5 wt.% to about 35 wt.%, in some embodiments about 10 wt.% to about 32 wt.%, and in some embodiments about 15 wt.% to about 30 wt.%, of the copolymer.

[0039]

[0042] Other suitable olefin copolymers may be “epoxy-functionalized” in that they contain, on average, two or more epoxy functional groups per molecule. Copolymers may also contain epoxy-functional monomer units. An 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 itaconate. Other suitable monomers may also be employed to help achieve a 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, in some embodiments about 2 wt.% to about 15 wt.%, and in some embodiments about 3 wt.% to about 10 wt.%.

[0040]

[0043] If used, the impact modifier typically constitutes about 0.5 to about 60 parts by weight, in some embodiments about 1 to about 50 parts by weight, and in some embodiments 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, in some embodiments about 0.5 wt.% to about 25 wt.%, and in some embodiments about 1 wt.% to about 20 wt.%.

[0041] D. Laser-activatable coatings

[0044] 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, when the additive is exposed to a laser, metallic emission occurs. In this way, the laser draws a pattern of conductive elements on the component, leaving behind a rough surface containing embedded metallic 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 that may contain two or more metal oxide cluster arrangements within a definable crystal formation. For example, the overall crystal formation can be expressed by the following general formula: AB2O4 or ABO2 It may have, During the ceremony, A is a metal cation with a valency of 2 or greater, such as cadmium, chromium, manganese, nickel, zinc, copper, cobalt, iron, magnesium, tin, and titanium, as well as combinations thereof; B is a metal cation with a valency of trivalent or greater, such as antimony, chromium, iron, aluminum, nickel, manganese, and tin, as well as combinations thereof.

[0042]

[0045] Typically, in the above formula, A provides the major cationic component of the first metal oxide cluster, and B provides the major cationic component of the second metal oxide cluster. These oxide clusters may have the same structure 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. In either case, the clusters together can provide a single, identifiable 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 oxide / antimony (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, the laser-activatable additive may also have a core-shell configuration as described in WO2018 / 130972, etc. 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.).

[0043]

[0046] If laser-activatable additives are used, they typically constitute about 0.1 wt.% to about 30 wt.%, in some embodiments about 0.5 wt.% to about 20 wt.%, and in some embodiments about 1 wt.% to about 10 wt.% of the polymer composition. Of course, the polymer composition may also not contain laser-activatable additives such as spinel crystals (i.e., 0 wt.%), or such additives may be present in small concentrations, for example, about 1 wt.% or less, in some embodiments about 0.5 wt.% or less, and in some embodiments about 0.001 wt.% to about 0.2 wt.%.

[0044] E. Other optional additives

[0047] The polymer composition may contain various other additional additives, examples of which include lubricants, thermally conductive fillers, pigments (e.g., carbon black), antioxidants, stabilizers, surfactants, waxes, flame retardants, anti-drip 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 enhance properties and processability. For example, a lubricant capable of withstanding the processing conditions of the liquid crystal polymer without causing substantial decomposition may be used in the polymer composition. Examples of such lubricants include fatty acid esters, their salts, esters, fatty acid amides, organophosphate esters, and engineering plastic materials, as well as hydrocarbon waxes of a type commonly used as a lubricant during the processing of mixtures thereof. Suitable fatty acids typically have a carbon chain with a main chain of about 12 to about 60 carbon atoms, such as myristic acid, palmitic acid, stearic acid, arachidic acid, montanic acid, octadecenoic acid, and parinalic acid. Suitable esters include fatty acid esters, aliphatic alcohol esters, wax esters, glycerol esters, glycol esters, and complex esters. Fatty acid amides include aliphatic primary amides, aliphatic secondary amides, methylene and ethylenebisamides, as well as alkanolamides such as palmitic acid amide, stearic acid amide, oleic acid amide, and N,N'-ethylenebisstearate amide. Also suitable are metal salts of fatty acids such as calcium stearate, zinc stearate, and magnesium stearate; and hydrocarbon waxes such as paraffin wax, polyolefin and oxidized polyolefin wax, and microcrystalline wax. Particularly suitable lubricants are acids, salts, or amides of stearic acid, such as pentaerythritol tetrastearate, calcium stearate, or N,N'-ethylenebisstearate amide.When used, the lubricant typically constitutes about 0.05 wt.% to about 1.5 wt.% of the polymer composition, and in some embodiments, about 0.1 wt.% to about 0.5 wt.% (based on weight).

[0045]

[0048] The components used to form the polymer composition can be combined using any of the various techniques known in the industry. In one particular embodiment, for example, bio-LCP and other optional additives can be melt-processed 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 melt-processed in an extruder having multiple temperature zones. The temperature of each zone is typically set within a range of about -60°C to about 25°C relative to the melt temperature of the liquid crystal polymer. As an example, the mixture may be melt-processed using a twin-screw extruder, for example, a Leistritz 18 mm co-rotating fully intermeshing twin-screw extruder. A general-purpose screw design may be used to melt-process the mixture. In one embodiment, the mixture containing all the components can be fed into the feed port of a first barrel using a capacitive feeder. In another embodiment, as is well known, different components may be added at different addition points in the extruder. For example, the liquid crystal polymer may be applied at the feed port, and specific additives (e.g., dielectric fillers) may be supplied to the same or different temperature zones located downstream thereof. In either case, the resulting mixture may be melted and mixed and then extruded through a die. The extruded polymer composition may then be quenched in a water bath, solidified and granulated in a pelletizer, and subsequently dried.

[0046]

[0049] Despite containing bio-LCP, the polymer composition can exhibit various properties similar to those formed from conventional types of liquid crystal polymers. For example, the polymer composition can exhibit excellent melt processing properties. For example, the polymer composition may have a very low melt viscosity, e.g., about 0.1 to about 100 Pa·s, in some embodiments 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 about 1 to about 35 Pa·s, which is determined according to ISO 11443:2021 at a shear rate of 1,000 seconds -1 and 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 can be, for example, about 280 °C to about 400 °C, in some embodiments about 290 °C to about 380 °C, in some embodiments about 300 °C to about 350 °C. Even at such melt temperatures, the ratio of the heat deflection temperature under load (the "DTUL"), a measure of short-term heat resistance, to the melt temperature can still be relatively high. For example, this ratio can range from about 0.5 to about 1.00, in some embodiments about 0.6 to about 0.95, in some embodiments about 0.65 to about 0.85. Specific DTUL values can be, for example, about 200 °C or higher, in some embodiments about 220 °C or higher, in some embodiments about 230 °C to about 300 °C, in some embodiments about 240 °C to about 280 °C. Among others, such high DTUL values enable the use of high speed and reliable surface mounting processes for connecting the structure to other components.

[0047]

[0050] The polymer composition may also have high impact strength, which is useful when forming thin layers. The composition, for example, has an impact strength of approximately 0.5 kJ / m² when measured at a temperature of 23°C according to ISO test number ISO179-1:2010. 2 Alternatively, it may have a higher notched Charpy impact strength, and in some embodiments, it may be about 1 to about 60 kJ / m 2 In some embodiments, the concentration is approximately 2 to 50 kJ / m³. 2 In some embodiments, approximately 5 to approximately 45 kJ / m³ 2 It may have a notched Charpy impact strength. The composition may also have excellent tensile and flexural mechanical properties. For example, a polymer composition may exhibit a tensile strength of about 20 to about 500 MPa, in some embodiments, about 50 to about 400 MPa, in some embodiments, about 70 to about 350 MPa; a tensile fracture strain of about 0.4% or higher, in some embodiments, about 0.5% to about 10%, in some embodiments, about 0.6% to about 3.5%; and / or a tensile modulus of about 5,000 MPa to about 20,000 MPa, in some embodiments, about 8,000 MPa to about 20,000 MPa, in some embodiments, about 10,000 MPa to about 20,000 MPa. Tensile properties can be determined at a temperature of 23°C according to ISO test number 527:2019. The polymer composition may also exhibit a flexural strength of about 20 to about 500 MPa, in some embodiments, about 50 to about 400 MPa, in some embodiments, about 100 to about 350 MPa; a flexural elongation of about 0.4% or higher, in some embodiments, about 0.5% to about 10%, in some embodiments, about 0.6% to about 3.5%; and / or a flexural modulus of about 5,000 MPa to about 20,000 MPa, in some embodiments, about 8,000 MPa to about 20,000 MPa, in some embodiments, about 10,000 MPa to about 15,000 MPa. Flexural properties can be measured at a temperature of 23°C according to 178:2019.

[0048]

[0051] Once formed, polymer compositions can be molded into any of the various shapes of parts using techniques known in the industry. For example, molded parts can be formed using a one-component injection molding process in which dried and preheated plastic granules are injected into a mold. Regardless of the molding technique employed, polymer compositions are well suited for forming electronic components with small dimensional tolerances. For example, such components generally have at least one micro-sized dimension (e.g., thickness, width, height, etc.), for example, about 500 micrometers or less, in some embodiments about 50 to about 450 micrometers, and in some embodiments about 100 to about 400 micrometers.

[0049]

[0052] 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 connection 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 enough to accommodate the required number of connection pins within a given space. This, in turn, requires that the pitch of the pin insertion passages and the width of the opposing walls separating these passages are also small. For example, the walls may have a width of about 500 micrometers or less, in some embodiments about 50 to about 450 micrometers, and in some embodiments about 100 to about 400 micrometers. The polymer compositions of the present invention are particularly well suited for forming the walls of a fine-pitch connector. It will also be understood that, in addition to or instead of the walls, any other parts of the connector housing can 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 a 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.

[0050]

[0053] Naturally, the polymer composition can also be used in a variety of other components. For example, the polymer composition can be molded into a planar substrate for use in electronic components. The substrate may be thin, for example, about 500 micrometers or less, in some embodiments about 50 to about 450 micrometers, and in some embodiments about 100 to about 400 micrometers thick. In one embodiment, for example, the planar substrate can be applied with one or more conductive elements using various known techniques (e.g., laser direct structuring, electroplating, etc.). The conductive elements can serve a variety of purposes. In one embodiment, for example, the conductive elements form an integrated circuit, such as an integrated circuit used in a SIM card. In another embodiment, the conductive elements form various types of antennas, for example, 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, hybrids of these designs, etc. The resulting antenna structure can be incorporated into a relatively compact portable electronic component housing with relatively small available internal space, as described above, for example.

[0051]

[0054] Planar substrates formed from the polymer compositions described above may also be used in other applications. For example, in one embodiment, a planar substrate can 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 sits on the base. The base, in turn, sits on an optional mainboard. The base and / or mainboard are particularly suitable for formation from the polymer compositions described above due to their relatively thin nature. The lens assembly may have any of the various configurations known in the art, examples of which include fixed-focus lenses and / or autofocus lenses. In one embodiment, for example, the lens assembly may be in the form of a hollow barrel housing the lens, which communicates with and is controlled by a circuit to an image sensor located on the mainboard. The barrel may have any of the various shapes, such as rectangular or cylindrical. In certain embodiments, the barrel may also be formed from a polymer composition and may have wall thicknesses within the range described above. It will be understood that other components of the camera module may also be formed from polymer compositions. For example, a polymer film (e.g., a polyester film) and / or an insulating cap may cover the lens assembly. In some embodiments, the film and / or cap may also be formed from a polymer composition.

[0052]

[0055] Further other potential electronic components that may utilize polymer compositions include, for example, mobile phones, laptop computers, small portable computers (e.g., ultra-small lightweight computers, netbooks, and tablet computers), smartwatch devices, pendant devices, headphones and earpiece devices, media players with wireless communication capabilities, handheld computers (sometimes also called portable personal information terminals), remote controllers, GPS devices, handheld gaming 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 components.

[0053]

[0056] The following test methods can be used to determine one or more of the characteristics identified above.

[0057] Melt viscosity: Melt viscosity (Pa·s) was measured in accordance with ISO 11443:2021 using a Dynisco LCR7001 capillary rheometer for 400 seconds. -1 or 1,000s -1 The shear rate and melting temperature can be measured 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 entrance angle of 180°. The barrel diameter may be 9.55 mm + 0.005 mm, and the rod length may be 233.4 mm.

[0054]

[0058] Melting temperature: The melting temperature ("Tm") can be determined by differential scanning calorimetry ("DSC") as is well known in the industry. The melting temperature is the differential scanning calorimetry (DSC) peak melting temperature, as determined by ISO 11357-3:2018. Samples were heated and cooled at 20°C / min using DSC measurements performed on a TA Q2000 instrument, as described in ISO standard 10350, following the DSC procedure.

[0055]

[0059] 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 strip sample 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 sample is lowered into a silicone oil bath, where the temperature can be increased at 2°C / min until the sample deflects by 0.25 mm (0.32 mm in the case of ISO test number 75-2:2013).

[0056]

[0060] Tensile modulus, tensile stress, and tensile elongation: Tensile properties can be tested according to ISO 527:2019 (technically equivalent to ASTM D638). Modulus and strength measurements may be performed on the same test strip sample 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.

[0057]

[0061] Bending modulus, bending stress, and bending elongation: Bending properties can be tested according to ISO 178:2019 (technically equivalent to ASTM D790). This test may be performed on a support span of 64 mm. The test may be performed on the center portion of an uncut ISO 3167 multipurpose bar. The test temperature may be 23°C, and the test speed may be 2 mm / min.

[0058]

[0062] Charpy impact strength: Charpy properties can be tested according to ISO 179-1:2010 (technically equivalent to ASTM D256-10, Method B). This test may be performed using a Type 1 specimen size (80 mm length, 10 mm width, and 4 mm thickness). When testing notched impact strength, the notch may be a Type A notch (base circle radius of 0.25 mm). The specimen may be cut from the center of a multipurpose bar using a single-tooth milling machine. The test temperature may be 23°C.

[0059]

[0063] These and other modifications and variations of the present invention can be carried out by those skilled in the art without departing from the essence and scope of the invention. In addition, it should be understood that aspects of the various embodiments are interchangeable, either whole or in part. Furthermore, those skilled in the art will understand that the foregoing description is merely an example and is not intended to limit the invention, and is therefore further described in the appended claims.

Claims

1. A method for forming biobiphenol monomers for use in liquid crystal polymers, To provide biodialkylphenols derived from bionaphtha; Oxidative coupling of the biodialkylphenol to form an alkylated biphenol; and Dealkylation of alkylated phenols to form biobiphenols. The above method, including.

2. The method according to claim 1, wherein the biodialkylphenol comprises 2,4-dialkylphenol, 2,6-dialkylphenol, or a combination thereof.

3. The method according to claim 1, wherein the alkylated biphenol comprises 2,2',6,6'-tetraalkyl-4,4'-biphenol.

4. The method according to claim 1, wherein oxidative coupling is performed in the presence of a catalyst.

5. The method according to claim 1, wherein the dealkylation comprises contacting the alkylated phenol with an acid.

6. The method according to claim 1, wherein the biodialkylphenol is formed by reacting a biophenol with isobutylene, and the biophenol is derived from the bionaphtha.

7. The method according to claim 6, 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 a biophenol, and the biocumene is derived from the bionaphtha.

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

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

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

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

12. The method according to claim 11, 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.

13. The method according to claim 1, wherein the biobiphenol monomer is bio-4,4'-biphenol.

14. A bio-4,4'-biphenol monomer formed by the method described in claim 1.

15. A bioliquid crystal polymer comprising repeating units derived from the bio-4,4'-biphenol monomer described in claim 14.

16. A bioliquid crystal polymer comprising repeating units derived from one or more biphenols, repeating units derived from one or more of any selection aromatic hydroxycarboxylic acids, repeating units derived from one or more of any selection dicarboxylic acids, and repeating units derived from one or more of any selection aromatic diols, The bioliquid crystal polymer comprises one or more biphenols, including bio-4,4'-biphenol derived from bionaphtha.

17. The bioliquid crystal polymer according to claim 16, wherein the bioliquid crystal polymer contains repeating units derived from bio-4,4'-biphenol in an amount of 6 mol.% to about 30 mol.%.

18. The bioliquid crystal polymer according to claim 16, wherein the polymer further comprises repeating units derived from 4-hydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, terephthalic acid, isophthalic acid, 2,6-naphthylenedicarboxylic acid, hydroquinone, 4-aminophenol, acetaminophen, or combinations thereof.

19. The bioliquid crystal polymer according to claim 16, wherein the thermotropic liquid crystal polymer is fully aromatic.

20. The bioliquid crystal polymer according to claim 16, wherein the polymer composition has a melting temperature of about 280°C to about 400°C.

21. The bio-liquid crystal polymer according to claim 16, wherein the polymer has a bio-content of about 5 wt.% to 70 wt.% based on the total weight of the monomers used in the polymer.

22. The polymer composition according to claim 15, wherein the composition contains the bio-liquid crystal polymer and one or more optionally selected additives.

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

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