Bio-based biphenols for forming bio-based liquid crystal polymers

Abstract

Techniques are provided for forming bio-based biphenol monomers (e.g., "bio-based BP") derived from bio-based naphtha and bio-based liquid crystal polymers ("bio-based LCPs") formed therefrom.

Description

[0001] Related applications

[0002] This application is based on and claims priority to U.S. Provisional Patent Application No. 63 / 495,160, filed April 10, 2023, which is incorporated herein by reference. Background Technology

[0003] Liquid crystal polymers are commonly used in a variety of high-performance applications, such as high-voltage connectors, medical products, and camera modules. These 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-naphthoic acid (“NDA”)) with one or more aromatic diols (e.g., hydroquinone (“HQ”), 4,4'-biphenyl (“BP”), etc.) to form ester repeating units. BP constitutes a significant portion of the aromatic diols used in most commercially available liquid crystal polymers. Traditionally, BP has been produced from crude oil via a catalytic cracking process. However, recently, there has been a demand for more carbon-neutral methods. To achieve carbon neutrality, companies must remove an equal amount of carbon dioxide emitted into the atmosphere to achieve net-zero carbon emissions. On the other hand, carbon-negative companies remove more carbon from the atmosphere than they release. Given the significant efforts made by global companies to become carbon-neutral or carbon-negative, there is a need for methods to produce biphenyl and liquid crystal polymers in a more sustainable manner without significantly altering the properties of these polymers. Summary of the Invention

[0004] According to one embodiment of the present invention, a method for forming a bio-biphenol monomer for liquid crystal polymers is disclosed. The method includes providing a bio-biphenol derived from bio-biphenol naphtha, oxidatively coupling the bio-biphenol to form an alkylated biphenol, and dealkylating the alkylated phenol to form a bio-biphenol.

[0005] According to another embodiment of the present invention, a bio-based liquid crystal polymer is disclosed, comprising repeating units derived from one or more biphenols, optionally repeating units derived from one or more hydroxycarboxylic acids, optionally repeating units derived from one or more dicarboxylic acids, and optionally repeating units derived from one or more aromatic diols. The one or more aromatic biphenols include bio-based 4,4'-biphenol derived from bio-based naphtha.

[0006] Other features and aspects of the invention are described in more detail below. Detailed Implementation

[0007] Those skilled in the art will understand that this discussion is merely a description of exemplary embodiments and is not intended to limit the broader aspects of the invention.

[0008] Generally, this disclosure relates to techniques for forming bio-based biphenol monomers derived from bio-based naphtha and bio-based liquid crystal polymers (“Bio-based LCPs”) formed therefrom. Ultimately, the bio-based LCPs and compositions formed from such polymers can be certified based on the ISCC+ standard proposed by the International Sustainability and Carbon Certification (“ISCC”) system. ISCC is a globally applicable sustainability certification system covering all sustainable feedstocks, including agricultural and forestry biomass, circular and bio-based materials, and renewable energy. ISCC follows a quality balance approach, in which the renewable content of the polymer can be verified. In quality balance, renewable feedstocks are attributed to selected products according to their individual formulations, taking into account all yields and losses. Only feedstocks used as production feedstocks (but not as energy) are considered for quality balance. Key criteria for applying the quality balance approach include feedstock eligibility, chain of custody, and product declarations. The quality balance approach can track the quantity and sustainability characteristics of recycled and / or bio-based feedstocks in the value chain and verifiably attribute them to the final product. In one embodiment, the liquid crystal polymers described herein can be made from carbon-negative or carbon-neutral components under the quality balance approach.

[0009] Various embodiments of the present invention will now be described in more detail.

[0010] I. Bio-based biphenol

[0011] As described above, the bio-based biphenol disclosed herein is derived from "bio-based naphtha". The term "bio-based naphtha" generally refers to naphtha produced from renewable sources. Bio-based naphtha is a hydrocarbon composition primarily containing alkanes that can be converted into bio-based aromatic compounds (e.g., bio-based benzene). The hydrocarbon content typically has 8 to 24 carbons, and in some cases 10 to 18 carbons. To form bio-based naphtha, a bio-based distillate feedstock is typically provided, comprising a complex mixture of naturally occurring fats and / or oils (e.g., vegetable-based fats and oils such as cotton, coconut, corn, palm, peanut, flaxseed, rice, rapeseed, olive, soybean, sunflower, linola, animal fats, tall oil, castor oil, etc.) and animal-based fats and oils (e.g., butter or milk fat)). The feedstock can be provided in an unused (original) state and / or obtained from waste products (e.g., cooking oils, inedible highly saturated oils, waste cooking oils, byproducts of vegetable oil refining, and mixtures thereof). Natural fats and oils primarily consist of triglycerides and a certain amount of free fatty acids (FFA). Many different types of triglycerides are produced in nature, whether from plant or animal sources. It has been found that fatty acids in fats and oils are esterified into glycerol (triacylglycerol). The acyl group is a long chain (C) that is usually terminally esterified with a carboxyl group. 12 -C 22 Hydrocarbons. Fats and oils are characterized by the chemical composition and structure of their fatty acid moiety. The fatty acid moiety may be saturated or contain one or more double bonds. The sources of the aforementioned fats and / or oils may include fatty acids such as saturated fatty acids (e.g., hexanoic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, heptadecanic acid, stearic acid, arachidic acid, behenic acid, ceramide, etc.) and / or unsaturated fatty acids (e.g., myristoleic acid, palmitoleic acid, heptadecanic acid, oleic acid, linolenic acid, alpha-linolenic acid, gadolinic acid, ricinoleic acid, rosin, etc.). For example, tall oil contains myristic acid, stearic acid, arachidic acid, oleic acid, linolenic acid, and gadolinic acid.

[0012] Bio-based distillate feedstocks can be categorized based on their free fatty acid (FFA) content as follows: refined oils, such as soybean oil or refined rapeseed oil (FFA < 1.5%); low-FFA yellow oils and animal fats (FFA < 4%); and high-FFA oils and animal fats (FFA > 20%). In some cases, refining of the feedstock may be necessary (e.g., physical refining, chemical refining, etc.) to remove most of the non-triglyceride and non-fatty acid components. For example, physical refining can remove FFA, as well as unsaponifiables and other impurities, through stripping, thus eliminating soap production and minimizing neutral oil loss. However, when heated to the temperatures required for steam distillation, degumming pretreatment of crude fats and oils may be necessary to remove impurities that darken or otherwise contribute to inferior products. Degumming processes may include treating crude oil with water, salt solutions, enzymes, caustic soda, or dilute acids (such as phosphoric acid, citric acid, or maleic acid) to remove phospholipids, waxes, pro-oxidants, and other impurities. The degumming process converts phospholipids into hydrated gums, which are insoluble in oil and can be easily separated as sludge through sedimentation, filtration, or centrifugation.

[0013] The refined oil may contain an unsaturated or substantially unsaturated liquid or substantially liquid triglyceride fraction (phase L) and a saturated or substantially saturated solid or substantially solid triglyceride fraction (phase S). Solid phase S can then be converted into linear or substantially linear alkanes as “bio-based naphtha.” More specifically, the refined oil can be fractionated into phases L and S by a fractional crystallization method involving controlled cooling during which triglycerides with substantially saturated acyl moieties in the complex mixture crystallize and precipitate from the mixture to form phase S, while triglycerides with substantially unsaturated acyl moieties remain liquid to form phase L. The two phases are then separated by simple filtration, decantation, or centrifugation. In one embodiment, fractionation can be “dry fractionation” or “dry winterization,” which involves the removal of solids through controlled crystallization and separation techniques or dry processing (sometimes also called dewaxing) using solvents. The fractionation process has two main stages, the first being a crystallization stage. As the temperature of molten fats and oils or their solutions decreases, crystals grow, and their solubility at the final or separation temperature determines the triglyceride composition of the formed crystals and their mother liquor. The separation process is the second step in fractionation. Several options can be used, such as vacuum filters, centrifuges, conical screen-vortex centrifuges, hydraulic presses, membrane filter presses, or decanters. Fractionation can also be carried out in the presence of solvents such as alkanes, alkyl acetates, ethers, ketones, alcohols, or chlorinated hydrocarbons.

[0014] Once obtained, phase S can be converted into straight-chain or substantially straight-chain alkanes as bio-based naphtha using known processes such as thermal decarboxylation (e.g., using soap feedstock obtained from chemically refined fats and oils), catalytic decarboxylation (e.g., using fatty acid feedstock obtained from physically refined oils and fats), and catalytic hydrodeoxygenation (using triglycerides and / or fatty acid feedstocks)). Hydrodeoxygenation is frequently employed, ultimately involving the removal of oxygen atoms from fats and oils. Hydrodeoxygenation is preferably carried out in a continuous fixed-bed reactor, a continuous stirred-tank reactor, or a slurry reactor containing a solid catalyst. The catalyst may comprise, for example, Ni, Mo, Co, or mixtures thereof (e.g., NiW, NiMo, CoMo, NiCoW, NiCoMo, NiMoW, and CoMoW oxides or sulfides) preferably supported on high surface area carbon, alumina, silica, titanium dioxide, or zirconium oxide as the catalytically 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, magnesium oxide, zinc oxide, spinel (Mg2Al2O4, ZnAl2O4), perovskite (BaTiO3, ZnTiO3), calcium silicate (e.g., calcareous silicate), alumina, silica, or mixtures thereof. Preferably, the support for the catalytically active phase exhibits low acidity, preferably neutral or basic, to avoid hydroisomerization reactions that would lead to branched alkanes and cracking. Hydrodeoxygenation can 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, at a pressure of about 1 MPa to about 10 MPa, and at a hydrogen to refined oil ratio of about 100 to about 2000, and in some embodiments about 350 to about 1500.

[0015] Regardless of how it is formed, the resulting feedstock containing bio-based naphtha can be subjected to steam cracking to obtain bio-based aromatic compounds (e.g., bio-based benzene). A steam cracker is a complex industrial facility that can be divided into three main zones, each with various types of equipment and very specific functions: (i) a hot zone, including: pyrolysis or cracking furnaces, quenching exchangers and quenching rings, and columns for the thermal separation system; (ii) a compression zone, including: cracked gas compressors, purification and separation columns, and dryers; and (iii) a cold zone, including: cold boxes, demethanizers, fractionation columns for the cold separation system, C2 and C3 converters, and a gasoline hydrostabilization reactor. Hydrocarbon cracking can be carried out in a tubular reactor within a direct-fired heater (furnace). Various tube sizes and configurations can be used, such as coils, U-tubes, or straight tube layouts. Each furnace consists of a convection zone for recovering waste heat and a radiative zone where pyrolysis occurs. The feedstock-steam mixture is preheated in the convection section to approximately 530°C to 650°C, or the feedstock is preheated in the convection section and then mixed with dilution steam before flowing into the radiant zone. Pyrolysis occurs in the radiant zone at a variable temperature of 750°C to 950°C. The steam / feedstock (steam / [hydrocarbon feedstock]) weight ratio can be from approximately 0.2 kg / kg to approximately 1.0 kg / kg. For steam cracking furnaces, severity can be adjusted by the following: temperature, residence time, total pressure, and partial pressure of hydrocarbons. The effluent from the pyrolysis furnace contains unreacted feedstock, olefins (mainly ethylene and propylene), hydrogen, methane, a mixture of C4 compounds (mainly isobutylene and butadiene), aromatic compounds in the C6 to C8 range, ethane, propane, dienes (acetylene, methylacetylene, propadiene), and heavier hydrocarbons boiling within the temperature range of fuel oil. The pyrolysis gas is rapidly quenched to 338°C to 510°C to stop the pyrolysis reaction, minimizing the continuous reaction, and the sensible heat in the gas is recovered by generating high-pressure steam in a parallel transmission line heat exchanger (TLE).

[0016] The resulting mixed hydrocarbon feed can then be supplied to a "de-aromatization unit," a refining unit used to separate aromatic hydrocarbons (e.g., bio-based benzene). Such de-aromatization processes are described in Folkins (2000) Benzene, Ullmann's Encyclopedia of Industrial Chemistry. A specific method for separating aromatic hydrocarbons from a mixture of aromatic and aliphatic hydrocarbons is solvent extraction, as described, for example, in WO2012 / 135111, which is incorporated herein by reference. Preferred solvents for aromatic solvent extraction are sulfolane, tetraethylene glycol, and N-methylpyrrolidone, which are commonly used solvents in commercially available aromatic compound extraction processes. These substances are typically used in combination with other solvents or other chemicals (sometimes referred to as co-solvents) such as water and / or alcohols. 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. 5,880,325, the entire contents of which are incorporated herein by reference. Alternatively, other known methods besides solvent extraction, such as molecular sieve separation or boiling point-based separation, can be used to separate heavy aromatic compounds in dearomatization processes.

[0017] Once obtained, the resulting bio-based benzene can be subsequently converted to bio-based phenol, which is a reactant used to produce bio-based biphenol. In this respect, bio-based benzene can initially be converted to bio-based cumene (isopropylbenzene). For example, a suitable method involves an alkylation reaction using propylene and bio-based benzene feedstock. Typical propylene feedstock can be an almost pure polymer-grade material or can contain significant amounts of propane, as typically found in refined-grade propylene. Typical bio-based benzene feedstock can contain benzene (99.9 wt.% minimum) and toluene (0.05 wt.% minimum). The alkylation reactor can be operated in a gas phase, liquid phase, or mixed phase. At lower temperatures during liquid phase operation, no xylene impurities are generated, and a high-quality cumene product is produced. Temperatures are typically from about 100°C to about 310°C, and pressures are typically from about 8 bar to 50 bar. The alkylation reactor can contain an effective amount of alkylation catalyst, such as a solid acid catalyst (e.g., solid oxide zeolite). Examples include zeolite β, zeolite X, zeolite Y, mordenite, octahedral zeolite, zeolite ω, UZM-8, MCM-22, MCM-36, MCM-49, and MCM-56.

[0018] In an alkylation reactor, bio-based benzene is alkylated with propylene to form bio-based cumene (isopropylbenzene). However, some polyisopropylbenzene is also formed, which is primarily di-substituted and tri-substituted propylbenzene. To minimize the production of dialkylation products of benzene, it is generally desirable to maintain an excess molar amount of benzene throughout the reaction zone, with a benzene:propylene ratio of about 4:1 to about 16:1, more preferably about 8:1. A transalkylation reactor can also be used to transalkylate the polyisopropylbenzene produced in the alkylation reactor to form additional cumene. Suitable conditions and catalysts can be the same as those described in the alkylation reactor. The effluents from the alkylation reactor and the transalkylation reactor undergo separation operations to separate the benzene, cumene product, polyisopropylbenzene, and byproduct stream using distillation columns, as described in U.S. Patent Publication No. 2008 / 0293986, which is incorporated herein by reference. For example, a first distillation column for recovering excess benzene from the reactor effluent can be employed. The benzene column overhead distillate (primarily benzene) is typically recycled to the alkylator and the transalkylator. A second distillation column can be used to recover cumene from the bottom of the cumene column. The cumene product is typically the net overhead distillate from the cumene column. Alternatively, a third distillation column, specifically a polyisopropylbenzene (PPB) column, can be used to recover the PPB recirculation stream from the bottom of the cumene column. PPB is recovered from the PPB column as an overhead distillate and is typically recycled to the transalkylator.

[0019] Once formed, the bio-based cumene can then be reacted to form bio-based phenol using a process known as the "cumene process." More specifically, the bio-based cumene can first be oxidized to yield cumene hydroperoxide radicals. This can occur through the oxidation of cumene in an alkaline medium, where the hydroperoxide is stable. The bio-based cumene can be emulsified in an alkaline aqueous solution (such as sodium carbonate) with a pH of 8.5 to 10.5 using an emulsifier (such as sodium stearate). Oxidation with air or oxygen can occur at a moderately elevated temperature of about 70°C to about 130°C. Subsequently, the cumene hydroperoxide undergoes cracking, during which an acid catalyst is added, and the hydroperoxide decomposes into bio-based phenol, acetone, and other byproducts. The acid catalyst used can be any acidic material, such as phosphoric acid, sulfuric acid, and SO2. For example, the cumene hydroperoxide can be treated with dilute sulfuric acid (5% to 25% concentration) at a temperature of about 50°C to about 70°C. After pyrolysis, the reaction mixture can be separated and the oil layer distilled to obtain bio-based phenol, acetone, unreacted cumene, α-methylstyrene, acetophenone, and tar.

[0020] Bio-based phenols can then be converted into bio-based biphenols. For example, bio-based phenols can be initially alkylated via Friedel-Crafts alkylation of a hydrocarbon (e.g., isobutylene) in the presence of a solid alkylation catalyst (e.g., aluminum phenolate). Such methods are well known in the art and are described, for example, in U.S. Patent No. 2,684,389, which is incorporated herein by reference. The reaction can be configured to form bio-based dialkylphenols, such as bio-based 2,4-di-tert-butylphenol and / or bio-based 2,6-di-tert-butylphenol:

[0021] C6H5OH + 2 CH2=C(CH3)2 → ((CH3)3C)2C6H3OH

[0022] Once formed, dialkylphenols (at least one of which is a bio-based dialkylphenol) are oxidatively coupled to form a bio-based biphenol. Such oxidative coupling reactions are described, for example, in U.S. Patent Publication No. 2003 / 0050515, which is incorporated herein by reference. In one embodiment, for example, bio-based 2,4-dialkylphenols and / or bio-based 2,6-dialkylphenols are oxidatively coupled together (alone or in combination) in the presence of a catalyst (e.g., a copper-amino complex) to produce a bio-based alkylated biphenol (e.g., bio-based 2,2',6,6'-tetraalkyl-4,4'-biphenol). A one-step reaction scheme may be employed in some cases. Alternatively, a multi-step reaction scheme may be employed in which 2,4-dialkylphenols and / or 2,6-dialkylphenols react in a stepwise manner. For example, the first step may include using oxygen as an oxidant to couple 2,6-dialkylphenol to synthesize alkylated biphenylquinone (e.g., 3,3',5,5'-tetraalkyl-4,4'-biphenylquinone). The second step may include using 3,3',5,5'-tetraalkyl-4,4'-biphenylquinone as an oxidant to couple 2,6-dialkylphenol to synthesize alkylated biphenylphenol (e.g., 2,2',6,6'-tetraalkyl-4,4'-biphenylphenol).

[0023] If desired, the dialkylphenol (e.g., 2,6-dialkylphenol) can initially be dissolved in a solvent (e.g., methanol, ethanol, isopropanol, butanol, etc.). Excess phenol is typically used in the reaction. The reaction temperature can readily and typically ranges from about 30°C to about 50°C. Typically, after about 35% to 40% of the initial 2,6-dialkylphenol has been converted to the corresponding 3,3',5,5'-tetraalkyl-4,4'-biphenylquinone, the addition of oxygen can be stopped, and the reaction can proceed in the absence of oxygen. At this point, the solvent can be removed by distillation for reuse, and then water generated as a reaction byproduct can be removed by distillation at a higher temperature. For the second stage of the reaction, the temperature can be increased to maintain the reaction mixture in liquid form, typically from about 130°C to about 160°C. The presence of a catalyst allows the intermediate 3,3',5,5'-tetraalkyl-4,4'-biphenylquinone to act as an oxidant for subsequent coupling with 2,6-dialkylphenol. After consuming 3,3',5,5'-tetraalkyl-4,4'-biphenylquinone, the reaction mixture typically contains about 70% to 80% 2,2',6,6'-tetraalkyl-4,4'-biphenol and 20% to 30% 2,6-dialkylphenol. The reaction mixture is then cooled to about 60°C, and the solvent is added back to the reaction mixture. Within a few minutes, 2,2',6,6'-tetraalkyl-4,4'-biphenol can be completely precipitated and removed by filtration or centrifugation, while 2,6-dialkylphenol and the active catalyst remain in the filtrate. After adding fresh 2,6-dialkylphenol and optionally fresh catalyst, these mother liquors can be reused to start another cycle for the production of 2,2',6,6'-tetraalkyl-4,4'-biphenol.

[0024] Bio-based biphenols (e.g., bio-based 4,4'-biphenol) can then be produced from alkylated biphenols (e.g., 2,2',6,6'-tetra-tert-butyl-4,4'-biphenol) via dealkylation. Dealkylation methods may include contacting the alkylated biphenol with an acid (or optionally a mixture of an acid and a solvent). The dealkylation reaction is typically carried out at a temperature of about 130°C to about 170°C. Examples of suitable solvents that can be used in the reaction mixture include, for example, hydrocarbons having 7 to 9 carbons, and halogenated hydrocarbons with boiling points of about 80°C to about 130°C. Examples of suitable acids that can be used for dealkylation include, for example, sulfonic acids, such as methanesulfonic acid, sulfuric acid, toluenesulfonic acid, aluminum phenolate, etc.

[0025] II. Bio-based liquid crystal polymers ("bio-based LCPs")

[0026] As described above, the resulting bio-based biphenols are particularly suitable for forming bio-based liquid crystal polymers (“Bio-based LCPs”). Bio-based LCPs generally contain aromatic repeating units derived from the aforementioned bio-based biphenols. Examples of such biphenols may include, for example, 4,4'-biphenol, 3,3'-dihydroxybiphenyl, 3,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, bis(4-hydroxyphenyl)ethane, etc., and their alkyl, alkoxy, aryl, and halogen substituents and combinations thereof. Bio-based 4,4'-biphenol (“Bio-based BP”) is particularly suitable. Ideally, all biphenols used in the liquid crystal polymer are bio-based biphenols derived from bio-based naphtha. However, this is by no means necessary, and a portion of such biphenols may also be derived from conventional fossil fuel sources (e.g., petroleum) as known in the art. Regardless, repeating units derived from biphenol (e.g., bio-based biphenol) 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. In one specific embodiment, for example, the liquid crystal polymer may contain 6 mol.% to 30 mol.% of repeating units derived from bio-based biphenol, about 8 mol.% to about 28 mol.% in some embodiments, and about 10 mol.% to about 25 mol.% in some embodiments.

[0027] Bio-based LCPs may also contain aromatic repeating units derived from other types of aromatic diols (such as hydroxyphenol, naphthalene glycol, etc.), such as hydroquinone, resorcinol, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, etc., and their alkyl, alkoxy, aryl, and halogen substituents, and combinations thereof. Other particularly suitable aromatic diols may include, for example, hydroquinone (“HQ”). When used, repeating units derived from such other aromatic diols (e.g., HQ) 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.

[0028] Aromatic hydroxycarboxylic acids, such as hydroxybenzoic acids (e.g., 4-hydroxybenzoic acid, 4'-hydroxyphenyl-4-benzoic acid, 3'-hydroxyphenyl-4-benzoic acid, 4'-hydroxyphenyl-3-benzoic acid, etc.); hydroxynaphthic acids (e.g., 2-hydroxy-6-naphthic acid (“HNA”); 2-hydroxy-5-naphthic acid; 3-hydroxy-2-naphthic acid; 2-hydroxy-3-naphthic acid, etc.); and their alkyl, alkoxy, aryl, and halogen substituents, may also be used. Bio-based 4-hydroxybenzoic acid (“HBA”) and 2-hydroxy-6-naphthic acid are particularly suitable. When used, 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 75 mol.%; and repeating units derived from hydroxynaphthyl 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 specific embodiment, for example, the liquid crystal polymer may contain 40 mol.% to about 85 mol.% of repeating units derived from HBA, in some embodiments about 45 mol.% to about 82 mol.% and in some embodiments about 50 mol.% to about 80 mol.%.

[0029] Alternatively, repeating aromatic dicarboxylic acid units derived from aromatic dicarboxylic acids, their alkyl, alkoxy, aryl, and halogen substituents, and combinations thereof, may be used. Examples of aromatic dicarboxylic acids include 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, etc. Particularly suitable aromatic dicarboxylic acids may 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. Repeating units, such as those derived from aromatic amides (e.g., para-acetaminophen (“APAP”)) and / or aromatic amines (e.g., 4-aminophenol (“AP”), 3-aminophenol, 1,4-phenylenediamine, 1,3-phenylenediamine, etc.), may also be used. When 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 mol.% in some embodiments. It should also be understood that various other monomer repeating units can be incorporated into the polymer. For example, in some 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.). Of course, in other embodiments, the polymer may be "fully aromatic" because it lacks repeating units derived from non-aromatic (e.g., aliphatic or alicyclic) monomers.

[0030] Regardless of the specific composition and properties of the polymer, bio-based LCPs can be prepared by initially introducing aromatic monomers (e.g., aromatic hydroxycarboxylic acids, aromatic dicarboxylic acids, etc.) for forming repeating units and / or aromatic monomers (e.g., aromatic diols, aromatic amides, aromatic amines, etc.) into a reactor vessel to initiate a polycondensation reaction. The specific conditions and steps employed in such reactions are well known and can be described in more detail below: 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 WO 2004 / 058851. There are no particular limitations on the vessel used for the reaction, although it is generally desirable to use vessels typically used for reactions of high-viscosity fluids. Examples of such reaction vessels may include stirred tank-type devices with agitators having stirring blades of variable shape (e.g., anchor type, multi-stage type, spiral ribbon type, spiral shaft type, etc., or modified shapes thereof). Other examples of such reaction vessels may include mixing devices typically used for resin kneading, such as kneaders, roller mills, Banbury mixers, etc.

[0031] If desired, the reaction can be carried out by acetylation of a monomer known in the art. This can be accomplished by adding an acetyling agent (e.g., acetic anhydride) to the monomer. Acetylation is typically initiated at a temperature of about 90°C. During the initial stage of acetylation, reflux can be employed to maintain the vapor phase temperature below the temperature at which the acetic acid byproducts 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. If reflux is used, the vapor phase temperature is typically above the boiling point of acetic acid, but kept low enough to retain residual acetic anhydride. For example, acetic anhydride evaporates at a temperature of about 140°C. Therefore, it is particularly desirable to provide a vapor phase reflux at a temperature of about 110°C to about 130°C to the reactor. To ensure that the reaction is substantially complete, an excess of acetic anhydride can be used. The amount of excess anhydride will vary depending on the specific acetylation conditions employed (including the presence or absence of reflux). It is not uncommon to use an excess of acetic anhydride of about 1 mol.% to about 10 mol.% based on the total molar number of hydroxyl groups present in the reactants.

[0032] Acetylation can occur in a separate reactor vessel, or it can occur in situ within a polymerization reactor vessel. When using a separate reactor vessel, one or more monomers can be introduced into the acetylation reactor and subsequently transferred to the polymerization reactor. Similarly, one or more monomers can be introduced directly into the reactor vessel without undergoing pre-acetylation.

[0033] In addition to monomers and optional acetylation agents, other components may be included in the reaction mixture to aid 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). Based on the total weight of the repeating unit precursors, such catalysts are typically used in amounts from about 50 ppm to about 500 ppm. When using a separate reactor, it is generally desirable to apply the catalyst to the acetylation reactor rather than the polymerization reactor, although this is by no means necessary.

[0034] Typically, the reaction mixture is heated to an elevated temperature within the polymerization reactor vessel to initiate melt polycondensation of the reactants. Polycondensation can occur, for example, in a temperature range of about 200°C to about 400°C. For instance, a suitable technique for forming aromatic polyesters may include charging a precursor monomer and acetic anhydride into the reactor, heating the mixture to a temperature of about 90°C to about 150°C to acetylate the hydroxyl groups of the monomer (e.g., to form acetoxy groups), and then raising the temperature to about 200°C to about 400°C for melt polycondensation. As the final polymerization temperature approaches, volatile byproducts of the reaction (e.g., acetic acid) can be removed, thereby readily achieving the desired molecular weight. The reaction mixture is typically stirred during polymerization to ensure good heat and mass transfer, and consequently, good material homogeneity. The rotational speed of the stirrer can vary during the reaction, but is typically in the range of about 10 rpm to about 100 rpm, and in some embodiments, about 20 rpm to about 80 rpm. To increase the molecular weight of the melt, the polymerization reaction can also be carried out under vacuum, which is beneficial for removing volatiles formed in the final stages of polycondensation. A vacuum can be created by applying suction pressure, for example, in the range of about 5 pounds per square inch (“psi”) to about 30 psi, and in some implementations about 10 psi to about 20 psi.

[0035] Following melt polymerization, the molten polymer is typically extruded from the reactor through an extrusion orifice fitted with a die of the desired configuration, cooled, and collected. Typically, the melt is extruded through a perforated die to form a filament, which is then placed in a water bath, granulated, and dried. In some embodiments, the melt-polymerized polymer may also undergo subsequent solid-state polymerization to further increase its molecular weight. Solid-state polymerization can be carried out in the presence of a gas (e.g., air, inert gas, etc.). Suitable inert gases may include, for example, nitrogen, helium, argon, neon, krypton, xenon, etc., and combinations thereof. The solid-state polymerization reactor vessel can be virtually any design capable of maintaining the polymer at the desired solid-state polymerization temperature for the desired residence time. Examples of such vessels may be those with fixed beds, static beds, moving beds, fluidized beds, etc. The temperature at which solid-state polymerization takes place can vary, but is typically in the range of about 200°C to about 400°C. Of course, the polymerization time will vary based on the temperature and the target molecular weight. However, in most cases, the solid-state polymerization time will be about 2 hours to about 12 hours, and in some embodiments, about 4 hours to about 10 hours.

[0036] Once formed, the resulting bio-based LCP can have a “bio-based content” of about 1 wt.% to 100 wt.% based on the total weight of the monomers (repeating units) used in the polymer, about 2 wt.% to about 90 wt.% in some embodiments, about 5 wt.% to about 70 wt.% in some embodiments, and about 10 wt.% to about 60 wt.% in some embodiments. As used herein, the term “bio-based content” generally refers to the weight percentage of monomers (repeating units) derived from bio-based naphtha. Therefore, it should be understood that this weight percentage can include bio-based biphenyls (e.g., bio-based 4,4'-biphenyls) as described herein, as well as other monomeric components that may also be derived from bio-based naphtha, such as bio-based 4-hydroxybenzoic acid (“bio-based HBA”), bio-based terephthalic acid (“bio-based TA”), bio-based isophthalic acid (“bio-based IA”), bio-based hydroquinone (“bio-based HQ”), and bio-based 4-hydroxybenzoic acid (“bio-based HBA”). Bio-based 2-hydroxy-6-naphthoic acid (“Bio-based HNA”), bio-based 2,6-naphthoic acid (“Bio-based NDA”), bio-based 4-aminophenol (“Bio-based AP”), bio-based p-acetaminophenol (“Bio-based APAP”), etc. Despite such a high bio-based content, the resulting bio-based LCPs can still exhibit properties similar to those of liquid crystal polymers formed from conventional fossil fuel sources. That is, bio-based LCPs are still considered “thermotropic” because they can have a rod-like structure and exhibit crystallization behavior in their molten state (e.g., thermotropic nematic state). Bio-based LCPs also typically have high melting temperatures, such as 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. Melting temperatures can be determined using differential scanning calorimetry (“DSC”) as is known in the art, such as by ISO 11357-3:2018.

[0037] III. polymer composition

[0038] Bio-based LCPs can be in pure form (i.e., a composition containing 100 wt.% bio-based LCPs) or blended with other components to form a polymer composition. In such embodiments, the bio-based LCPs typically constitute about 10 wt.% to about 90 wt.% of the polymer composition, in some embodiments about 20 wt.% to about 80 wt.% of the polymer composition, in some embodiments about 25 wt.% to about 70 wt.% of the polymer composition, and in some embodiments about 30 wt.% to about 60 wt.% of the polymer composition. In such embodiments, other additives also constitute about 10 wt.% to about 90 wt.% of the polymer composition, in some embodiments about 20 wt.% to about 80 wt.% of the polymer composition, in some embodiments about 30 wt.% to about 75 wt.% of the polymer composition, and in some embodiments about 40 wt.% to about 70 wt.% of the polymer composition. If desired, other additives can also be derived from sustainable sources, such as recycled materials, renewable materials, bio-based materials, etc. For example, based on the total weight of the composition, the total “sustainable content” of the polymer composition is typically from about 5 wt.% to 100 wt.%, from about 10 wt.% to about 90 wt.% in some embodiments, and from about 20 wt.% to about 80 wt.% in some embodiments. The term “sustainable content” generally refers to the weight percentage of components derived from sustainable sources. For example, for a composition containing only bio-based LCPs, “sustainable content” is the same as “bio-based content” (the weight percentage of monomers derived from bio-based naphtha). For compositions containing bio-based LCPs, the “sustainable content” of other sustainable materials (e.g., recycled materials), non-sustainable materials (e.g., fossil fuel-based materials, virgin materials, etc.) can be determined as follows:

[0039]

[0040] Various examples of other additives that can be used in polymer compositions are described below.

[0041] A. Mineral packing

[0042] 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.% of the polymer composition, about 2 wt.% to about 45 wt.% in some embodiments, and about 5 wt.% to about 40 wt.% in some embodiments. The properties of the mineral fillers used in the polymer composition (such as mineral particles, mineral fibers (or “whiskers”), etc., and blends thereof) can vary. 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, based on the Mohs hardness scale, the hardness value can be about 2.0 or greater, about 2.5 or greater in some embodiments, about 3.0 or greater in some embodiments, about 3.0 to about 11.0 in some embodiments, about 3.5 to about 11.0 in some embodiments, and about 4.5 to about 6.5 in some embodiments.

[0043] Typically, any of a variety of different types of mineral particles can be used in polymer compositions, such as those formed from natural and / or synthetic silicate minerals (such as talc, mica, silica (e.g., amorphous silica), alumina, hydrous kaolinite, kaolinite, illite, montmorillonite, vermiculite, palygorskite, pyrophyllite, calcium silicate, aluminum silicate, wollastonite, etc.; sulfates, carbonates, phosphates, fluorides, borates, etc.). Particularly suitable particles include talc, calcium carbonate (CaCO3), copper carbonate hydroxide (Cu2CO3(OH)2); calcium fluoride (CaFl2); calcium pyrophosphate (Ca2P2O7), anhydrous calcium hydrogen phosphate (CaHPO4), hydrated aluminum phosphate (AlPO4·2H2O); silicon dioxide (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 combinations thereof. Talc, mica, calcium carbonate, and barium sulfate are particularly suitable. Mica in any form can generally be used, including, 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), Lithium mica (K(Li,Al) 2-3 (AlSi3)O 10 (OH)2), glauconite (K,Na)(Al,Mg,Fe)2(Si,Al)4O 10 (OH)2, etc.

[0044] In some embodiments, the mineral particles (such as barium sulfate and / or calcium sulfate particles) may have a shape that is generally granular or nodular in nature. In such embodiments, the particles may have a median size (e.g., diameter) of about 0.5 micrometers to about 20 micrometers, in some embodiments about 1 micrometer to about 15 micrometers, in some embodiments about 1.5 micrometers to about 10 micrometers, and in some embodiments about 2 micrometers to about 8 micrometers, as determined by laser diffraction techniques (e.g., using a Horiba LA-960 particle size analyzer) according to ISO 13320:2009. In other embodiments, it may also be desirable to employ flake-like mineral particles (such as mica particles) having a relatively high aspect ratio (e.g., average diameter divided by average thickness) (e.g., about 4 or greater, in some embodiments about 8 or greater, and in some embodiments about 10 to about 500). In such embodiments, the average diameter of the particles may be, for example, about 5 micrometers to about 200 micrometers, in some embodiments about 8 micrometers to about 150 micrometers, and in some embodiments about 10 micrometers to about 100 micrometers. Similarly, the average thickness, as determined by laser diffraction techniques (e.g., using a Horiba LA-960 particle size analyzer) according to ISO 13320:2009, can be about 2 micrometers or less, about 5 nanometers to about 1 micrometer in some embodiments, and about 20 nanometers to about 500 nanometers in some embodiments. The mineral particles can also have a narrow size distribution. That is, at least about 70% by volume of the particles, at least about 80% by volume in some embodiments, and at least about 90% by volume in some embodiments, can have sizes within the aforementioned ranges.

[0045] Similarly, suitable mineral fibers may include those derived from the following compounds: silicates, such as neosilicates, tansilicates, chain silicates (e.g., calcium chain silicates, such as wollastonite; calcium magnesium chain silicates, such as tremolite; calcium magnesium iron chain silicates, such as actinolite; magnesium iron chain silicates, such as anthocyanin; etc.), folin silicates (e.g., aluminum folin silicates, such as palygorskite), reticulate silicates, etc.; sulfates, such as calcium sulfate (e.g., dehydrated or anhydrous gypsum); mineral wool (e.g., rock wool or slag wool); etc. Particularly suitable are fibers with the desired hardness value, including fibers derived from chain silicates (such as wollastonite (Mohs hardness 4.5 to 5.0), which are commercially available under the trade name Nyglos® (e.g., Nyglos® 4W or Nyglos® 8)). The mineral fibers can have a median width (e.g., diameter) of about 1 micrometer to about 35 micrometers, in some embodiments about 2 micrometers to about 20 micrometers, in some embodiments about 3 micrometers to about 15 micrometers, and in some embodiments about 7 micrometers to about 12 micrometers. The mineral fibers can also have a narrow size distribution. That is, at least about 60% by volume of the fibers, in some embodiments at least about 70% by volume of the fibers, and in some embodiments at least about 80% by volume of the fibers can have dimensions within the above ranges. In addition to having the above-described size characteristics, the mineral fibers can also have a relatively high aspect ratio (average length divided by median width) to help further improve the mechanical properties and surface quality of the resulting polymer composition. For example, the mineral fibers can have an aspect ratio 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 can, for example, range from about 1 micrometer to about 200 micrometers, in some embodiments about 2 micrometers to about 150 micrometers, in some embodiments about 5 micrometers to about 100 micrometers, and in some embodiments about 10 micrometers to about 50 micrometers.

[0046] B. Fiber filler

[0047] Fiber fillers can also be used in polymer compositions. Fiber fillers typically comprise fibers with high tensile strength relative to their mass. For example, the ultimate tensile strength of the fibers (as determined according to ASTM D2101) is typically from about 1,000 MPa to about 15,000 MPa, in some embodiments from about 2,000 MPa to about 10,000 MPa, and in some embodiments from about 3,000 MPa to about 6,000 MPa. To help maintain the desired properties, these high-strength fibers can be formed from materials that are generally insulating in nature, such as glass, ceramics (e.g., alumina or silica), aromatic polyamides (e.g., Kevlar® sold by EI du Pont de Nemours, Wilmington, Del.), polyolefins, polyesters, etc. Glass fibers (such as E-glass, A-glass, C-glass, D-glass, AR-glass, R-glass, S1-glass, S2-glass, etc.) are particularly suitable. All or part of these fibers can be recycled if desired.

[0048] Although the fibers used in the fiber filler can have a variety of sizes, fibers with a certain aspect ratio can help improve the mechanical properties of the resulting polymer composition. That is, fibers having an aspect ratio (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 advantageous. Such fibers can, for example, have a weight-average length of about 100 micrometers to about 800 micrometers, about 120 micrometers to about 500 micrometers in some embodiments, about 150 micrometers to about 350 micrometers in some embodiments, and about 200 micrometers to about 300 micrometers in some embodiments. Similarly, fibers can have a nominal diameter of about 6 micrometers to about 35 micrometers, and about 9 micrometers to about 18 micrometers in some embodiments. The relative amount of fiber filler can also be selectively controlled to help achieve the desired mechanical and thermal properties. For example, the fiber filler can 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.

[0049] C. Impact modifier

[0050] Impact modifiers may also be used in polymer compositions. For example, an impact modifier may be a polymer containing olefin monomer units derived from one or more α-olefins. Examples of such monomers include, for instance, 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 having one or more methyl, ethyl, or propyl substituents; 1-hexene having one or more methyl, ethyl, or propyl substituents; 1-heptene having one or more methyl, ethyl, or propyl substituents; 1-octene having one or more methyl, ethyl, or propyl substituents; 1-nonene having one or more methyl, ethyl, or propyl substituents; 1-decene substituted with ethyl, methyl, or dimethyl; 1-dodecene; and styrene. Particularly desirable α-olefin monomers are ethylene and propylene. Olefin polymers may be in the form of copolymers containing other monomer units known in the art. For example, another suitable monomer may include "(meth)acrylic acid" monomers, which include acrylic acid and methacrylic acid monomers, as well as their salts or esters, such as acrylate and methacrylate monomers. Examples of such (meth)acrylic acid monomers may include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-pentyl acrylate, isoamyl 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, 2-hydroxyethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, n-pentyl methacrylate, n-hexyl methacrylate, isoamyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, 2-ethylbutyl methacrylate, methylcyclohexyl methacrylate, cinnamyl methacrylate, crotonyl methacrylate, cyclohexyl methacrylate, cyclopentyl methacrylate, 2-ethoxyethyl methacrylate, isobornyl methacrylate, etc., and combinations thereof. In one embodiment, for example, the impact modifier may be ethylene methacrylate copolymer (“EMAC”). When used, the relative portions of the monomer components can be selectively controlled. The α-olefin monomer may, for example, constitute 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)acrylate monomer) 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.

[0051] Other suitable olefin copolymers can be those that are “epoxy-functionalized” because they contain two or more epoxy functional groups per molecule on average. The copolymer may also contain epoxy-functionalized monomer units. An example of such units is an epoxy-functionalized (meth)acrylate monomer component. For example, suitable epoxy-functionalized (meth)acrylate monomers may include, but are not limited to, those containing 1,2-epoxy groups, such as glycidyl acrylate and glycidyl methacrylate. Other suitable epoxy-functionalized monomers include allyl glycidyl ether, ethyl glycidyl acrylate, and itaconic acid glycidyl ester. Other suitable monomers may also be used to help achieve the desired molecular weight. In one specific embodiment, for example, the copolymer may be a terpolymer formed from an epoxy-functionalized (meth)acrylate monomer component, an α-olefin monomer component, and a non-epoxy-functionalized (meth)acrylate monomer component. The copolymer may be, for example, poly(ethylene-co-butyl acrylate-co-glycidyl methacrylate). When used, epoxy-functionalized (meth)acrylic acid 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.

[0052] When used, the impact modifier typically comprises about 0.5 parts by weight to about 60 parts by weight, in some embodiments about 1 part by weight to about 50 parts by weight, and in some embodiments about 2 parts by weight to about 30 parts by weight, based on every 100 parts by weight of the liquid crystal polymer used in the composition. For example, the impact modifier may comprise 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.%

[0053] D. Laser-activated additives

[0054] While not strictly necessary, a polymer composition can be "laser-activated" in the sense that it contains an additive that can be activated by a laser direct forming ("LDS") process. In this process, the additive is exposed to a laser that induces metal release. The laser then patterns the conductive elements onto the part, leaving a roughened surface containing embedded metal particles. These particles act as nuclei for crystal growth during subsequent plating processes (e.g., copper, gold, nickel, silver, zinc, tin, etc.). Laser-activated additives generally comprise oxide crystals that can include two or more metal oxide cluster configurations within a definable crystal formation. For example, the overall crystal formation can have the following general formula:

[0055] AB2O4 or ABO2

[0056] in,

[0057] A is a metallic cation with a valence of divalent or higher, such as cadmium, chromium, manganese, nickel, zinc, copper, cobalt, iron, magnesium, tin, titanium, and combinations thereof; and

[0058] B is a metal cation with a valence of trivalent or higher, such as antimony, chromium, iron, aluminum, nickel, manganese, tin, and combinations thereof.

[0059] Typically, A in the above formula provides the main cationic component of the first metal oxide cluster, and B provides the main cationic 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. In any case, the clusters together can provide a single identifiable crystal type 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 this invention and is available from Shepherd Color Co. under the trade name “Shepherd Black 1GM”. In some cases, the laser-activated additive may also have a core-shell configuration, as described in WO 2018 / 130972. In these types of additives, the shell component is typically laser-activated, while the core can be any general compound, such as inorganic compounds (e.g., titanium dioxide, mica, talc, etc.).

[0060] When used, laser-activated additives typically constitute 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. Of course, the polymer composition may also be free of (i.e., 0 wt.%) such laser-activated additives (such as spinel crystals) 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).

[0061] E. Other optional additives

[0062] Polymer compositions may also contain a variety of other additives, such as lubricants, thermally conductive fillers, pigments (e.g., carbon black), antioxidants, stabilizers, surfactants, waxes, flame retardants, anti-dripping additives, nucleating agents (e.g., boron nitride), abrasives (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 performance and processability. For example, lubricants that can withstand the processing conditions of liquid crystal polymers without substantially decomposing can be used in polymer compositions. Examples of such lubricants include fatty acid esters, their salts; esters, fatty acid amides, organophosphate esters, and hydrocarbon waxes, including mixtures thereof, are commonly used as lubricants in the processing of engineering plastics materials. Suitable fatty acids typically have a main carbon chain of about 12 to about 60 carbon atoms, such as myristic acid, palmitic acid, stearic acid, arachidic acid, linalic acid, octadecanoic acid, parinric acid, etc. 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 ethylene bisamides, and alkanolamides, such as palmitamide, stearamide, oleamide, N,N'-ethylene bisstearamide, etc. Also suitable are metal salts of fatty acids, such as calcium stearate, zinc stearate, magnesium stearate, etc.; hydrocarbon waxes, including paraffin wax, polyolefin and oxidized polyolefin waxes, and microcrystalline waxes. Particularly suitable lubricants are acids, salts, or amides of stearic acid, such as pentaerythritol tetrastearate, calcium stearate, or N,N'-ethylene bisstearamide. 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.% (by weight).

[0063] The components used to form the polymer composition can be combined using any of a variety of different techniques known in the art. In one specific embodiment, for example, the bio-based LCP and other optional additives can be melt-processed as a mixture within an extruder to form the polymer composition. The mixture can 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 can be melt-processed in an extruder comprising multiple temperature zones. The temperatures of the individual zones are typically set between about -60°C and about 25°C relative to the melt temperature of the liquid crystal polymer. For example, the mixture can be melt-processed using a twin-screw extruder (e.g., a Leistritz 18-mm co-rotating fully intermeshing twin-screw extruder). A general screw design can be used to melt-process the mixture. In one embodiment, the mixture comprising all components can be fed into a feed throat in a first barrel via a volumetric feeder. In another embodiment, as is known, different components can be added at different addition points within the extruder. For example, a liquid crystal polymer can be applied at the feed throat, and certain additives (e.g., dielectric fillers) can be supplied in the same or different temperature range downstream. In any case, the resulting mixture can be melted and blended, then extruded through a die. The extruded polymer composition can then be quenched and cured in a water bath, granulated in a granulator, and then dried.

[0064] Despite containing bio-based LCPs, the polymer compositions can still exhibit a variety of properties similar to those formed with conventional types of liquid crystal polymers. For example, the polymer compositions can exhibit excellent melt processability. For instance, the polymer compositions can have a melt processability of 1,000 seconds according to ISO 11443:2021. -1The ultra-low melt viscosity, measured at a shear rate and at a temperature about 15°C above the melt temperature of the polymer composition, is such as about 0.1 Pa·s to about 100 Pa·s, in some embodiments about 0.2 Pa·s to about 75 Pa·s, in some embodiments about 0.5 Pa·s to about 65 Pa·s, in some embodiments about 0.1 Pa·s to about 50 Pa·s, in some embodiments about 0.2 Pa·s to about 45 Pa·s, in some embodiments about 0.5 Pa·s to about 40 Pa·s, and in some embodiments about 1 Pa·s to about 35 Pa·s. The polymer composition may also exhibit excellent thermal properties. The melt temperature of the composition may be, 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. Even at such melting temperatures, the ratio of the load flexural temperature (“DTUL”) (a measure of short-term heat resistance) to the melt temperature remains relatively high. For example, the ratio can 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 ​​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, and in some embodiments about 240°C to about 280°C. Such high DTUL values ​​particularly allow for the use of high-speed and reliable surface-mount processes to mate the structure with other components.

[0065] The polymer composition can also exhibit high impact strength, which is useful when forming thin layers. For example, as determined according to ISO test number ISO 179-1:2010 at a temperature of 23°C, the composition can have an impact strength of about 0.5 kJ / m². 2 Or greater, in some embodiments about 1 kJ / m 2 Approximately 60 kJ / m 2 In some implementations, it is approximately 2 kJ / m 2 Approximately 50 kJ / m 2 In some implementations, it is approximately 5 kJ / m 2 Approximately 45 kJ / m 2The notched impact strength of the simply supported beam. The tensile and flexural mechanical properties of the composition can also be good. For example, the polymer composition can exhibit tensile strengths of about 20 MPa to about 500 MPa, in some embodiments about 50 MPa to about 400 MPa, and in some embodiments about 70 MPa to about 350 MPa; tensile fracture strains of about 0.4% or greater, in some embodiments about 0.5% to about 10%, and in some embodiments about 0.6% to about 3.5%; and / or tensile modulus of about 5,000 MPa to about 20,000 MPa, in some embodiments about 8,000 MPa to about 20,000 MPa, and in some embodiments about 10,000 MPa to about 20,000 MPa. Tensile properties can be determined according to ISO test number 527:2019 at a temperature of 23°C. The polymer composition may also exhibit a flexural strength of about 20 MPa to about 500 MPa, in some embodiments about 50 MPa to about 400 MPa, and in some embodiments about 100 MPa to about 350 MPa; a flexural elongation of about 0.4% or greater, in some embodiments about 0.5% to about 10%, and 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, and in some embodiments about 10,000 MPa to about 15,000 MPa. Flexural properties can be determined according to 178:2019 at a temperature of 23°C.

[0066] Once formed, the polymer composition can be molded into any of a variety of different shaped parts using techniques known in the art. For example, the shaped parts can 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 well-suited for forming electronic components with small size tolerances. For example, such parts typically include at least one micro-dimension (e.g., about 500 micrometers or less, about 50 to about 450 micrometers in some embodiments, and about 100 to about 400 micrometers in some embodiments) of a dimension (e.g., thickness, width, height, etc.).

[0067] One such component is a fine-pitch electrical connector. More specifically, such connectors are typically used for the detachable mounting of a central processing unit (“CPU”) to a printed circuit board. The connector may include insertion channels configured to receive contact pins. These channels are defined by opposing walls that can be formed from a thermoplastic resin. To help achieve the 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, requires a small pitch of the pin insertion channels and a small width of the opposing walls separating these channels. For example, the walls may have a width of about 500 micrometers or less, about 50 micrometers to about 450 micrometers in some embodiments, and about 100 micrometers to about 400 micrometers in some embodiments. The polymer compositions of the present invention are particularly suitable for forming the walls of fine-pitch connectors. In addition to or in place of the walls, it should be understood that any other part of the connector housing may also be formed from the polymer composition. For example, the connector may also include a shield surrounding the housing. Some or all of the shield may be formed from the polymer composition. For example, the housing and the shield may each be a one-piece structure integrally molded from the polymer composition. Similarly, the shielding element can be a two-piece structure comprising a first housing and a second housing, each of which can be formed from a polymer composition.

[0068] Of course, 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 electronic components. The substrate can be thin, such as having a thickness of about 500 micrometers or less, about 50 micrometers to about 450 micrometers in some embodiments, and about 100 micrometers 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 forming, electroplating, etc.). The conductive elements can be used for a variety of different 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, such as antennas with resonant elements, formed by patch antenna structures, inverted F-type antenna structures, slotted and open slotted antenna structures, loop antenna structures, monopole, dipole, planar inverted F-type antenna structures, hybrids of these designs, etc. The resulting antenna structures can be incorporated into the housings of relatively compact portable electronic components, such as those described above, where the available internal space is relatively small.

[0069] The planar substrate formed from the above-described polymer composition can also be used in other applications. For example, in one embodiment, the planar substrate can be used to form a base for a compact camera module (“CCM”) typically used in wireless communication devices (e.g., cellular phones). The compact camera module may include a lens assembly covering the base. The base, in turn, covers an optional motherboard. Due to their relatively thin nature, the base and / or motherboard are particularly suitable for being formed from the polymer composition described above. The lens assembly can have any of a variety of configurations known in the art and can include a fixed-focus lens and / or an autofocus lens. In one embodiment, for example, the lens assembly has a hollow cylindrical form that houses a lens in communication with an image sensor located on the motherboard and controlled by circuitry. The cylinder can have any of a variety of shapes (e.g., rectangular, cylindrical, etc.). In some embodiments, the cylinder may also be formed from the polymer composition and have a wall thickness 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., polyester film) and / or a thermally insulating cap may cover the lens assembly. In some embodiments, the film and / or cap may also be formed from the polymer composition.

[0070] Other possible electronic components that can utilize this polymer composition include, for example, cellular phones, laptops, small portable computers (e.g., ultra-portable computers, netbooks, and tablets), watch devices, pendant devices, headsets and handset devices, media players with wireless communication capabilities, handheld computers (sometimes also called personal digital assistants), remote controls, global positioning system (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 electronic devices, printer parts, etc.

[0071] The following testing methods can be used to determine one or more of the above-mentioned performance characteristics.

[0072] Melt viscosity: can be measured at 400s according to ISO 11443:2021. -1 Or 1,000s -1 The melt viscosity (Pa·s) was determined using a Dynisco LCR 7001 capillary rheometer at a shear rate and a temperature 15°C above the melting temperature (e.g., approximately 325°C). The rheometer orifice (die) can 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 can be 9.55 mm ± 0.005 mm, and the rod length can be 233.4 mm.

[0073] Melting temperature: The melting temperature (“Tm”) can be determined by differential scanning calorimetry (“DSC”) as known in the art. As determined according to ISO 11357-3:2018, the melting temperature is the peak melting temperature of the differential scanning calorimetry (DSC). Under the DSC procedure, as described in ISO standard 10350, DSC measurements are performed on a TA Q2000 instrument, with the sample heated and cooled at 20°C per minute.

[0074] Load flexure temperature (“DTUL”): The load flexure temperature can be determined according to ISO 75-2:2013 (technically equivalent to ASTM D648). More specifically, a three-point bending test along the edge can be performed on a test strip sample with a length of 80 mm, a thickness of 10 mm, and a width of 4 mm, where the specified load (maximum external fiber stress) is 1.8 MPa. The sample can be placed in a silicone oil bath where the temperature is increased at 2°C per minute until it flexes to 0.25 mm (0.32 mm for ISO test number 75-2:2013).

[0075] 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 can be performed on identical test strips with a length of 80 mm, a thickness of 10 mm, and a width of 4 mm. The test temperature can be 23°C, and the test speed can be 1 mm / min or 5 mm / min.

[0076] Flexural modulus, flexural stress, and flexural elongation: Flexural properties can be tested according to ISO 178:2019 (technically equivalent to ASTM D790). This test can be performed over a 64 mm support span. The test can also be performed on the center portion of an uncut ISO 3167 multipurpose bar. The test temperature can be 23°C, and the test speed can be 2 mm / min.

[0077] Impact strength of simply supported beams: The performance of simply supported beams can be tested according to ISO 179-1:2010 (technically equivalent to ASTM D256-10, Method B). Type I specimens (80 mm length, 10 mm width, 4 mm thickness) can be used for this test. When testing notched impact strength, the notch can be a Type A notch (0.25 mm bottom radius). The specimen can be cut from the center of a multi-purpose bar using a single-tooth milling machine. The test temperature can be 23°C.

[0078] These and other modifications and variations can be made to the invention by those skilled in the art without departing from the spirit and scope thereof. Furthermore, it should be understood that aspects of the various embodiments can be interchanged in whole or in part. Moreover, those skilled in the art will understand that the foregoing description is merely illustrative and not intended to limit the invention further described in the appended claims. Claims (as amended under Article 19 of the Treaty) 1. A method for forming a bio-based biphenol monomer for liquid crystal polymers, the method comprising: Provides bio-based dialkylphenols derived from bio-based naphtha; Oxidative coupling of the bio-based dialkylphenols to form alkylated biphenols; and The alkylated phenol is dealkylated to form the bio-based biphenol. 2. The method according to claim 1, wherein the bio-based dialkylphenol 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 the oxidative coupling is carried out in the presence of a catalyst. 5. The method of claim 1, wherein the dealkylation comprises contacting the alkylated phenol with an acid. 6. The method of claim 1, wherein the bio-based dialkylphenol is formed by reacting a bio-based phenol with isobutylene, wherein the bio-based phenol is derived from the bio-based naphtha. 7. The method of claim 6, wherein the bio-based phenol is formed by oxidizing bio-based cumene to form hydroperoxide radicals, and then cleaving the cumene hydroperoxide radicals in the presence of an acid catalyst to form bio-based phenol, wherein the bio-based cumene is derived from the bio-based naphtha. 8. The method of claim 7, wherein the bio-based cumene is formed by alkylating a bio-based benzene, wherein the bio-based benzene is derived from the bio-based naphtha. 9. The method of claim 8, wherein the bio-based naphtha is subjected to a steam cracking process to form the bio-based benzene. 10. The method of claim 1, wherein the bio-based naphtha is formed from a bio-based distillate feedstock, the bio-based distillate feedstock comprising a complex mixture of naturally occurring fats and / or oils. 11. The method of claim 10, wherein the bio-based distillate feedstock comprises fats and / or oils derived from cotton, coconut, corn, palm, peanut, flaxseed, rice, rapeseed, olive, soybean, sunflower, linola, animal fats, tall oil, castor oil, butter, milk, or combinations thereof. 12. The method of claim 11, wherein the bio-based naphtha is formed by a method comprising fractionating the bio-based distillate feedstock into a substantially liquid triglyceride phase L and a saturated or substantially saturated solid or substantially solid triglyceride phase S, wherein the bio-based naphtha is derived from phase S. 13. The method according to claim 1, wherein the bio-based biphenol monomer is bio-based 4-4'-biphenol. 14. A bio-based 4-4'-biphenol monomer formed by the method of claim 1. 15. A bio-based liquid crystal polymer comprising repeating units derived from the bio-based 4,4'-biphenol monomer of claim 14. 16. A bio-based liquid crystal polymer comprising repeating units derived from one or more biphenols, optionally repeating units derived from one or more aromatic hydroxycarboxylic acids, optionally repeating units derived from one or more dicarboxylic acids, and optionally repeating units derived from one or more aromatic diols, wherein the one or more biphenols include bio-based 4,4'-biphenol derived from bio-based naphtha. 17. The bio-based liquid crystal polymer of claim 16, wherein the bio-based liquid crystal polymer contains 6 mol.% to about 30 mol.% of repeating units derived from bio-based 4,4'-biphenol. 18. The bio-based liquid crystal polymer of 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-naphthoic acid, hydroquinone, 4-aminophenol, p-acetaminophenol, or combinations thereof. 19. The bio-based liquid crystal polymer of claim 16, wherein the thermotropic liquid crystal polymer is completely aromatic. 20. The bio-based liquid crystal polymer of claim 16, wherein the polymer composition has a melting temperature of about 280°C to about 400°C. 21. The bio-based liquid crystal polymer of claim 16, wherein the polymer has a bio-based content of about 5 wt.% to 70 wt.% based on the total weight of the monomers used in the polymer. 22. The polymer composition of claim 15, wherein the composition comprises the bio-based liquid crystal polymer and one or more optional additives. 23. The polymer composition of 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.

Claims

1. A method for forming a bio-based biphenol monomer for liquid crystal polymers, the method comprising: Provides bio-based dialkylphenols derived from bio-based naphtha; Oxidative coupling of the bio-based dialkylphenols to form alkylated biphenols; and The alkylated phenol is dealkylated to form the bio-based biphenol.

2. The method according to claim 1, wherein the bio-based dialkylphenol 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 the oxidative coupling is carried out in the presence of a catalyst.

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

6. The method of claim 1, wherein the bio-based dialkylphenol is formed by reacting a bio-based phenol with isobutylene, wherein the bio-based phenol is derived from the bio-based naphtha.

7. The method of claim 6, wherein the bio-based phenol is formed by oxidizing bio-based cumene to form hydroperoxide radicals, and then cleaving the cumene hydroperoxide radicals in the presence of an acid catalyst to form bio-based phenol, wherein the bio-based cumene is derived from the bio-based naphtha.

8. The method of claim 7, wherein the bio-based cumene is formed by alkylating a bio-based benzene, wherein the bio-based benzene is derived from the bio-based naphtha.

9. The method of claim 8, wherein the bio-based naphtha is subjected to a steam cracking process to form the bio-based benzene.

10. The method of claim 1, wherein the bio-based naphtha is formed from a bio-based distillate feedstock, the bio-based distillate feedstock comprising a complex mixture of naturally occurring fats and / or oils.

11. The method of claim 10, wherein the bio-based distillate feedstock comprises fats and / or oils derived from cotton, coconut, corn, palm, peanut, flaxseed, rice, rapeseed, olive, soybean, sunflower, linola, animal fats, tall oil, castor oil, butter, milk, or combinations thereof.

12. The method of claim 11, wherein the bio-based naphtha is formed by a method comprising fractionating the bio-based distillate feedstock into a substantially liquid triglyceride phase L and a saturated or substantially saturated solid or substantially solid triglyceride phase S, wherein the bio-based naphtha is derived from phase S.

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

14. A bio-based 4-4'-biphenol monomer formed by the method of claim 1.

15. A bio-based liquid crystal polymer comprising repeating units derived from the bio-based 4,4'-biphenol monomer of claim 14.

16. A bio-based liquid crystal polymer comprising repeating units derived from one or more biphenols, optionally repeating units derived from one or more aromatic hydroxycarboxylic acids, optionally repeating units derived from one or more dicarboxylic acids, and optionally repeating units derived from one or more aromatic diols, wherein the one or more biphenols include bio-based 4,4'-biphenol derived from bio-based naphtha.

17. The bio-based liquid crystal polymer of claim 15, wherein the bio-based liquid crystal polymer contains 6 mol.% to about 30 mol.% of repeating units derived from bio-based 4,4'-biphenol.

18. The bio-based liquid crystal polymer of claim 15, wherein the polymer further comprises repeating units derived from 4-hydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, terephthalic acid, isophthalic acid, 2,6-naphthoic acid, hydroquinone, 4-aminophenol, p-acetaminophenol, or combinations thereof.

19. The bio-based liquid crystal polymer of claim 15, wherein the thermotropic liquid crystal polymer is completely aromatic.

20. The bio-based liquid crystal polymer of claim 15, wherein the polymer composition has a melting temperature of about 280°C to about 400°C.

21. The bio-based liquid crystal polymer of claim 15, wherein the polymer has a bio-based content of about 5 wt.% to 70 wt.% based on the total weight of the monomers used in the polymer.

22. The polymer composition of claim 15, wherein the composition comprises the bio-based liquid crystal polymer and one or more optional additives.

23. The polymer composition of 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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