Polyetherketoneketone
Polyetherketoneketone (PEKK) is a semi-crystalline thermoplastic polymer within the polyaryletherketone (PAEK) family, characterized by a repeating molecular structure featuring ether linkages and two ketone groups connected by benzene rings, which confer exceptional thermal stability, mechanical strength, and chemical resistance suitable for demanding engineering applications.[1][2] First synthesized in the 1960s, it was commercialized by Arkema starting in the 2010s under the Kepstan® brand; PEKK is synthesized via Friedel-Crafts acylation of diphenyl ether with mixtures of terephthaloyl (T) and isophthaloyl (I) chlorides derived from terephthalic and isophthalic acids, with customizable T/I ratios (such as 60/40, 70/30, or 80/20) that modulate its crystallization rate, melting point, and processability.[1][2] This structural versatility distinguishes PEKK from related PAEK polymers like polyetheretherketone (PEEK), due to its structure featuring two ketone groups per ether linkage (compared to PEEK's single ketone), with adjustable T/I ratios (typically 60/40 to 80/20) that enhance rigidity and polarity while allowing lower processing temperatures compared to PEEK's single ketone per unit.[3][4] Key mechanical properties include a tensile strength of 100-150 MPa, flexural modulus of 2.8-4.0 GPa, and compressive strength up to 180 MPa, enabling PEKK to withstand high loads and impacts in structural components.[5][2] Thermally, it supports continuous use temperatures up to 260°C, with glass transition temperatures around 160-165°C and melting points varying from 305°C to 358°C depending on the T/I ratio, making it ideal for high-heat environments without degradation.[1] Chemically, PEKK exhibits outstanding resistance to acids, bases, solvents, and hydrolysis, retaining over 90% of its mechanical integrity after prolonged exposure to harsh media like toluene or steam.[5] Its biocompatibility, evidenced by low bacterial adhesion and minimal inflammatory response, has earned FDA approval for medical implants, further broadening its utility.[2] PEKK finds primary applications in aerospace (e.g., aircraft brackets and engine components for its lightweight strength), oil and gas (downhole tools resistant to extreme pressures), medical devices (dental prostheses, spinal cages, and orthopedic implants due to bone-like elasticity reducing stress shielding), and additive manufacturing (3D-printed parts via filament or powder processes, leveraging its tunable crystallization for better layer adhesion).[1][2] Compared to PEEK, PEKK offers similar performance but with advantages in processing ease and higher compressive strength (up to 80% greater in unreinforced forms), though it may incur higher costs due to specialized synthesis.[6][2] Ongoing research explores PEKK composites with carbon fibers or mica fillers to enhance conductivity and printability for emerging fields like regenerative medicine and sustainable electronics.[7][8]Overview and History
Definition and Chemical Identity
Polyetherketoneketone (PEKK) is a semi-crystalline thermoplastic polymer within the polyaryletherketone (PAEK) family, characterized by its high thermal stability and mechanical strength. Its systematic chemical name is poly(oxy-1,4-phenylenecarbonyl-1,4-phenylenecarbonyl-1,4-phenylene), and it features a repeating unit with the general formula [–O–C₆H₄–CO–C₆H₄–CO–]ₙ, where the central dicarbonyl-linked phenylene rings incorporate a mixture of terephthaloyl (T, 1,4-linked) and isophthaloyl (I, 1,3-linked) isomers.[9][10] This structure distinguishes PEKK by having one ether linkage and two ketone linkages per repeat unit, contributing to its unique balance of processability and performance. The specific identity of PEKK is defined by the ratio of T to I units, which varies across commercial grades such as 60/40, 70/30, and 80/20, influencing the polymer's chain linearity and overall rigidity. Higher T content promotes a more extended, para-oriented conformation, resulting in a stiffer molecular architecture, while increasing I incorporation introduces meta linkages that enhance solubility and melt processability without fundamentally altering the core chemistry. A 100% T composition yields the most rigid variant due to its fully linear backbone.[11][12] The nomenclature "polyetherketoneketone" reflects the single ether (–O–) linkage combined with two ketone (–CO–) groups in the repeating unit, differentiating it from related PAEK polymers. PEKK was first synthesized in the 1960s as part of early research into high-performance materials.[13][14]| Polymer | Acronym | Linkages per Repeat Unit | Repeating Unit Formula |
|---|---|---|---|
| Poly(ether ketone) | PEK | 1 ether, 1 ketone | [–O–C₆H₄–CO–]ₙ |
| Poly(ether ether ketone) | PEEK | 2 ethers, 1 ketone | [–O–C₆H₄–O–C₆H₄–CO–]ₙ |
| Poly(ether ketone ketone) | PEKK | 1 ether, 2 ketones | [–O–C₆H₄–CO–C₆H₄–CO–]ₙ |
Development and Commercialization
Polyetherketoneketone (PEKK) was first synthesized in 1962 by DuPont researchers, including D.C. Bonner, using Friedel-Crafts acylation as part of efforts to develop high-temperature-resistant materials for the Apollo space program.[17] This invention addressed the need for polymers capable of withstanding extreme thermal and mechanical stresses in aerospace environments, marking an early milestone in the polyaryletherketone (PAEK) family.[18] Subsequent patents in the 1970s and 1980s built on this foundation, refining synthesis methods to improve yield and polymer properties for potential industrial use.[17] DuPont initiated commercialization of PEKK in 1988, targeting aerospace applications where its superior thermal stability offered advantages over existing materials.[19] However, the intricate synthesis process—requiring precise control of polymerization conditions and substantial capital for specialized equipment—posed significant challenges, restricting early production to small volumes and limiting market penetration beyond niche sectors.[13] In the late 2000s, Arkema partnered with Oxford Performance Materials (OPM) and developed PEKK using a synthesis method based on early DuPont technology, launching the Kepstan® brand through dedicated production facilities in France and the United States.[20] By the 2010s, PEKK transitioned from primarily aerospace uses to broader adoption in oil and gas, medical devices, and transportation, driven by demand for lightweight, durable composites.[13] The global market reached about $457 million in 2023, reflecting this growth, with projections for a compound annual growth rate (CAGR) of 9.2% through 2030 as applications diversify.[21] Key players include Arkema (with Kepstan®), Solvay (with NovaSpire™), and Oxford Performance Materials (with OXPEKK®); notably, Arkema introduced the Kepstan® 6000 series copolymers in 2013, optimized for slower crystallization and lower melt temperatures to facilitate injection molding and extrusion in high-performance parts. In 2017, Solvay began PEKK resin production in the United States to support aerospace thermoplastic composites, and Hexcel acquired OPM's aerospace and defense business. As of June 2024, Arkema granted an exclusive technology license to SEQENS to manufacture PEKK for long-term medical implantable applications.[22][23][24][25][26]Chemical Structure and Synthesis
Molecular Structure
Polyetherketoneketone (PEKK) is an aromatic thermoplastic polymer belonging to the polyaryletherketone (PAEK) family, characterized by a linear backbone consisting of ether (-O-) and consecutive ketone (-C=O-) linkages connecting phenylene rings. The molecular structure is derived from the polymerization of diphenyl ether (C12H10O), which provides the ether linkages after acylation on its phenyl rings, with terephthaloyl chloride (1,4-benzenedicarbonyl dichloride, providing para-oriented "T" units) and isophthaloyl chloride (1,3-benzenedicarbonyl dichloride, providing meta-oriented "I" units). This results in a copolymer with the general repeating unit depicted as: \left[ -\ce{O-C6H4-C(=O)-C6H4-C(=O)}- \right]_n where the central \ce{-C6H4-} group between the two carbonyls is either para-linked (from T) or meta-linked (from I), and all other phenylenes are para-substituted for optimal chain linearity.[27] The idealized polymerization can be represented as the Friedel-Crafts acylation reaction involving diphenyl ether and the diacid chlorides in the presence of a Lewis acid catalyst, yielding the polymer chain with elimination of HCl byproducts, though the exact stoichiometry depends on the T/I monomer feed ratio. Structural variations arise primarily from the T/I ratio, which controls the proportion of para versus meta linkages in the diketone segments; for instance, a 60/40 T/I ratio promotes more amorphous character due to disrupted chain packing from meta distortions, while an 80/20 T/I ratio enhances crystallinity by favoring linear, para-dominant sequences that facilitate better intermolecular alignment. Commercial grades of PEKK exploit these ratios to tailor processability and performance, as detailed in production contexts.[28] The molecular architecture of PEKK is confirmed through spectroscopic techniques, with infrared (IR) spectroscopy revealing a characteristic absorption peak at approximately 1645 cm-1 attributable to the stretching vibration of the ketone carbonyl (C=O) groups conjugated with aromatic rings. Proton nuclear magnetic resonance (1H NMR) spectra exhibit signals for aromatic protons in the 7.0–8.0 ppm range, reflecting the deshielded environments of the phenylene protons adjacent to electron-withdrawing ether and ketone functionalities, while 13C NMR confirms the distinct carbon environments of the carbonyl (around 190–200 ppm) and aromatic carbons.[29]Synthesis Methods
Polyetherketoneketone (PEKK) is primarily synthesized through electrophilic Friedel-Crafts acylation, a polycondensation reaction between diphenyl ether and a mixture of terephthaloyl chloride (T-cl) and isophthaloyl chloride (I-cl) under anhydrous conditions. This method employs a Lewis acid catalyst, typically aluminum chloride (AlCl₃), in solvents such as nitrobenzene or ortho-dichlorobenzene, with reaction temperatures ranging from 50°C to 120°C to facilitate progressive catalyst addition and minimize side reactions. The process generates HCl as a byproduct, and the T/I ratio in the diacid chloride mixture is adjusted during monomer feed to influence polymer crystallinity, commonly targeting ratios of 55/45 to 75/25 for balanced properties.[30][14][31] The reaction mechanism involves electrophilic attack by the activated acyl chloride on the electron-rich diphenyl ether, forming ether-ketone linkages iteratively. A representative equation for the polymerization is: \ce{(C6H5)2O + n [ClC(O)C6H4C(O)Cl]_{T/I} -> [-OC6H4C(O)C6H4C(O)-]_{n,T/I} + 2n HCl} where the subscript denotes the T/I isomer mix. Following polymerization, the crude product is purified by dissolution in a solvent like ortho-dichlorobenzene and precipitation into methanol or water, followed by filtration, washing, and vacuum drying at 120°C, yielding high-molecular-weight polymers (Mw 50,000–100,000 g/mol) at 90–95% efficiency.[30][32][17] An alternative nucleophilic aromatic substitution route involves the polycondensation of bis(4-hydroxybenzoyl)benzene (meta/para isomers) with bis(4-fluorobenzoyl)benzene (meta/para isomers) in diphenyl sulfone solvent at 300–340°C, catalyzed by alkali metal carbonates such as Na₂CO₃ (0.95–1.06 mol equivalents). This two-stage process—initial heating at 180–270°C followed by higher-temperature completion—enhances thermal stability (Td >490°C) and reduces residual halogens (<900 ppm) compared to the electrophilic method.[31][33][31] Synthesis challenges include managing high temperatures that promote branching or degradation, ensuring anhydrous environments to avoid hydrolysis in electrophilic variants, and controlling monomer stoichiometry for consistent molecular weight distribution. Yields remain high (90–95%) but require rigorous purification to remove catalysts and byproducts, particularly chlorine residues in electrophilic products (up to 5750 ppm if unaddressed).[33][17][31]Physical and Thermal Properties
Thermal Characteristics
Polyetherketoneketone (PEKK) exhibits a glass transition temperature (Tg) of approximately 162°C, which remains largely independent of the terephthaloyl/isophthaloyl (T/I) ratio in its copolymer structure.[34] This value, determined via differential scanning calorimetry (DSC) at a heating rate of 20°C/min, indicates the temperature at which the amorphous regions of the polymer transition from a glassy to a rubbery state, influencing its dimensional stability in high-temperature environments.[34] The melting temperature (Tm) of PEKK varies significantly with the T/I ratio, ranging from ~300°C to 365°C across commercial grades. For instance, grades with higher T/I ratios like 80/20 in the KEPSTAN 8000 series reach 355–360°C, as measured by DSC on the second heating cycle.[35][36] Grades with 60/40 T/I ratio, such as those in the KEPSTAN 6000 series, exhibit very slow crystallization kinetics and typically do not show a distinct Tm under standard processing and DSC conditions due to their pseudo-amorphous nature, though a Tm around 300°C can be observed after annealing or very slow cooling to induce crystallization.[37][35] This variability allows tailoring of processing conditions, with crystallinity levels further modulating the observed Tm.[35] PEKK demonstrates exceptional thermal stability, with decomposition onset temperatures exceeding 500°C in air and a 5% weight loss occurring at approximately 572°C under thermogravimetric analysis (TGA).[38] The heat deflection temperature (HDT) under load reaches up to ~300°C at 0.45 MPa for semi-crystalline grades, enabling sustained performance in demanding thermal applications.[36] The coefficient of thermal expansion (CTE) is low, typically 23–27 × 10^{-6} /K below Tg as measured by dynamic mechanical analysis (DMA) in tension, minimizing dimensional changes with temperature fluctuations.[34][36] In terms of flammability, PEKK achieves a UL 94 V-0 rating at 0.8 mm thickness and a limiting oxygen index (LOI) of 38–43%, signifying self-extinguishing behavior and low smoke generation upon exposure to flame.[34][36] These properties, combined with minimal toxic gas emissions, make PEKK suitable for safety-critical uses in aerospace and transportation.[37]Crystallinity and Morphology
Polyetherketoneketone (PEKK) is a semi-crystalline thermoplastic polymer that can achieve degrees of crystallinity from 20% to 40% under optimized conditions such as annealing or slow cooling, influenced primarily by the terephthalic/isophthaloyl (T/I) ratio in its copolymer structure. However, as-processed crystallinity under typical commercial conditions (e.g., moderate to fast cooling rates) is generally low: for instance, <5% for 60/40 T/I ratios (often considered amorphous or pseudo-amorphous), ~3-15% for 70/30, and up to ~30% for 80/20, as measured by differential scanning calorimetry (DSC). These variations arise because the meta-oriented isophthalic units disrupt chain packing, slowing crystallization kinetics and favoring amorphous regions, whereas para-oriented terephthalic units promote ordered structures. Crystallinity is quantified using techniques like DSC, which analyzes enthalpy changes during melting, and X-ray diffraction (XRD), which assesses peak intensities indicative of crystalline order.[39][40] The crystal structure of PEKK consists of an orthorhombic unit cell, with Form 1 featuring a two-chain packing arrangement (dimensions a = 0.769 nm, b = 0.606 nm, c = 1.016 nm along the fiber axis) and Form 2 involving one- or two-chain variants, depending on processing. This orthorhombic lattice enables efficient chain alignment in the crystalline domains, as confirmed by XRD analysis of melt-crystallized samples. Annealing treatments at 200–250°C significantly enhance crystallinity; for instance, isothermal annealing of a 60/40 PEKK grade at 245°C for 60 minutes can increase it from an initial low level to 26–35%, promoting perfection of the crystal lattice and altering thermal transitions such as multiple endotherms observed in DSC.[28][40] Morphologically, PEKK exhibits spherulitic growth in melt-crystallized specimens, where radial lamellae form from instantaneous nucleation sites, as visualized by hot-stage optical microscopy. The spherulite size and density vary with melt holding time and cooling rates, with slower cooling fostering larger spherulites and higher overall crystallinity. Amorphous regions interspersed within this spherulitic matrix provide ductility, while higher crystallinity elevates the modulus and stiffness but diminishes toughness, as brittle failure dominates in densely packed crystalline cores.[40][41] Rapid cooling, conversely, produces predominantly amorphous films or structures suitable for applications requiring flexibility over rigidity.[40][41]Mechanical and Chemical Properties
Mechanical Performance
Polyetherketoneketone (PEKK) exhibits exceptional mechanical performance, characterized by high strength, stiffness, and toughness, making it suitable for demanding structural applications. In semi-crystalline grades, such as those in Arkema's KEPSTAN® 8000 series, PEKK demonstrates a yield tensile strength ranging from 100 to 116 MPa, with elongation at break typically between 3% and >30%, indicating varying ductility depending on the T/I ratio before failure.[36] The stress-strain curve for these grades shows an initial linear elastic region followed by yielding and extensive plastic deformation, culminating in ductile failure without brittle fracture, which enhances its energy absorption capacity under load. Values vary by T/I ratio; e.g., higher T content (as in 8003) increases modulus but reduces ductility.[36] The Young's modulus of semi-crystalline PEKK is in the range of 3.6 to 4.1 GPa, providing stiffness comparable to or slightly superior to polyetheretherketone (PEEK), which has a modulus of approximately 3.5 GPa; this difference arises from PEKK's higher ketone-to-ether ratio, resulting in a more rigid molecular backbone.[36][42] Flexural strength reaches 167 to 187 MPa, allowing PEKK to withstand bending loads effectively while maintaining structural integrity.[36] Impact resistance is notable, with notched Izod values of 35 to 45 J/m for unfilled semi-crystalline grades, reflecting good toughness even at low temperatures down to -30°C.[43] Fatigue resistance is robust, enduring up to 10^7 cycles at 50% of ultimate tensile strength under tensile-tensile loading, which supports long-term cyclic durability in dynamic environments.[44] Creep behavior is minimal under sustained loads, even at elevated temperatures up to 200°C, where PEKK shows lower deformation rates than PEEK due to its enhanced thermal stability and crystallinity.[45] This low creep, combined with inherent chemical resistance, ensures sustained mechanical integrity over extended service life.[45]| Property | Value (Semi-Crystalline Grades) | Test Method | Source |
|---|---|---|---|
| Tensile Strength (Yield) | 100-116 MPa | ISO 527 | Arkema TDS 8000 Series[36] |
| Elongation at Break | 3->30% | ISO 527 | Arkema TDS 8000 Series[36] |
| Young's Modulus | 3.6-4.1 GPa | ISO 527 | Arkema TDS 8000 Series[36] |
| Flexural Strength | 167-187 MPa | ISO 178 | Arkema TDS 8000 Series[36] |
| Notched Izod Impact | 35-45 J/m | ASTM D256 | Gharda Plastics Datasheet[43] |
| Fatigue Cycles (at 50% UTS) | Up to 10^7 | Cyclic Tensile | Literature on CF/PEKK Analogues[44] |
Chemical Resistance
Polyetherketoneketone (PEKK) exhibits exceptional resistance to hydrocarbons, oils, and fuels, showing no significant swelling or degradation even at elevated temperatures up to 250°C, which makes it particularly suitable for demanding applications in the oil and gas industry. For instance, it demonstrates excellent compatibility (rated E, indicating no attack) with gasoline, heptane, hexane, fuel oil, lubricating oil, motor oil, manufactured gas, natural gas, and kerosene at temperatures ranging from 23°C to 200°C.[46] PEKK maintains stability in dilute acids and bases, with excellent resistance (rated E) to 10% hydrochloric acid and sulfuric acid (<40% concentration) up to 100°C, as well as to 20-60% sodium hydroxide and anhydrous ammonia up to 200°C; however, exposure to concentrated acids or bases at temperatures exceeding 300°C can lead to limited hydrolysis and reduced performance.[46] In terms of solvent compatibility, PEKK is insoluble in common organic solvents such as acetone and dimethylformamide (DMF) at 23-100°C, and shows only slight absorption (less than 1 wt%) in chlorinated solvents like methylene chloride at ambient temperatures, preserving its structural integrity without dissolution.[46] PEKK demonstrates robust resistance to radiation and hydrolysis, remaining stable under gamma sterilization doses up to 100 kGy with minimal changes in crystallinity or mechanical properties, particularly in its semi-crystalline forms; its low water absorption (0.1-0.5 wt%) further contributes to hydrolysis resistance in humid or steam environments up to 200°C.[47][48][46] Regarding long-term aging, PEKK offers high oxidative stability in air at 250°C for over 1000 hours, with negligible degradation in thermal or mechanical properties, enabling reliable performance in oxidative environments.[49] This chemical inertness helps preserve PEKK's mechanical integrity in harsh conditions, complementing its intrinsic strength.[46]Production and Processing
Manufacturing Processes
Polyetherketoneketone (PEKK) is produced on an industrial scale through nucleophilic polycondensation, where the ratio of terephthaloyl (T) to isophthaloyl (I) units is controlled to tailor crystallization rates and melting points, typically ranging from 60/40 to 80/20 for commercial grades.[1] Batch reactor processes allow for precise adjustment of T/I ratios by sequential addition of monomers such as 1,4-bis(4-fluorobenzoyl)benzene and mixtures of terephthalic and isophthalic acids in the presence of alkali metal carbonates, with reaction temperatures escalating from 200–260°C to 300–340°C to drive polymerization.[31] Forming techniques for PEKK resin into parts leverage its high melt viscosity and thermal stability. Injection molding is widely used for high-volume components, with barrel temperatures set between 340–360°C in the rear zones progressing to 350–360°C at the nozzle, and mold temperatures of 230–250°C to promote controlled crystallization without warping.[50] Extrusion processes produce filaments, films, and profiles at similar melt temperatures of 340–380°C, allowing for the creation of stock shapes suitable for subsequent machining. Compression molding is particularly effective for fiber-reinforced PEKK composites, involving consolidation of prepregs under pressure at 350–400°C to achieve high fiber volume fractions and uniform distribution, resulting in parts with enhanced mechanical integrity.[51] Additive manufacturing expands PEKK's utility for complex geometries, especially in aerospace. Fused deposition modeling (FDM) or fused filament fabrication (FFF) employs PEKK filaments extruded at nozzle temperatures of 350–400°C, with heated build chambers maintaining 120–160°C to minimize thermal gradients and warping.[52] Laser sintering processes, such as selective laser sintering (SLS), use PEKK powders sintered at laser energies calibrated for melting points of 300–360°C, with build chamber temperatures held at 250–300°C to support layer fusion and reduce residual stresses in high-performance parts like turbine components.[53] Post-processing is essential to optimize PEKK's semi-crystalline structure. Annealing at temperatures around 260°C for several hours increases crystallinity from as-printed levels of 10–20% to 25–35%, enhancing tensile strength and modulus while relieving internal stresses from rapid cooling during forming.[52] Recycling of PEKK involves melt reprocessing of scrap or failed parts, but degradation from repeated thermal cycles limits incorporation to about 20% recycled content in virgin resin blends to avoid significant reductions in molecular weight and mechanical properties, such as a 60% drop in tensile strength after multiple cycles.[54]Commercial Grades and Suppliers
Polyetherketoneketone (PEKK) is commercially available in various grades differentiated primarily by the terephthalic/isophthalic (T/I) acid ratio in their copolymer structure, which influences crystallinity, melting temperature, and processing characteristics. Arkema, the leading producer, offers the Kepstan® series with three main variants: the 6000 series (60/40 T/I ratio) for slower crystallizing, amorphous-like behavior suitable for complex molding; the 7000 series (70/30 T/I ratio) for balanced properties; and the 8000 series (80/20 T/I ratio) for higher crystallinity and thermal stability. For example, Kepstan® 6002, a medium-flow grade in the 6000 series, is processable at temperatures around 340°C and exhibits a melting point of approximately 305°C, making it ideal for injection molding and extrusion. In contrast, Kepstan® 8000 series grades feature a higher melting point of 358°C, enabling applications requiring elevated thermal resistance.[1] Other notable variants include Solvay's NovaSpire™ PEKK resins, which are tailored for aerospace composites and additive manufacturing, often in carbon fiber-reinforced forms for enhanced stiffness. RTP Company provides compounded PEKK in its 4100 series, focusing on custom formulations with high mechanical load-bearing capabilities and flame retardancy for specialized engineering needs. Regional producers like Shandong Kaisheng New Materials Technology Co., Ltd. offer cost-competitive PEKK grades for industrial applications in Asia. Evonik participates in the broader polyaryletherketone (PAEK) market and has partnerships for PEKK in medical applications, though specific offerings focus on compounded high-flow variants for injection molding with limited public specifications.[24][55][56]| Grade Series | T/I Ratio | Key Specifications | Typical Applications |
|---|---|---|---|
| Arkema Kepstan® 6000 (e.g., 6002) | 60/40 | Tm ~305°C, processable at 340°C, amorphous/slow crystallizing | Injection molding, films, 3D printing |
| Arkema Kepstan® 8000 | 80/20 | Tm ~358°C, fast crystallizing, high strength | Composites, high-heat parts |
| Solvay NovaSpire™ | Varies (copolymer) | Reinforced options, high flow for AM | Aerospace structures, coatings |
| RTP 4100 Series | Varies (compounded) | High toughness, flame retardant | Custom mechanical components |