Polyetherimides and compositions and articles made therefrom

Abstract

A polyetherimide includes repeating units derived from a dianhydride selected from the group consisting of 4, 4 '-((propane-2, 2-diylbis (4, 1-phenylene)) bis (oxy)) bis (isobenzofuran-1, 3-dione), a first diamine, and a second diamine; or 4, 4 '-([1, 1'-diphenyl]-4, 4 '-diylbis (oxy)) bis (isobenzofuran-1, 3-dione); the first diamine comprises 9, 9-bis (4-aminophenyl) fluorene; the polyetherimides may exhibit a desired combination of properties, and the second diamine includes a diaminodiphenyl ether, 4, 4 '-diaminodiphenyl sulfone, m-phenylenediamine, or p-phenylenediamine The polyetherimides may exhibit a desired combination of properties, methods of making the polyetherimides, and polymer compositions and articles including the polyetherimides are also disclosed.

Description

[0001] Related applications

[0002] This application claims the benefit of European patent application No. 23153988.3 filed on January 30, 2023, the contents of which are incorporated herein by reference in their entirety. Background Art

[0003] Polyimides, especially polyetherimides (PEI), are high-performance polymers with a glass transition temperature (Tg) greater than 180°C. These polymers further have high strength, heat resistance, and modulus, as well as broad chemical resistance. Polyetherimides are widely used in applications as diverse as automotive and electrical / electronic applications because these compositions provide good mechanical and thermal properties.

[0004] The use of known polyetherimides in some high-temperature applications has been limited. For example, some polyetherimides have Tg values ​​that are not high enough to withstand lead-free soldering processes. Other polyetherimides with higher Tg values ​​can often exhibit high moisture absorption, reduced thermal stability, SO2 outgassing, low dimensional stability, low IR transmittance, and high viscosity that may be undesirable for some applications.

[0005] Thus, there remains a continuing need in the art for new polyetherimides that exhibit improved thermal properties (e.g., high Tg and high thermal stability) and good flow properties. It would be further advantageous to retain most of the favorable properties associated with known polyetherimides. Summary of the Invention

[0006] The polyetherimide includes repeating 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'-diphenyl]-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 of the present disclosure is a polymer composition comprising a polyetherimide.

[0008] Another aspect of the present disclosure is an article comprising the polyetherimide or polymer composition.

[0009] A method for making a polyetherimide comprises combining a dianhydride and a diamine under conditions effective to provide the polyetherimide.

[0010] The above described and other features are exemplified by the following detailed description. DETAILED DESCRIPTION

[0011] Described herein are polyetherimides comprising repeating units derived from specific combinations of monomers. The inventors have unexpectedly discovered that the polyetherimides according to the present disclosure can exhibit a combination of desirable properties, for example, high melt flow, good optical properties, and good thermal properties, as further described herein.

[0012] Thus, one aspect of the present disclosure is a polyetherimide.The polyetherimide includes repeating 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'-diphenyl]-4,4'-diylbis(oxy))bis(isobenzofuran-1,3-dione) as shown in formula (I) and (II), respectively.

[0014]

[0015] In one aspect, the dianhydride is 4,4′-((propane-2,2-diylbis(4,1-phenylene))bis(oxy))bis(isobenzofuran-1,3-dione) (ie, a dianhydride according to formula (I)). The dianhydride according to formula (I) may also be referred to herein as “3,3′-BPADA.”

[0016] In one aspect, the dianhydride is 4,4′-((1,1′-diphenyl]-4,4′-diylbis(oxy))bis(isobenzofuran-1,3-dione) (ie, a dianhydride according to formula (II)). The dianhydride according to formula (II) may also be referred to herein as “3,3′-BPoDA.”

[0017] The poly(etherimide) may optionally further comprise additional repeating units derived from the polymerization of a dianhydride different from the dianhydride according to formula (I) and formula (II). The dianhydride different from the dianhydride according to formula (I) and formula (II) may be present in the poly(etherimide) in an amount of 0 to 2 weight percent, or 0 to 1.5 weight percent, or 0 to 1 weight percent, or 0 to 0.5 weight percent, or 0 to 0.1 weight percent, each based on the total moles of the dianhydride. In one aspect, the polyetherimide does not comprise repeating units derived from any dianhydride except the dianhydride according to formula (I) or formula (II).

[0018] When present, the dianhydride other than the dianhydride according to formula (I) or formula (II) may have formula (III) or (IV)

[0019]

[0020] wherein T is -O- or a group of formula -OZO-, wherein the divalent bond of the -O- or -OZO- group is at the 3,3', 3,4', 4,3', or 4,4' position, and Z is optionally substituted with 1 to 6 C 1-8 Alkyl groups, 1-8 halogen atoms, or a combination thereof substituted aromatic C 6-24 a monocyclic or polycyclic group; and R 1 and R 2 are independently hydrogen, C 1-8 Alkyl, halogen, or a combination thereof, preferably hydrogen. Preferably, Z can be a group derived from a dihydroxy compound of formula (V)

[0021]

[0022] Among them, 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 In one aspect, the poly(etherimide) further comprises a second dianhydride of formula (III), provided that the second dianhydride of formula (III) is different from the dianhydride according to formula (I) or formula (II). In one aspect, the poly(etherimide) further comprises a second dianhydride of formula (IV). In one aspect, the polyetherimide may not include repeating units derived from formula (III), formula (IV), or both.

[0023] Dianhydrides are polymerized with first and second diamines to provide the polyetherimides of the present disclosure.The first diamine includes 9,9-bis(4-aminophenyl)fluorene, which may also be referred to herein as "BAF" and is shown in Formula (VI).

[0024]

[0025] The second diamine comprises diaminodiphenyl ether (also referred to herein as "DADE"), 4,4'-diaminodiphenyl sulfone (also referred to herein as "DDS"), m-phenylenediamine (also referred to herein as "mPD"), or p-phenylenediamine (also referred to herein as "pPD"). DADE, DDS, mPD, and pPD are shown in Formulas (VII) to (X), respectively.

[0026]

[0027] In one aspect, the polyetherimide does not include repeating units derived from fluorine-substituted diamines. In other words, in some aspects, the polyetherimide does not include any fluorine substituents along the polymer backbone. For example, the polyetherimide may not include repeating units derived from fluorine-containing diamines, such as bistrifluoromethylbenzylamine (TFMB) (e.g., 2,2'-bistrifluoromethylbenzylamine). Advantageously, for regulatory reasons, it may be desirable to include a polyetherimide that does not include fluorine substituents. For example, it may be desirable to provide a composition having less than 5000ppm of fluorine, or less than 1000ppm of fluorine, or less than 100ppm of elemental fluorine. In addition, previous work has relied on the inclusion of fluorine substituents to increase the transparency of the material, however, as shown in the following working examples, this is not necessary for achieving the desired optical properties of the compositions according to the present disclosure.

[0028] In one aspect, the polyetherimide comprises repeating units derived from a first diamine comprising 9,9-bis(4-aminophenyl)fluorene and a second diamine comprising diaminodiphenyl ether. In one aspect, the polyetherimide comprises repeating units derived from a first diamine comprising 9,9-bis(4-aminophenyl)fluorene and a second diamine comprising 4,4'-diaminodiphenyl sulfone. In one aspect, the polyetherimide comprises repeating units derived from a first diamine comprising 9,9-bis(4-aminophenyl)fluorene and a second diamine comprising m-phenylenediamine. In one aspect, the polyetherimide comprises repeating units derived from a first diamine comprising 9,9-bis(4-aminophenyl)fluorene and a second diamine comprising p-phenylenediamine.

[0029] In one specific aspect, the polyetherimide includes repeating units derived from a dianhydride comprising 4,4′-((propane-2,2-diylbis(4,1-phenylene))bis(oxy))bis(isobenzofuran-1,3-dione), the first diamine comprises 9,9-bis(4-aminophenyl)fluorene, and the second diamine comprises 4,4′-diaminodiphenyl ether.

[0030] In one specific aspect, the polyetherimide includes repeating units derived from a dianhydride comprising 4,4′-((propane-2,2-diylbis(4,1-phenylene))bis(oxy))bis(isobenzofuran-1,3-dione), the first diamine comprises 9,9-bis(4-aminophenyl)fluorene, and the second diamine comprises 4,4′-diaminodiphenyl sulfone.

[0031] In one specific aspect, the polyetherimide includes repeating units derived from a dianhydride comprising 4,4'-((1,1'-diphenyl]-4,4'-diylbis(oxy))bis(isobenzofuran-1,3-dione), the first diamine comprises 9,9-bis(4-aminophenyl)fluorene, and the second diamine comprises diaminodiphenyl ether.

[0032] In one specific aspect, the polyetherimide includes repeating units derived from a dianhydride comprising 4,4′-((propane-2,2-diylbis(4,1-phenylene))bis(oxy))bis(isobenzofuran-1,3-dione), the first diamine comprises 9,9-bis(4-aminophenyl)fluorene, and the second diamine comprises m-phenylenediamine.

[0033] In one specific aspect, the polyetherimide includes repeating units derived from a dianhydride comprising 4,4′-((propane-2,2-diylbis(4,1-phenylene))bis(oxy))bis(isobenzofuran-1,3-dione), the first diamine comprises 9,9-bis(4-aminophenyl)fluorene, and the second diamine comprises p-phenylenediamine.

[0034] In one aspect, the first diamine can be present in an amount of 10 to 98 mole percent, based on the total moles of the first and second diamines. Within this range, the first diamine comprising 9,9-bis(4-aminophenyl)fluorene can be present in an amount of at least 20 mole percent, or at least 30 mole percent, or at least 40 mole percent, or at least 50 mole percent, or at least 60 mole percent, or at least 70 mole percent, or at least 80 mole percent, based on the total moles of each of the first and second diamines. Also within this range, the first diamine comprising 9,9-bis(4-aminophenyl)fluorene can be present in an amount of up to 97 mole percent, or up to 95 mole percent, or up to 90 mole percent, or up to 80 mole percent, or up to 70 mole percent, or up to 60 mole percent, or up to 50 mole percent, or up to 40 mole percent, or up to 30 mole percent, or up to 20 mole percent, each based on the total moles of the first and second diamines.

[0035] The second diamine can be present in a complementary amount so that the total moles of the first diamine and the second diamine add up to 100 mole percent. For example, based on the total moles of the first diamine and the second diamine, the second diamine can be present in an amount of 2 to 90 mole percent. Within this range, each based on the total moles of the first diamine and the second diamine, the second diamine can be present in an amount of at least 3 mole percent, or at least 5 mole percent, or at least 10 mole percent, or at least 20 mole percent, or at least 30 mole percent, or at least 40 mole percent, or at least 50 mole percent, or at least 60 mole percent, or at least 70 mole percent, or at least 80 mole percent. Also within this range, each based on the total moles of the first diamine and the second diamine, the second diamine can be present in an amount of at most 80 mole percent, or at most 70 mole percent, or at most 60 mole percent, or at most 50 mole percent, or at most 40 mole percent, or at most 30 mole percent, or at most 20 mole percent.

[0036] In a specific aspect, the first diamine may be present in an amount of 60 to 98 mole percent, preferably 65 to 75 mole percent, or 75 to 85 mole percent, and the second diamine may be present in an amount of 2 to 40 mole percent, preferably 25 to 35 mole percent, or 15 to 25 mole percent, each based on the total moles of the first diamine and the second diamine.

[0037] The polyetherimide may optionally further include at least one chain end derived from a chain terminator (also known as an end capping agent). Chain terminators may 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 in the polyetherimide. Exemplary chain terminators include certain monoamines (e.g., aniline), monoacid anhydrides (e.g., phthalic anhydride), monophenolic compounds, and the like. In one aspect, the chain terminator may preferably be a monoamine chain terminator or a monoanhydride chain terminator, more preferably aniline or phthalic anhydride. However, it should be understood that the polyetherimide disclosed herein can be produced with any desired weight average molecular weight (Mw) and with any end caps. For example, the chain terminator may be present in an amount of 1 mol % to 10 mol %, based on the total moles of dianhydride, diamine, and chain terminator.

[0038] The polyetherimides of the present disclosure 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, or 35,000 g / mol to 55,000 g / mol, or 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) relative to polystyrene standards, eluting with dichloromethane.

[0039] The polyetherimides of the present disclosure may exhibit one or more advantageous properties. For example, the polyetherimide may 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 one aspect, the polyetherimide may exhibit a melt flow rate greater than 7 g / 10 min, as measured at 367°C under a 6.7 kg load. The polyetherimide may be transparent. For example, the polyetherimide may exhibit a percent transmittance of at least 80% at 850 nm. The polyetherimide may exhibit a combination of the foregoing properties. For example, the polyetherimide may exhibit a melt flow rate greater than 7 g / 10 min, as measured at 367°C under a 6.7 kg load, and a transmittance of at least 80% at 850 nm. In one aspect, the polyetherimide may exhibit a glass transition temperature greater than 275°C and a melt flow rate greater than 7 g / 10 min, as measured at 367°C under a 6.7 kg load. In one aspect, the polyetherimide can exhibit a glass transition temperature greater than 275° C. and a transmittance of at least 80% at 850 nm. In one aspect, the polyetherimide can exhibit a glass transition temperature greater than 275° C. and a melt flow rate greater than 7 g / 10 min as measured at 367° C. under a 6.7 kg load, and a transmittance of at least 80% at 850 nm. In one aspect, the polyetherimide can exhibit a yellowness index less than 125. In one aspect, the polyetherimide can exhibit a glass transition temperature greater than 275° C., a melt flow rate greater than 7 g / 10 min as measured at 367° C. under a 6.7 kg load, and a yellowness index less than 125.

[0040] In a specific aspect, the polyetherimide comprises, consists essentially of, or consists of repeating 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 can exhibit a melt flow rate greater than 9 g / 10 min as measured at 367° C. under a 6.7 kg load; and a transmittance at 850 nm of at least 80%. The polyetherimide can optionally exhibit a transmittance of at least 80% at 400° C. and 5000 s according to ASTM D3835. -1 The polyetherimide may optionally exhibit a viscosity greater than 200 Pa-s as measured at 400° C. The polyetherimide may optionally exhibit a glass transition temperature greater than 275° C. as measured by differential scanning calorimetry. The polyetherimide may optionally exhibit a yellowness index less than 125.

[0041] Methods for preparing polyetherimides represent another aspect of the present disclosure. A method for preparing a polyetherimide composition by contacting a dianhydride, a first diamine, and a second diamine under conditions effective to provide a polyetherimide. The conditions effective to provide the polyetherimide may include a temperature of 170° C. to 380° C. and a solids content of 1 to 50 weight percent, preferably 20 to 40 weight percent, and more preferably 25 to 35 weight percent. Polymerization may be carried out for 2 to 24 hours, preferably 3 to 16 hours. Polymerization may be carried out under reduced pressure, atmospheric pressure, or elevated pressure. In one aspect, the method may optionally further include devolatilizing the polyetherimide at 360 to 390° C. for 1 to 30 minutes. The dianhydride and the first and second diamines may be contacted in the presence of a solvent. Exemplary solvents can 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, triethylene glycol dimethyl ether, benzonitrile, 3-nitrotoluene, 2-nitrotoluene, 1-nitrotoluene, 1,3-dimethyl-2-imidazolidinone, dimethylacetamide, diphenyl ether, phenethyl ether, sulfolane, or combinations thereof. In one aspect, the solvent comprises o-dichlorobenzene.

[0042] The polyetherimide of the present disclosure can be used to form a polymer composition. Polymer compositions comprising polyetherimide represent another aspect of the present disclosure. The polymer composition can optionally include one or more thermoplastic polymers different from the polyetherimide. For example, such a polymer composition can include 1 weight percent to 99 weight percent of a polyetherimide according to the present disclosure and 1 weight percent to 99 weight percent of a second polymer, or 10 weight percent to 90 weight percent of a polyetherimide and 10 weight percent to 90 weight percent of a second polymer.

[0043] Illustrative examples of the second polymer include, but are not limited to, polyacetal, poly(C 1-6 alkyl) acrylate, polyacrylamide, polyacrylonitrile, polyamide, polyamideimide, polyanhydride, polyarylene ether, polyarylene ether ketone, polyarylene ketone, polyarylene sulfide, polyarylene sulfone, polybenzothiazole, polybenzoxazole, polybenzimidazole, polycarbonate, polyester, poly(C 1-6 alkyl) methacrylate, polymethacrylic acid amide, cycloolefin polymer, polyolefin, polyoxadiazole, polyoxymethylene, polyphthalimide, polysilazane, polysiloxane, polystyrene, polysulfide, polysulfonamide, polysulfonate, polythioester, polytriazine, polyurea, polyurethane, vinyl polymer, or a combination thereof.

[0044] Polymer composition can comprise the various additives that are usually incorporated into the composition of these types, and condition is to select any additive to not significantly adversely affect the performance of the expectation of composition.Exemplary additive comprises antioxidant, heat stabilizer, light stabilizer, ultraviolet light (UV) absorbing additive, quencher, plasticizer, lubricant, releasing agent, antistatic agent, visual effect additive such as dyestuff, pigment and light effect additive, flame retardant, anti-dripping agent and radiation stabilizer.Particle filler and reinforcing filler can also be present, and comprise mineral filler, flaky filler, carbon nanotube, flaky nano clay, carbon nanowire, carbon nanosphere, carbon-metal nanosphere, carbon nanorod, carbon-metal nanorod, nanoparticle, insoluble polymer, glass fiber, carbon fiber, glass-carbon fiber, talcum (comprising fibrous, modular, needle-shaped and flaky talcum), graphite, fibrillated fluoropolymer, polymer fiber and filament, weaving fiber, metallic particle, inorganic fiber, single crystal fiber or " whisker " etc.The combination of additive can be used. The above additives may be present individually in an amount of 0.005 wt % to 10 wt % or in combination in an amount of 0.005 wt % to 20 wt %, preferably 0.01 wt % to 10 wt %, based on the total weight of the composition.

[0045] Also provided herein are articles comprising polyetherimides or polymer compositions comprising polyetherimides. The polyetherimides can be formed into articles using any suitable technique, for example, melt processing techniques. Melt molding methods can include injection molding, extrusion molding, blow molding, rotational molding, embossing, and injection blow molding. For example, the melt molding method can be injection molding. In some embodiments, extrusion molding may be particularly suitable for the polyetherimides of the present disclosure. The polyetherimides can be formed into sheets or films by casting, blowing, or extrusion. These can be further thermoformed into articles and structures that can be oriented from the melt or at a later stage of composition processing. The polyetherimides can be overmolded onto articles made from different materials or by different methods. These articles can also be formed using techniques such as compression molding or stamping extrusion. These articles can be further formed into other shapes by machining. Exemplary articles include fibers, films, sheets, foams, filaments, molded articles, extruded articles, or powders. The properties of the polyetherimides of the present disclosure may be particularly suitable for forming thin-walled molded articles. In one aspect, the article can be an extruded film or an extruded sheet. The polyetherimides of the present disclosure may also be particularly suitable for use in optoelectronic applications. Specifically, the polyetherimides may be used in optoelectronic articles such as transmitters, receivers, connectors, lenses, waveguides, and the like.

[0046] The polyetherimides of the present disclosure are further illustrated by the following non-limiting examples.

[0047] Example

[0048] The materials used in this example are described in Table 1. The materials used in the following examples were not identified as having any fluorine-containing impurities as accepted.

[0049] Table 1

[0050]

[0051]

[0052] The polymer of this example was prepared according to the following general procedure. The required amount of each monomer was added to a reactor, followed by the addition of o-dichlorobenzene to provide a solid content of 30%. The contents of the reactor were stirred and heated to a temperature of 190°C under nitrogen. The reaction mixture was heated under reflux for five hours. The progress of the reaction was monitored by analyzing the molecular weight over time using gel permeation chromatography (GPC). Once the desired molecular weight was obtained, the solvent was removed from the reactor. The molten polymer was separated by passing it through an extruder to a water-cooled pelletizer.

[0053] The resulting polymers were characterized according to the following tests and test methods.

[0054] Molecular weights were determined by gel permeation chromatography in dichloromethane relative to polystyrene standards. When dichloromethane alone was insufficient for complete dissolution, samples were dissolved in dichloromethane or a 50:50 mixture of hexafluoroisopropanol and dichloromethane (HFIP / DCM).

[0055] The glass transition temperature (Tg) was determined using differential scanning calorimetry (DSC) under nitrogen according to ASTM D3418. The test was performed using a DSC Q2000 DSC instrument by heating from -10°C to 300°C at a rate of 20°C / min, and Tg was determined from the second heating cycle by the inflection point. g value.

[0056] The melt flow rate (MFR) was measured according to ASTM D1238 at a temperature of 367° C. and a load of 6.7 kg.

[0057] Viscosity change is a measure of the change in viscosity of a polymer after being held at a specified elevated temperature for a specified time. As described herein, viscosity change is the change in melt viscosity after a 30 minute hold at 400°C in a parallel plate rheometer. The sample was run in the parallel plates at 6.28 rad / s, 5% strain, from 0 to 1800 seconds.

[0058] IR transmission at 550 nm, 850 nm, 1150 nm, and 1310 nm was determined according to ASTM D1003 using injection molded 1 mm thick plaques.

[0059] Notched Izod impact (NII) strength was measured according to ASTM D256 using a 5.5 J pendulum and at 23°C.

[0060] Thermogravimetric analysis (TGA) measurements were performed using a TAQ800 TGA. Samples were heated from 40°C to 800°C at a heating rate of 20°C / min under nitrogen or air. The onset temperature was the extrapolated onset temperature measured by the intersection of the tangent lines according to ISO 11358-1. The percent weight loss was calculated from the initial mass and the mass at 800°C.

[0061] Capillary rheometry (viscosity) was performed according to ASTM D3835 at 400°C for 5000 s -1 The heat deflection temperature (HDT) was determined at 1.82 MPa according to ASTM D648. Tensile properties were characterized according to ASTM D638. Flexural properties were characterized according to ASTM D790. Yellowness index (YI) was characterized according to ASTM D1925. The solution yellowness index can be obtained by the same method, except that the polymer is dissolved in dichloromethane at a polymer concentration of 3.5 wt% and then the yellowness is measured according to the same ASTM standards. The material was also visually analyzed in sunlight to assess the basic color of the material.

[0062] Film integrity is measured by forming a thin film (approximately 0.05 mm) from a separate solid on a hydraulic press set to a temperature of 380°C. The sample is pressed until no voids remain on the 4 mm line. The sample is then folded in half in the void-free section, forming a crease at the folded edge. Sample films that remain intact and uncracked at the folded edge are considered to have maintained integrity (indicated as "yes" in the table below), while samples that fail to fold or form cracks are considered to have failed (indicated as "no" in the table below). When pressed under these conditions, which are similar to the temperature of an injection molding machine, thermoplastic materials with viable viscosities should be formable.

[0063] The polymer compositions and properties are summarized in Table 2. The amount of each component is given as mole percent (mol %).

[0064] Table 2a

[0065]

[0066] “-” means no data is generated

[0067] Table 2b

[0068]

[0069]

[0070] "-" means no data was generated, "*" means no film could be formed for testing

[0071] Desired properties include high T g (e.g., greater than 275°C), good melt flow rate (e.g., greater than 7 g / 10 min), and good IR transmittance. As can be seen from the data in Table 2, the polymers according to Examples 1-3 and 6-11 each met the desired Tg. The polymers according to Examples 1, 2, 6, and 8-9 each met the desired MFR. Examples 2, 7, and 9 each had good IR transmittance at both 850 nm and 1150 nm. In some instances, particularly for those where high molecular weight polymers were achieved, molding was attempted but unsuccessful (i.e., the composition could not be molded). In such cases, performance testing (e.g., IR transmission, NII) of molded samples required did not result in the generation of any data. In contrast, the comparative examples were observed to be deficient in at least one desired characteristic. Comparative Example 7 illustrates that the use of BPDA as the anhydride component does not provide the desired properties. Comparative Example 8 shows that the addition of a fluorine-containing component did not improve the transparency of the resulting composition. Comparative Example 8 has 8,100 ppm (0.81 wt %) of elemental fluorine, which was intentionally added from the addition of TFMB to the backbone. The exact amount of fluorine can be determined by ion chromatography.

[0072] It would be particularly advantageous to provide a polymer composition having a combination of the above properties. As can be seen from the data in Table 2, the polymer composition according to Example 2 can advantageously provide a Tg of 283°C, an MFR of 11 g / 10 min, and an IR transmittance of 84% at 850 nm and 79% at 1150 nm.

[0073] Based on the data in Table 2, polymers based on 3,3'-BPADA / BAF / DADE (e.g., polymers according to Examples 1 to 3) and 3,3'-BPoDA / BAF / DADE (e.g., polymers according to Examples 8 to 10) were selected for further characterization. Blends of polymers of varying molecular weights were also extruded, molded, and tested. The compositions and properties are summarized in Table 3 below.

[0074] Table 3

[0075]

[0076]

[0077] Table 4 shows the optical properties of molded samples of the polymer according to Example 2 and a blend of the polymers according to Examples 10 and 8 in a weight ratio of 1:3 (referred to as Example 18 in Table 3). For comparison, Table 4 also shows the optical properties of a commercially available polyetherimide (available as ULTEMTM 1010 resin obtained from SABIC). For Example 2 and Example E18 (E9 / E7 blend), at a thickness of 1 mm, and for ULTEM TM 1010 resin at 3.2 mm, the percent transmittance is recorded. The refractive index (RI) of each sample is also provided in Table 4. As shown in Table 4, the refractive index of E2 is similar to that of ULTEM TM 1010 Resin Datasheet Values. The optical properties summarized in Table 4 indicate that the polymers disclosed herein may be particularly well suited for optical applications.

[0078] Table 4

[0079]

[0080] Table 5 shows the results of optical property tests of the polymer according to the composition of Example 2.

[0081] Table 5

[0082]

[0083]

[0084] The present invention further encompasses the following aspects.

[0085] Aspect 1: A polyetherimide comprising repeating 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'-diphenyl]-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.

[0086] Aspect 2: The polyetherimide according to aspect 1, wherein the dianhydride is 4,4′-((propane-2,2-diylbis(4,1-phenylene))bis(oxy))bis(isobenzofuran-1,3-dione).

[0087] Aspect 3: The polyetherimide of Aspect 1 or 2, wherein the dianhydride is 4,4′-([1,1′-diphenyl]-4,4′-diylbis(oxy))bis(isobenzofuran-1,3-dione).

[0088] Aspect 4: The polyetherimide of Aspect 2 or 3, wherein the first diamine is 9,9-bis(4-aminophenyl)fluorene and the second diamine is 4,4′-diaminodiphenyl ether.

[0089] Aspect 5: The polyetherimide of Aspect 2, wherein the first diamine is 9,9-bis(4-aminophenyl)fluorene and the second diamine is 4,4′-diaminodiphenyl sulfone.

[0090] Aspect 6: The polyetherimide of any one of aspects 1 to 5, wherein the polyetherimide has a weight average molecular weight of 30,000 to 65,000 g / mol, preferably 35,000 to 45,000 g / mol, as determined by gel permeation chromatography in dichloromethane relative to polystyrene standards.

[0091] Aspect 7: The polyetherimide of any of aspects 1 to 6, wherein the polyetherimide exhibits a glass transition temperature greater than 275°C as determined by differential scanning calorimetry.

[0092] Aspect 8: The polyetherimide of any one of Aspects 1 to 7, wherein the polyetherimide exhibits one or more of: a melt flow rate greater than 7 g / 10 min as measured at 367° C. under a 6.7 kg load; or a transmittance of at least 80% at 850 nm; or a yellowness index less than 125 as measured according to ASTM D1925; or less than 5000 ppm, or less than 1000 ppm, or less than 100 ppm of elemental fluorine as determined using combustion ion chromatography.

[0093] Aspect 9: The polyetherimide according to 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; wherein the polyetherimide has a weight average molecular weight of 35,000 g / mol to 45,000 g / mol; and wherein the polyetherimide exhibits: a flow rate of 100 s at 400°C and 5000 s according to ASTM D3835. -1 and a melt flow rate greater than 9 g / 10 min measured at 367° C. under a 6.7 kg load; and a transmittance of at least 80% at 850 nm.

[0094] Aspect 10: The polyetherimide of Aspect 9, wherein the polyetherimide exhibits a glass transition temperature greater than 275°C, preferably greater than 275°C to 290°C, as determined by differential scanning calorimetry.

[0095] Aspect 11: The polyetherimide according to any one of claims 1 to 10, wherein the first diamine is present in an amount of 60 mol% to 98 mol%, and the second diamine is present in an amount of 2 mol% to 40 mol%, each based on the total moles of the first diamine and the second diamine.

[0096] Aspect 12: A polymer composition comprising the polyetherimide of any one of aspects 1 to 11.

[0097] Aspect 12: An article comprising the polyetherimide of any one of aspects 1 to 11 or the polymer composition of aspect 12.

[0098] Aspect 13: The article according to aspect 12, wherein the article is an optical article, preferably a lens or an optoelectronic component.

[0099] Aspect 14: A method for making the polyetherimide according to any one of aspects 1 to 10, comprising combining a dianhydride, a first diamine, and a second diamine under conditions effective to provide the polyetherimide.

[0100] Alternatively, the compositions, methods, and articles may 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 formulated so as to be free of or essentially free of any material (or species), step, or component that is otherwise not necessary to achieve the function or purpose of the compositions, methods, and articles.

[0101] All ranges disclosed herein include endpoints, and endpoints can be combined independently of each other. "Combination" includes blends, mixtures, alloys, reaction products, etc. The terms "first", "second", etc. do not represent any order, quantity or importance, but are used to distinguish one element from another. Unless otherwise specified herein or clearly contradicted by the context, the terms "one" and "a kind of" and "the" do not represent quantity restrictions, but are interpreted as covering the singular and plural. Unless otherwise explicitly stated, "or" means "and / or". Mentioning "an aspect" throughout the specification means that the specific elements described in conjunction with the aspect are included in at least one aspect described herein, and may or may not be present in other aspects. The term "combination thereof" as used in this article includes one or more listed elements and is open, allowing the presence of one or more unnamed similar elements. In addition, it should be understood that the elements described can be combined in any suitable manner in various aspects.

[0102] Unless specified to the contrary herein, all test standards are the most current 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 standards appear.

[0103] 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 belongs. 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 from this application takes precedence over the conflicting term from the incorporated reference.

[0104] Compounds are described using standard nomenclature. For example, any position not substituted by any indicator group is understood to have its valency filled by a bond or hydrogen atom as indicated. A dash ("-") that is not between two letters or symbols is used to indicate the point of attachment of a substituent. For example, -CHO connects through the carbon of a carbonyl group.

[0105] As used in this article, the term "alkyl", whether used alone or as a prefix, suffix or fragment of another term, refers to a residue that only contains carbon and hydrogen. The residue can be aliphatic or aromatic, straight chain, cyclic, bicyclic, branched, saturated or unsaturated. It can also contain a combination of aliphatic, aromatic, straight chain, cyclic, bicyclic, branched, saturated and unsaturated hydrocarbon parts. However, when the alkyl residue is described as substituted, it can optionally contain heteroatoms on and above the carbon and hydrogen members of the substituent residue. Therefore, when specifically described as substituted, the alkyl residue can also contain one or more carbonyls, amino, hydroxyl groups, etc., or it can contain heteroatoms in the main chain of the alkyl residue. The term "alkyl" refers to a branched or straight chain, saturated aliphatic alkyl group, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, sec-pentyl and n-hexyl and sec-hexyl. "Alkenyl" refers to a straight or branched monovalent hydrocarbon radical having at least one carbon-carbon double bond (e.g., vinyl (-HC=CH2)). "Alkoxy" refers to an alkyl radical attached via an oxygen (i.e., alkyl-O-), such as methoxy, ethoxy, and sec-butoxy. "Alkylene" refers to a straight or branched, saturated, divalent aliphatic hydrocarbon radical (e.g., methylene (-CH2-) or propylene (-(CH2)3-)). "Cycloalkylene" refers to a divalent cyclic alkylene radical, -C n H 2n-x, where x is the number of hydrogens replaced by cyclization. "Cycloalkenyl" refers to a monovalent group having one or more rings and one or more carbon-carbon double bonds in the ring, wherein all ring members are carbon (e.g., cyclopentyl and cyclohexyl). "Aryl" refers to an aromatic hydrocarbon group containing a specified number of carbon atoms, such as phenyl, cycloheptatrienone, indanyl, or naphthyl. "Arylene" refers to a divalent aryl group. "Alkylenarylene" refers to an arylene group substituted by an alkyl group. "Arylalkylene" refers to an alkylene group substituted by an aryl group (e.g., benzyl). The prefix "halo" refers to a group or compound comprising one or more fluorine, chlorine, bromine, or iodine substituents. There may be a combination of different halogen atoms (e.g., bromine and fluorine) or only chlorine atoms. The prefix "hetero" refers to a compound or group comprising at least one ring member of a heteroatom (e.g., 1, 2, or 3 heteroatoms), wherein the heteroatoms are each independently N, O, S, Si, or P. "Substituted" means that the compound or group is substituted with at least one (e.g., 1, 2, 3, or 4) substituents, each of which is independently C 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), thiocyanate (-SCN), toluenesulfonyl (CH3C6H4SO2-), C 3-12 Cycloalkyl, C 2-12 Alkenyl, C 5-12 Cycloalkenyl, C 6-12 Aryl, C 7-13 Arylalkylene, C 4-12 Heterocycloalkyl, and C 3-12 A heteroaryl group replaces a hydrogen atom provided that the normal valence of the substituted atom is not exceeded. The number of carbon atoms indicated in the group does not include any substituents. For example, -CH2CH2CN is a C2 alkyl group substituted with a nitrile.

[0106] While particular embodiments have been described, presently unforeseen or possibly unforeseen alternatives, modifications, variations, improvements, and substantial equivalents may occur to the applicant or others skilled in the art. Accordingly, the appended claims as filed and as they may be amended are intended to encompass all such alternatives, modifications, variations, improvements, and substantial equivalents.

Claims

1. A polyetherimide comprising repeating units derived from: Dianhydride, selected from 4,4'-((propane-2,2-diylbis(4,1-phenylene))bis(oxy))bis(isobenzofuran-1,3-dione); or 4,4'-([1,1'-diphenyl]-4,4'-diylbis(oxy))bis(isobenzofuran-1,3-dione); a first diamine comprising 9,9-bis(4-aminophenyl)fluorene; and The second diamine includes diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, m-phenylenediamine or p-phenylenediamine. 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 . The polyetherimide according to claim 1 , wherein the dianhydride is 4,4′-([1,1′-diphenyl]-4,4′-diylbis(oxy))bis(isobenzofuran-1,3-dione).

4. The polyetherimide according to claim 2 or 3, wherein the first diamine is 9,9-bis(4-aminophenyl)fluorene and the second diamine is 4,4'-diaminodiphenyl ether.

5. The polyetherimide of claim 2 or 3, wherein the first diamine is 9,9-bis(4-aminophenyl)fluorene and the second diamine is 4,4'-diaminodiphenyl sulfone.

6. The polyetherimide according to any one of claims 1 to 5, wherein the first diamine is present in an amount of 60 to 98 mol %, preferably 75 to 85 mol %, and the second diamine is present in an amount of 2 to 40 mol %, preferably 15 to 25 mol %, each based on the total moles of the first diamine and the second diamine.

7. The polyetherimide according to any one of claims 1 to 6, wherein the polyetherimide has a weight average molecular weight relative to polystyrene standards of 30,000 to 65,000 g / mol, preferably 35,000 to 45,000 g / mol, as determined by gel permeation chromatography in dichloromethane.

8. The polyetherimide of any one of claims 1 to 7, wherein the polyetherimide exhibits a glass transition temperature greater than 275°C as determined by differential scanning calorimetry.

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

10. The polyetherimide according to claim 1, in, 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; wherein the polyetherimide has a weight average molecular weight of 35,000 g / mol to 45,000 g / mol; and Among them, the above-mentioned polyetherimide exhibits: According to ASTM D3835 at 400℃ and 5000s -1 A viscosity greater than 200 Pa-s measured at 40°C; and a melt flow rate greater than 9 g / 10 min measured at 367° C. under a 6.7 kg load; and At least 80% transmittance at 850nm.

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 determined by differential scanning calorimetry.

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

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

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

15. A method for producing the polyetherimide according to any one of claims 1 to 11, comprising: The dianhydride, the first diamine, and the second diamine are combined under conditions effective to provide the polyetherimide.

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