Polyetherimide and compositions and articles made therefrom

Abstract

A polyetherimide comprising repeat units derived from a dianhydride selected from 4,4'-((propane-2,2-diylbis(4,1-phenylene))bis(oxy))bis(isobenzofuran-1,3-dione) or 4,4'-([1,1'-biphenyl]-4,4'-diylbis(oxy))bis(isobenzofuran-1,3-dione), a first diamine comprising 9,9-bis(4-aminophenyl)fluorene, and a second diamine comprising diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, m-phenylenediamine, or p-phenylenediamine. This polyetherimide can exhibit a desirable combination of properties. Also disclosed are a method for producing the polyetherimide, and polymer compositions and articles comprising the polyetherimide.

Description

[Technical Field]

[0001] This application relates to polyetherimides and compositions and articles made therefrom.

[0002] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims priority to European Patent Application Publication No. 23153988.3, ​​filed January 30, 2023, the entire contents of which are incorporated herein by reference. [Background technology]

[0003] Polyimides, particularly polyetherimides (PEI), are high-performance polymers with glass transition temperatures (Tg) exceeding 180°C. These polymers also possess high strength, heat resistance, and modulus, as well as broad chemical resistance. Polyetherimides are widely used in a variety of applications, including automotive and electrical / electronic applications, because their compositions exhibit good mechanical and thermal properties.

[0004] The use of known polyetherimides is limited in some high-temperature applications. For example, some polyetherimides have Tg values ​​that are not high enough to withstand lead-free soldering processes. Other polyetherimides with high Tg values ​​often exhibit high moisture absorption, poor thermal stability, SO2 outgassing, poor dimensional stability, poor IR transmittance, and high viscosity (which may be undesirable in some applications). Summary of the Invention [Problem to be solved by the invention]

[0005] Thus, there is a continuing need in the art for new polyetherimides that exhibit improved thermal performance (e.g., high Tg and high thermal stability) and good flow characteristics. It would be even more beneficial if they simultaneously possessed many of the advantageous properties associated with known polyetherimides. [Means for solving the problem]

[0006] A polyetherimide comprising repeat units derived from a dianhydride selected from 4,4'-((propane-2,2-diylbis(4,1-phenylene))bis(oxy))bis(isobenzofuran-1,3-dione) or 4,4'-([1,1'-biphenyl]-4,4'-diylbis(oxy))bis(isobenzofuran-1,3-dione), a first diamine comprising 9,9-bis(4-aminophenyl)fluorene, and a second diamine comprising diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, m-phenylenediamine, or p-phenylenediamine.

[0007] Another aspect disclosed herein is a polymer composition comprising the polyetherimide.

[0008] Another aspect disclosed herein is an article comprising the polyetherimide or the polymer composition.

[0009] A method for preparing the polyetherimide comprises combining a dianhydride and a diamine under conditions such that the polyetherimide is formed.

[0010] These and other features are illustrated by way of example in the detailed description that follows. DETAILED DESCRIPTION OF THE INVENTION

[0011] Described herein are polyetherimides containing repeat units derived from a particular combination of monomers. The inventors have unexpectedly discovered that the polyetherimides disclosed herein exhibit a favorable combination of properties, such as high melt flow, good optical properties, and good thermal properties, as further described herein.

[0012] Thus, one embodiment disclosed herein is a polyetherimide, which includes repeat units derived from a dianhydride, a first diamine, and a second diamine.

[0013] The dianhydride is selected from 4,4'-((propane-2,2-diylbis(4,1-phenylene))bis(oxy))bis(isobenzofuran-1,3-dione) or 4,4'-([1,1'-biphenyl]-4,4'-diylbis(oxy))bis(isobenzofuran-1,3-dione), represented by structural formulas (I) and (II), respectively. [ka] (I) [ka] (II)

[0014] In some embodiments, the dianhydride is 4,4'-((propane-2,2-diylbis(4,1-phenylene))bis(oxy))bis(isobenzofuran-1,3-dione) (i.e., the dianhydride represented by Structural Formula (I)). The dianhydride represented by Structural Formula (I) is sometimes referred to herein as "3,3'-BPADA."

[0015] In some embodiments, the dianhydride is 4,4'-([1,1'-biphenyl]-4,4'-diylbis(oxy))bis(isobenzofuran-1,3-dione) (i.e., the dianhydride represented by Structural Formula (II)). The dianhydride represented by Structural Formula (II) is sometimes referred to herein as "3,3'-BPoDA."

[0016] The poly(etherimide) can optionally further include additional repeat units derived from the polymerization of a dianhydride other than the dianhydride represented by Structural Formula (I) and Structural Formula (II). The amount of dianhydride other than the dianhydride represented by Structural Formula (I) and Structural Formula (II) present in the poly(etherimide) can be 0 to 2 weight percent (wt%), 0 to 1.5 wt%, 0 to 1 wt%, 0 to 0.5 wt%, or 0 to 0.1 wt%, based on the total moles of dianhydride. In some embodiments, the polyetherimide does not include repeat units derived from any dianhydride other than the dianhydride represented by Structural Formula (I) or Structural Formula (II).

[0017] When dianhydrides different from those represented by structural formula (I) or structural formula (II) are present, they can be represented by structural formula (III) or (IV), [ka] (III) or [ka] (IV) In the formula, T is -O- or a group represented by the structural formula -OZO- (the divalent bond of the -O- or -OZO- group is in the 3,3', 3,4', 4,3', or 4,4' positions), and Z is an aromatic C 6~24 Monocyclic or polycyclic groups (optionally 1 to 6 C 1~8 alkyl group, 1 to 8 halogen atoms, or a combination thereof), and R 1 and R 2 are each independently hydrogen, C 1~8 Z is an alkyl group, a halogen, or a combination thereof, preferably hydrogen. Preferably, Z is represented by structural formula (V): [ka] (V) In the formula, R a , R b, p, and q are as defined above, c is 0 to 4, and X a is -O-, -S-, -S(O)-, -SO2-, -C(O)-, or C 1~18 The repeating unit may be derived from a dihydroxy compound, which is an organic bridging group. In some embodiments, the poly(etherimide) further comprises a second dianhydride represented by Structural Formula (III), provided that the second dianhydride represented by Structural Formula (III) is not the same as the dianhydride represented by Structural Formula (I) or Structural Formula (II). In some embodiments, the poly(etherimide) further comprises a second dianhydride represented by Structural Formula (IV). In some embodiments, the polyetherimide may exclude repeating units derived from Structural Formula (III), Structural Formula (IV), or both.

[0018] The dianhydride is polymerized with a first diamine and a second diamine to produce the polyetherimide disclosed herein. The first diamine comprises 9,9-bis(4-aminophenyl)fluorene (sometimes referred to herein as "BAF"), which is represented by structural formula (VI). [ka] (VI)

[0019] The secondary diamine includes diaminodiphenyl ether (sometimes referred to herein as "DADE"), 4,4'-diaminodiphenyl sulfone (sometimes referred to herein as "DDS"), m-phenylenediamine (sometimes referred to herein as "mPD"), or p-phenylenediamine (sometimes referred to herein as "pPD"). DADE, DDS, mPD, and pPD are represented by structural formulas (VII)-(X), respectively. [ka] (VII) [ka] (VIII) [ka] (IX) [ka] (X)

[0020] In certain embodiments, the polyetherimides do not contain repeat units derived from fluorine-substituted diamines. Stated differently, in some embodiments, the polyetherimides do not contain any fluorine substituents along the polymer backbone. For example, the polyetherimides can exclude repeat units derived from fluorine-containing diamines, such as bistrifluoromethylbenzidine (TFMB) (e.g., 2,2'-bistrifluoromethylbenzidine). Advantageously, polyetherimides without fluorine substituents may be preferred for regulatory reasons. For example, compositions containing less than 5000 ppm fluorine, less than 1000 ppm fluorine, or less than 100 ppm elemental fluorine may be preferred. Furthermore, while prior work has anticipated adding fluorine substituents to increase the transparency of the material, as shown in the examples below, this is not necessary for the compositions disclosed herein to achieve the desired optical properties.

[0021] In some embodiments, the polyetherimide comprises repeat units derived from a first diamine comprising 9,9-bis(4-aminophenyl)fluorene and a second diamine comprising diaminodiphenyl ether. In some embodiments, the polyetherimide comprises repeat units derived from a first diamine comprising 9,9-bis(4-aminophenyl)fluorene and a second diamine comprising 4,4'-diaminodiphenyl sulfone. In some embodiments, the polyetherimide comprises repeat units derived from a first diamine comprising 9,9-bis(4-aminophenyl)fluorene and a second diamine comprising m-phenylenediamine. In some embodiments, the polyetherimide comprises repeat units derived from a first diamine comprising 9,9-bis(4-aminophenyl)fluorene and a second diamine comprising p-phenylenediamine.

[0022] In certain specific embodiments, the polyetherimide comprises repeat units derived from a dianhydride comprising 4,4'-((propane-2,2-diylbis(4,1-phenylene))bis(oxy))bis(isobenzofuran-1,3-dione), a first diamine comprising 9,9-bis(4-aminophenyl)fluorene, and a second diamine comprising 4,4'-diaminodiphenyl ether.

[0023] In certain specific embodiments, the polyetherimides comprise repeat units derived from a dianhydride comprising 4,4'-((propane-2,2-diylbis(4,1-phenylene))bis(oxy))bis(isobenzofuran-1,3-dione), a first diamine comprising 9,9-bis(4-aminophenyl)fluorene, and a second diamine comprising 4,4'-diaminodiphenylsulfone.

[0024] In certain specific embodiments, the polyetherimides comprise repeat units derived from a dianhydride comprising 4,4'-([1,1'-biphenyl]-4,4'-diylbis(oxy))bis(isobenzofuran-1,3-dione), a first diamine comprising 9,9-bis(4-aminophenyl)fluorene, and a second diamine comprising diaminodiphenyl ether.

[0025] In certain specific embodiments, the polyetherimides comprise repeat units derived from a dianhydride comprising 4,4'-((propane-2,2-diylbis(4,1-phenylene))bis(oxy))bis(isobenzofuran-1,3-dione), a first diamine comprising 9,9-bis(4-aminophenyl)fluorene, and a second diamine comprising m-phenylenediamine.

[0026] In certain specific embodiments, the polyetherimides comprise repeat units derived from a dianhydride comprising 4,4'-((propane-2,2-diylbis(4,1-phenylene))bis(oxy))bis(isobenzofuran-1,3-dione), a first diamine comprising 9,9-bis(4-aminophenyl)fluorene, and a second diamine comprising p-phenylenediamine.

[0027] In some embodiments, the amount of the first diamine present, based on the total moles of the first diamine and the second diamine, can be 10 mol% to 98 mol%. Within this range, the amount of the first diamine containing 9,9-bis(4-aminophenyl)fluorene present, based on the total moles of the first diamine and the second diamine, can be at least 20 mol%, at least 30 mol%, at least 40 mol%, at least 50 mol%, at least 60 mol%, at least 70 mol%, or at least 80 mol%. Further within this range, the amount of the first diamine containing 9,9-bis(4-aminophenyl)fluorene present, based on the total moles of the first diamine and the second diamine, can be up to 97 mol%, up to 95 mol%, up to 90 mol%, up to 80 mol%, up to 70 mol%, up to 60 mol%, up to 50 mol%, up to 40 mol%, up to 30 mol%, or up to 20 mol%.

[0028] The second diamine can be present in a complementary amount, such that the total moles of the first diamine and the second diamine add up to 100 mole percent. For example, the second diamine can be present in an amount from 2 mole percent to 90 mole percent, based on the total moles of the first diamine and the second diamine. Within this range, the second diamine can be present in an amount of at least 3 mole percent, at least 5 mole percent, at least 10 mole percent, at least 20 mole percent, at least 30 mole percent, at least 40 mole percent, at least 50 mole percent, at least 60 mole percent, at least 70 mole percent, or at least 80 mole percent, based on the total moles of the first diamine and the second diamine. Further within this range, the second diamine can be present in an amount up to 80 mole percent, up to 70 mole percent, up to 60 mole percent, up to 50 mole percent, up to 40 mole percent, up to 30 mole percent, or up to 20 mole percent, based on the total moles of the first diamine and the second diamine.

[0029] In certain specific embodiments, the first diamine can be present in an amount of 60 mol % to 98 mol %, desirably 65 mol % to 75 mol % or 75 mol % to 85 mol %, based on the total moles of the first diamine and the second diamine, and the second diamine can be present in an amount of 2 mol % to 40 mol %, desirably 25 mol % to 35 mol % or 15 mol % to 25 mol %, based on the total moles of the first diamine and the second diamine.

[0030] The polyetherimides can optionally further include at least one chain end derived from a chain terminator (also called an endcapping agent). Chain terminators can be used during the polymerization reaction. Chain terminators limit the rate of molecular weight growth and can therefore be used to control the molecular weight of the polyetherimide. Examples of chain terminators include certain monoamines (e.g., aniline), monoanhydrides (e.g., phthalic anhydride), monohydric phenol compounds, and the like. In some embodiments, the chain terminator is preferably a monoamine or monoanhydride chain terminator, more preferably aniline or phthalic anhydride. However, it should be understood that the polyetherimides disclosed herein can be prepared with any end cap and have any desired weight average molecular weight (Mw). The amount of chain terminator present can be, for example, 1 mol % to 10 mol % based on the total moles of dianhydride, diamine, and chain terminator.

[0031] The polyetherimides disclosed herein can have a weight average molecular weight of 30,000 g / mol to 65,000 g / mol. Within this range, the weight average molecular weight can be, for example, 35,000 g / mol to 60,000 g / mol, 35,000 g / mol to 55,000 g / mol, 35,000 g / mol to 50,000 g / mol, or 35,000 g / mol to 45,000 g / mol. Molecular weight can be determined using gel permeation chromatography (GPC) against polystyrene standards eluted with dichloromethane.

[0032] The polyetherimides disclosed herein can exhibit one or more advantageous properties. For example, the polyetherimides can exhibit a glass transition temperature greater than 275°C, e.g., greater than 275°C to 290°C, as measured by differential scanning calorimetry. In certain embodiments, the polyetherimides can exhibit a melt flow rate greater than 7 g / 10 min, as measured at 367°C under a 6.7 kg load. The polyetherimides can be transparent. For example, the polyetherimides can exhibit a percent transmittance of at least 80% at 850 nm. The polyetherimides can exhibit a combination of the aforementioned properties. For example, the polyetherimides can exhibit a melt flow rate greater than 7 g / 10 min and a percent transmittance of at least 80% at 850 nm, as measured at 367°C under a 6.7 kg load. In some embodiments, the polyetherimides may exhibit a glass transition temperature greater than 275°C and a melt flow rate greater than 7 g / 10 min when measured at 367°C under a 6.7 kg load. In some embodiments, the polyetherimides may exhibit a glass transition temperature greater than 275°C and a transmittance of at least 80% at 850 nm. In some embodiments, the polyetherimides may exhibit a glass transition temperature greater than 275°C and a melt flow rate greater than 7 g / 10 min when measured at 367°C under a 6.7 kg load and a transmittance of at least 80% at 850 nm. In some embodiments, the polyetherimides may exhibit a yellowness index of less than 125. In some embodiments, the polyetherimides may exhibit a glass transition temperature greater than 275°C and a melt flow rate greater than 7 g / 10 min when measured at 367°C under a 6.7 kg load and a yellowness index of less than 125.

[0033] In certain specific embodiments, the polyetherimide comprises, consists essentially of, or consists of repeat units derived from 4,4'-((propane-2,2-diylbis(4,1-phenylene))bis(oxy))bis(isobenzofuran-1,3-dione), a first diamine that is 9,9-bis(4-aminophenyl)fluorene, and a second diamine that is diaminodiphenyl ether. The polyetherimide may exhibit a melt flow rate of greater than 9 g / 10 min and a transmittance of at least 80% at 850 nm, measured at 367°C under a 6.7 kg load. The polyetherimide may optionally be oxidized at 400°C, 5000 s according to ASTM D3835. -1 The polyetherimide may optionally exhibit a viscosity of greater than 200 Pa·s, as measured by differential scanning calorimetry. The polyetherimide may optionally exhibit a glass transition temperature of greater than 275°C, as measured by differential scanning calorimetry. The polyetherimide may optionally exhibit a yellowness index of less than 125.

[0034] A method for producing the polyetherimide is another embodiment disclosed herein. The method for producing the polyetherimide includes contacting a dianhydride with a first diamine and a second diamine under conditions to form the polyetherimide. The conditions for forming the polyetherimide can include a temperature of 170°C to 380°C and a solids content of 1% to 50%, preferably 20% to 40%, more preferably 25% to 35%, by weight. The polymerization can be carried out for 2 to 24 hours, preferably 3 to 16 hours. The polymerization can be carried out under reduced pressure, atmospheric pressure, or elevated pressure. In some embodiments, the method can further include devolatilizing the polyetherimide at 360°C to 390°C for 1 to 30 minutes, if desired. The contacting of the dianhydride with the first and second diamines can be carried out in the presence of a solvent. Exemplary solvents include o-dichlorobenzene, p-dichlorobenzene, m-dichlorobenzene, m-cresol, p-cresol, o-cresol, N-methylpyrrolidone, veratrole, chlorobenzene, xylene, 1,2,4-trichlorobenzene, 1,3,4-trichlorobenzene, ethyl benzoate, triglyme, benzonitrile, 3-nitrotoluene, 2-nitrotoluene, 1-nitrotoluene, 1,3-dimethyl-2-imidazolidinone, dimethylacetamide, diphenyl ether, phenetole, sulfolane, or a combination thereof. In some embodiments, the solvent comprises o-dichlorobenzene.

[0035] The polyetherimides disclosed herein are believed to be useful in forming polymer compositions. Polymer compositions containing the polyetherimides are another aspect of the present disclosure. The polymer compositions can optionally include one or more thermoplastic polymers other than the polyetherimides. Such polymer compositions can include, for example, 1% to 99% by weight of the polyetherimides disclosed herein and 1% to 99% by weight of a second polymer, or 10% to 90% by weight of the polyetherimides and 10% to 90% by weight of a second polymer.

[0036] Examples of the second polymer include polyacetal, polyacrylic acid (C 1~6 alkyl), polyacrylamide, polyacrylonitrile, polyamide, polyamideimide, polyanhydride, polyarylene ether, polyarylene ether ketone, polyarylene ketone, polyarylene sulfide, polyarylene sulfone, polybenzothiazole, polybenzoxazole, polybenzimidazole, polycarbonate, polyester, polymethacrylic acid (C 1~6 alkyl), polymethacrylamide, cyclic olefin polymers, polyolefins, polyoxadiazoles, polyoxymethylene, polyphthalides, polysilazanes, polysiloxanes, polystyrenes, polysulfides, polysulfonamides, polysulfonates, polythioesters, polytriazines, polyureas, polyurethanes, vinyl polymers, or combinations thereof.

[0037] The polymeric compositions can contain a variety of additives typically added to compositions of this type, provided that the additives are selected so as not to significantly adversely affect the desired properties of the composition. Examples of additives include antioxidants, heat stabilizers, light stabilizers, ultraviolet (UV) absorbers, quenchers, plasticizers, lubricants, mold release agents, antistatic agents, visual effect additives (dyes, pigments, light effect additives, etc.), flame retardants, anti-drip agents, and radiation stabilizers. Particulate and reinforcing fillers can also be added, including inorganic fillers, flake fillers, carbon nanotubes, exfoliated nanoclays, carbon nanowires, carbon nanospheres, carbon-metal nanospheres, carbon nanorods, carbon-metal nanorods, nanoparticles, insoluble polymers, glass fibers, carbon fibers, glass-carbon fibers, talc (including fibrous, modular, acicular, and lamellar talc), graphite, fibrillated fluoropolymers, polymer fibers and filaments, woven fibers, metal particles, inorganic fibers, and single-crystal fibers or "whiskers." Combinations of additives can also be used. The foregoing additives can be present in amounts of 0.005% to 10% by weight each, or in combined amounts of 0.005% to 20% by weight, preferably 0.01% to 10% by weight, based on the total weight of the composition.

[0038] Articles comprising the polyetherimides or polymer compositions comprising the polyetherimides are also provided herein. The polyetherimides can be formed into articles using any suitable technique, such as melt processing. Melt processing techniques can include injection molding, extrusion, blow molding, rotational molding, coining, and injection blow molding. For example, the melt processing technique can be injection molding. In some embodiments, the polyetherimides disclosed herein are particularly suited for extrusion molding. The polyetherimides can be formed into sheets or films by casting, blowing, or extrusion. These can be further thermoformed into articles or structures from the melt or at a later stage in the processing of the composition. The polyetherimides can be molded over articles made from different materials or by other processes. The articles can also be formed using techniques such as compression molding or ram extrusion. The articles can be further formed into different shapes by machining. Examples of articles include fibers, films, sheets, foams, filaments, molded articles, extrusions, or powders. The properties of the polyetherimides disclosed herein are believed to be particularly suitable for forming thin-walled molded articles. In some embodiments, the articles can be extruded films or extruded sheets. The polyetherimides disclosed herein are also believed to be particularly suitable for use in optoelectronic applications. In particular, the polyetherimides can be used in optoelectronic components such as transmitters, receivers, connectors, lenses, and waveguides. [Example]

[0039] The polyetherimides disclosed herein are further illustrated by the following non-limiting examples.

[0040] The materials of the examples are listed in Table 1. Materials that were found to contain fluorine-containing impurities upon receipt were not used in the following examples.

[0041] [Table 1]

[0042] The example polymers were prepared according to the following general procedure: The desired amount of each monomer was added to a reactor, followed by o-dichlorobenzene to a solids content of 30%. The contents of the reactor were stirred and heated to a temperature of 190°C under a nitrogen atmosphere. The reaction mixture was heated to reflux for 5 hours. Molecular weight analysis was performed over time using gel permeation chromatography (GPC) to monitor the progress of the reaction. Once the desired molecular weight was reached, the solvent was removed from the reactor. The molten polymer was removed from the extruder through a water-cooled pelletizer.

[0043] The resulting polymers were characterized according to the following tests and test methods:

[0044] Molecular weights were determined by gel permeation chromatography in dichloromethane relative to polystyrene standards. Samples were dissolved in dichloromethane or, if not completely soluble in dichloromethane alone, in a 50:50 mixture of hexafluoroisopropanol and dichloromethane (HFIP / DCM).

[0045] Glass transition temperatures (Tg) were determined by differential scanning calorimetry (DSC) in a nitrogen atmosphere according to ASTM D3418 using a DSC Q2000 DSC instrument, with heating from -10°C to 300°C at a heating rate of 20°C / min. The Tg value was determined from the inflection point of the second heat cycle.

[0046] The melt flow rate (MFR) was determined in accordance with ASTM D1238 at a temperature of 367°C under a load of 6.7 kg.

[0047] Viscosity change is a measurement of the change in viscosity of a polymer after being held at a specific elevated temperature for a specific time. The viscosity change reported in the text is the change in melt viscosity after being held at 400°C for 30 minutes in a parallel plate rheometer. The sample was moved across the parallel plates at 6.28 radians per second (rad / s) and 5% strain from 0 to 1800 seconds.

[0048] IR transmittance at 550 nm, 850 nm, 1150 nm, and 1310 nm was determined according to ASTM D1003 using injection molded 1 mm thick plaques.

[0049] Notched Izod Impact (NII) strength was determined according to ASTM D256 using a 5.5 J pendulum at 23°C.

[0050] Thermal gravimetric analysis (TGA) measurements were performed on a TA Q800 TGA. Samples were heated in a nitrogen or air atmosphere from 40°C to 800°C at a heating rate of 20°C / min. The onset temperature was the extrapolated onset temperature determined from the intersection of the tangent lines according to ISO 11358-1. The mass loss rate was calculated from the initial mass and the mass at 800°C.

[0051] Capillary rheometry (viscosity) was measured at 400°C and 5000s according to ASTM D3835. -1 Heat deflection temperature (HDT) was determined according to ASTM D648 at 1.82 MPa. Tensile properties were determined according to ASTM D638. Flexural properties were determined according to ASTM D790. Yellowness index (YI) was determined according to ASTM D1925. The solution yellowness index can be determined in the same way by dissolving the polymer in methylene chloride to a polymer concentration of 3.5% by weight and measuring the yellowness according to the same ASTM standard. Additionally, the materials were visually observed in sunlight to assess the base color of the material.

[0052] Film integrity was measured by molding the removed solid into a thin film (~0.05 mm) in a hydraulic press settable to a temperature of 380°C. The sample was pressed until no voids remained along a 4 mm line. The sample was then folded in half along the void-free area, and a crease was made along the folded edge. Sample films whose folded edge remained intact were deemed to have retained their integrity (denoted "yes" in the table below); samples that could not be folded or cracked were deemed to have failed (denoted "no" in the table below). It is believed that any thermoplastic material with a viable viscosity can be compression molded under these conditions (same as the temperature of the injection molding machine).

[0053] The polymer compositions and properties are summarized in Table 2. The amount of each component is expressed in mole percent (mol%).

[0054] [Table 2]

[0055] [Table 3]

[0056] Desirable properties include a high Tg (e.g., greater than 275°C), a good melt flow rate (e.g., greater than 7 g / 10 min), and good IR transmittance. From the data in Table 2, it can be seen that the polymers of Examples 1-3 and 6-11 each have a desirable Tg. The polymers of Examples 1, 2, 6, and 8-9 each have a desirable MFR. Examples 2, 7, and 9 each have good IR transmittance at both 850 nm and 1150 nm. In some cases, particularly those resulting in high molecular weight polymers, molding attempts were unsuccessful (i.e., the compositions could not be molded). In these cases, molded samples failed to generate data for required property tests (e.g., IR transmittance, NII). On the other hand, the comparative examples were found to lack at least one of the desirable properties. Comparative Example 7 demonstrates that the use of BPDA as the anhydride component did not result in desirable properties. Comparative Example 8 demonstrates that the addition of a fluorine-containing component did not improve the transparency of the resulting compositions. Comparative Example 8 contains 8,100 ppm (0.81 wt%) of elemental fluorine, intentionally added by the addition of TFMB into the framework. The exact amount of fluorine may be determined by ion chromatography.

[0057] It would be particularly advantageous to provide a polymer composition that possesses the aforementioned combination of properties. The data in Table 2 show that the polymer composition of Example 2 advantageously exhibits a Tg of 283°C, a MFR of 11 g / 10 min, and an IR transmittance of 84% at 850 nm and 79% at 1150 nm.

[0058] Based on the data in Table 2, polymers based on 3,3'-BPADA / BAF / DADE (e.g., polymers in Examples 1-3) and 3,3'-BPoDA / BAF / DADE (e.g., polymers in Examples 8-10) were selected for further characterization. Blends of polymers with different molecular weights were also extruded, molded, and tested. The compositions and properties are summarized in Table 3 below.

[0059] [Table 4]

[0060] Table 4 lists the optical properties of samples molded from the polymer of Example 2, as well as a sample molded from a 1:3 weight ratio blend of the polymers of Examples 10 and 8 (referred to as Example 18 in Table 3). For comparison, Table 4 also lists the optical properties of a commercially available polyetherimide (obtained from SABIC as ULTEM™ 1010 resin). Percent transmission was recorded at a thickness of 1 mm for Examples 2 and 18 (the Example 9 / Example 7 blend) and at a thickness of 3.2 mm for ULTEM™ 1010 resin. The refractive index (RI) of each sample is also listed in Table 4. As shown in Table 4, the refractive index of Example 2 was the same as the data sheet value for ULTEM™ 1010 resin. The optical properties summarized in Table 4 demonstrate that the polymers disclosed herein may be particularly suitable for optical applications.

[0061] [Table 5]

[0062] Table 5 shows the results of optical property testing of the polymer with the composition of Example 2.

[0063] [Table 6]

[0064] The disclosure of the present application further includes the following aspects.

[0065] Aspect 1: A polyetherimide comprising repeat units derived from a dianhydride selected from 4,4'-((propane-2,2-diylbis(4,1-phenylene))bis(oxy))bis(isobenzofuran-1,3-dione) or 4,4'-([1,1'-biphenyl]-4,4'-diylbis(oxy))bis(isobenzofuran-1,3-dione), a first diamine comprising 9,9-bis(4-aminophenyl)fluorene, and a second diamine comprising diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, m-phenylenediamine, or p-phenylenediamine.

[0066] Embodiment 2: The polyetherimide of embodiment 1, wherein the dianhydride is 4,4'-((propane-2,2-diylbis(4,1-phenylene))bis(oxy))bis(isobenzofuran-1,3-dione).

[0067] Embodiment 3: The polyetherimide of embodiment 1 or 2, wherein the dianhydride is 4,4'-([1,1'-biphenyl]-4,4'-diylbis(oxy))bis(isobenzofuran-1,3-dione).

[0068] Embodiment 4: The polyetherimide of embodiment 2 or 3, wherein the first diamine is 9,9-bis(4-aminophenyl)fluorene and the second diamine is 4,4'-diaminodiphenyl ether.

[0069] Embodiment 5: The polyetherimide of embodiment 2, wherein the first diamine is 9,9-bis(4-aminophenyl)fluorene and the second diamine is 4,4'-diaminodiphenylsulfone.

[0070] Embodiment 6: The polyetherimide of any of Embodiments 1 to 5, wherein the polyetherimide has a weight average molecular weight of 30,000 g / mol to 65,000 g / mol, desirably 35,000 g / mol to 45,000 g / mol, as measured by gel permeation chromatography in dichloromethane relative to polystyrene standards.

[0071] Embodiment 7: The polyetherimide of any of Embodiments 1 through 6, wherein the polyetherimide exhibits a glass transition temperature greater than 275° C. as measured by differential scanning calorimetry.

[0072] Embodiment 8: The polyetherimide of any of Embodiments 1 to 7, wherein the polyetherimide exhibits one or more of: a melt flow rate greater than 7 g / 10 min, measured at 367° C. under a 6.7 kg load; at least 80% transmittance at 850 nm, as measured by ASTM D1925, less than 125; or elemental fluorine of less than 5000 ppm, less than 1000 ppm, or less than 100 ppm, as measured using combustion ion chromatography.

[0073]

[0023] Aspect 9. The polyetherimide of aspect 1, wherein the dianhydride is 4,4'-((propane-2,2-diylbis(4,1-phenylene))bis(oxy))bis(isobenzofuran-1,3-dione), the first diamine is 9,9-bis(4-aminophenyl)fluorene, and the second diamine is diaminodiphenyl ether; the polyetherimide has a weight average molecular weight of 35,000 g / mol to 45,000 g / mol; and the polyetherimide is sintered at 400°C for 5000 s according to ASTM D3835. -1 It exhibits a viscosity of greater than 200 Pa·s when measured at 200°C, a melt flow rate of greater than 9 g / 10 min when measured at 367°C under a 6.7 kg load, and a transmittance of at least 80% at 850 nm.

[0074] Embodiment 10: The polyetherimide of embodiment 9, wherein the polyetherimide exhibits a glass transition temperature greater than 275°C, desirably from greater than 275°C to 290°C, as measured by differential scanning calorimetry.

[0075] Aspect 11: The polyetherimide of any one of claims 1 to 10, wherein the first diamine is present in an amount of 60 mol % to 98 mol % based on the total moles of the first diamine and the second diamine, and the second diamine is present in an amount of 2 mol % to 40 mol % based on the total moles of the first diamine and the second diamine.

[0076] Embodiment 12: A polymer composition comprising the polyetherimide of any of embodiments 1 to 11.

[0077] Embodiment 13: An article comprising the polyetherimide of any of embodiments 1 to 11 or the polymer composition of embodiment 12.

[0078] Embodiment 14: The article of embodiment 13, wherein the article is an optical article, preferably a lens or an optoelectronic component.

[0079] Embodiment 15: A method of making the polyetherimide of any of Embodiments 1-11, the method comprising combining a dianhydride, a first diamine, and a second diamine under conditions such that the polyetherimide is formed.

[0080] The compositions, methods, and articles may alternatively comprise, consist of, or consist essentially of any suitable material, step, or component disclosed herein. The compositions, methods, and articles may additionally or alternatively be configured to exclude or be substantially free of any material (or species), step, or component that is not necessary to achieve the function or purpose of the compositions, methods, and articles.

[0081] All ranges disclosed herein are inclusive of their endpoints, and the endpoints are independently combinable with each other. "Combinations" includes blends, mixtures, alloys, reaction products, and the like. The terms "first," "second," and the like do not denote any order, quantity, or importance, but rather are used to distinguish one element from another. The terms "a," "an," and "the" do not denote limitations of quantity and should be construed to include both the singular and the plural unless otherwise indicated or clearly contradicted by context. "Or" means "and / or" unless expressly stated otherwise. References in the specification to "an embodiment" mean that a particular element described in connection with that embodiment is included in at least one embodiment described in the description, but may or may not be present in other embodiments. As used herein, the term "combination thereof" includes one or more of the listed elements and is open, meaning that one or more similar elements that are not listed may be present. Furthermore, it is understood that the listed elements can be combined in any suitable manner in various embodiments.

[0082] Unless otherwise specified in the text, all test standards are the most recent standards in effect as of the filing date of this application or, if priority is claimed, the filing date of the earliest priority application in which the test standard is listed.

[0083] Unless otherwise defined, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains. All cited patents, patent applications, and other references are incorporated herein by reference in their entirety. However, if a term in this application contradicts or conflicts with a term in an incorporated reference, the term in this application shall take precedence over the conflicting term from the incorporated reference.

[0084] Compounds are described using standard nomenclature. For example, any position not substituted with any indicated group shall have its valence filled at the indicated bond or with a hydrogen atom. A dash ("-") not between two letters or symbols is used to indicate the position at which a substituent is attached. For example, -CHO is attached at the carbon of the carbonyl group.

[0085] As used herein, the term "hydrocarbyl," whether used alone or as a prefix, suffix, or part of another term, refers to a residue containing only carbon and hydrogen. The residue can be aliphatic or aromatic, straight-chain, cyclic, bicyclic, branched, saturated, or unsaturated. It can also include combinations of aliphatic, aromatic, straight-chain, cyclic, bicyclic, branched, saturated, and unsaturated hydrocarbon groups. However, when a hydrocarbyl residue is described as substituted, it can optionally contain heteroatoms in addition to the carbon and hydrogen that make up the substituent residue. That is, when specified as substituted, the hydrocarbyl residue can also contain one or more carbonyl groups, amino groups, hydroxyl groups, etc., or it can contain heteroatoms within the backbone of the hydrocarbyl residue. The term "alkyl" refers to a branched or straight-chain, saturated aliphatic hydrocarbon group, e.g., methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, s-pentyl, n-, and s-hexyl. "Alkenyl" refers to a branched or straight-chain, monovalent hydrocarbon group containing at least one carbon-carbon double bond, e.g., ethenyl (-HC=CH). "Alkoxy" refers to an alkyl group attached through oxygen (i.e., alkyl-O-), e.g., methoxy, ethoxy, and sec-butyloxy groups. "Alkylene" refers to a branched or straight-chain, saturated divalent aliphatic hydrocarbon group, e.g., methylene (-CH-), propylene (-(CH)-). "Cycloalkylene" refers to a divalent cyclic alkylene group, -C. n H 2n-xwhere x is the number of hydrogens replaced by the cyclization. "Cycloalkenyl" refers to a monovalent group containing one or more rings and one or more carbon-carbon double bonds within the ring, where all ring members are carbon (e.g., cyclopentyl, cyclohexyl). "Aryl" refers to an aromatic hydrocarbon group containing the specified number of carbon atoms (e.g., phenyl, tropone, indanyl, naphthyl, etc.). "Arylene" refers to a divalent aryl group. "Alkylarylene" refers to an arylene group substituted with an alkyl group. "Arylalkylene" refers to an alkylene group substituted with an aryl group (e.g., benzyl). The prefix "halo" refers to a group or compound containing one or more fluoro, chloro, bromo, or iodo substituents. Combinations of different halo atoms (e.g., bromo and fluoro) or only chloro atoms may be present. The prefix "hetero" means a compound or group that contains at least one ring member that is a heteroatom (e.g., 1, 2, or 3 heteroatoms), where each heteroatom is independently N, O, S, Si, or P. "Substituted" means that the compound or group contains at least one (e.g., 1, 2, 3, or 4) substituents (each independently, C) in place of a hydrogen, provided that the normal valence of the substituted atom is not exceeded. 1~9 Alkoxy, C 1~9 Haloalkoxy, nitro (-NO2), cyano (-CN), C 1~6 Alkylsulfonyl (-S(=O)2-alkyl), C 6~12 Arylsulfonyl (-S(=O)2-aryl), thiol (-SH), thiocyano (-SCN), tosyl (CH3C6H4SO2-), C 3~12 Cycloalkyl, C 2~12 Alkenyl, C 5~12 Cycloalkenyl, C 6~12 Aryl, C 7~13 Aryl alkylene, C 4~12 Heterocycloalkyl, and C 3~12The number of carbon atoms shown for a group does not include the substituents. For example, -CHCHCN is a C alkyl group substituted with a nitrile.

[0086] While particular embodiments have been described, presently unforeseen or uncontemplated alternatives, modifications, variations, improvements, and substantial equivalents may be devised by applicant or others skilled in the art, and it is therefore intended that the appended claims, as filed and as they may be amended, shall embrace all such alternatives, modifications, variations, improvements, and substantial equivalents.

Claims

1. Polyetherimide, The polyetherimide is a dianhydride selected from 4,4'-((propane-2,2-diylbis(4,1-phenylene))bis(oxy))bis(isobenzofuran-1,3-dione) or 4,4'-([1,1'-biphenyl]-4,4'-diylbis(oxy))bis(isobenzofuran-1,3-dione); a primary diamine comprising 9,9-bis(4-aminophenyl)fluorene; a secondary diamine comprising diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, m-phenylenediamine, or p-phenylenediamine; A polyetherimide comprising repeating units derived from

2. 2. The polyetherimide of claim 1, wherein the dianhydride is 4,4'-((propane-2,2-diylbis(4,1-phenylene))bis(oxy))bis(isobenzofuran-1,3-dione).

3. 3. The polyetherimide according to claim 1, wherein the dianhydride is 4,4'-([1,1'-biphenyl]-4,4'-diylbis(oxy))bis(isobenzofuran-1,3-dione).

4. 4. The polyetherimide according to claim 2, wherein the first diamine is 9,9-bis(4-aminophenyl)fluorene and the second diamine is 4,4'-diaminodiphenyl ether.

5. 4. The polyetherimide according to claim 2, wherein the first diamine is 9,9-bis(4-aminophenyl)fluorene and the second diamine is 4,4'-diaminodiphenylsulfone.

6. 6. The polyetherimide of claim 1, wherein the first diamine is present in an amount of from 60 mole percent (mol %) to 98 mol %, preferably from 75 mol % to 85 mol %, based on the total moles of the first diamine and the second diamine; and the second diamine is present in an amount of from 2 mol % to 40 mol %, preferably from 15 mol % to 25 mol %, based on the total moles of the first diamine and the second diamine.

7. 7. The polyetherimide of claim 1, wherein the polyetherimide has a weight average molecular weight of from 30,000 g / mol to 65,000 g / mol, preferably from 35,000 g / mol to 45,000 g / mol, as measured by gel permeation chromatography in dichloromethane relative to polystyrene standards.

8. 8. The polyetherimide of claim 1, wherein the polyetherimide exhibits a glass transition temperature greater than 275°C as measured by differential scanning calorimetry.

9. 9. The polyetherimide according to claim 1, wherein the polyetherimide is a melt flow rate greater than 7 g / 10 min measured at 367° C. under a 6.7 kg load; at least 80% transmittance at 850 nm; a yellowness index of less than 125 as measured by ASTM D1925, or less than 5000 ppm, less than 1000 ppm, or less than 100 ppm elemental fluorine as measured by combustion ion chromatography; 1. A polyetherimide characterized by exhibiting one or more of the following:

10. 2. The polyetherimide of claim 1, the dianhydride is 4,4'-((propane-2,2-diylbis(4,1-phenylene))bis(oxy))bis(isobenzofuran-1,3-dione), the first diamine is 9,9-bis(4-aminophenyl)fluorene; the second diamine is diaminodiphenyl ether, the polyetherimide has a weight average molecular weight of 35,000 g / mol to 45,000 g / mol; The polyetherimide is ASTM D3835, 400°C, 5000s －１ a viscosity of greater than 200 Pa s when measured at a melt flow rate greater than 9 g / 10 min measured at 367°C under a load of 6.7 kg; at least 80% transmittance at 850 nm; A polyetherimide characterized by:

11. 11. The polyetherimide of claim 10, wherein the polyetherimide exhibits a glass transition temperature greater than 275°C, preferably greater than 275°C to 290°C, as measured by differential scanning calorimetry.

12. A polymer composition comprising the polyetherimide of any one of claims 1 to 11.

13. 13. An article comprising the polyetherimide of any one of claims 1 to 11 or the polymer composition of claim 12.

14. 14. The article according to claim 13, characterized in that the article is an optical article, preferably a lens or an optoelectronic component.

15. 12. A method for producing the polyetherimide of any one of claims 1 to 11, comprising the steps of: The process comprises combining the dianhydride, the first diamine, and the second diamine under conditions such that the polyetherimide is formed.

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