Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1003—Preparatory processes
  • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
  • C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/14—Polyamide-imides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

• a polyetherimide comprises 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'-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, meta-phenylene diamine, or para-phenylene diamine.
• Another aspect of the present disclosure is a polymer composition comprising the polyetherimide.
• Another aspect of the present disclosure is an article comprising the polyetherimide or the polymer composition.
• 22SHPP0074-WO-PCT (SS240080PCT) [0007]
• a method for the manufacture of the polyetherimide comprises combining the dianhydride and the diamine under conditions effective to provide the polyetherimide.
• DETAILED DESCRIPTION Described herein is a polyetherimide including repeating units derived from a particular combination of monomers.
• an aspect of the present disclosure is a polyetherimide.
• the polyetherimide comprises repeating units derived from a dianhydride, a first diamine, and a second diamine.
• 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) shown as Formulas (I) and (II), respectively.
• the dianhydride is the 4,4'-((propane-2,2-diylbis(4,1- phenylene))bis(oxy))bis(isobenzofuran-1,3-dione) (i.e., the dianhydride according to Formula (I)).
• the dianhydride according to Formula (I) may also be referred to as “3,3’-BPADA” herein.
• the dianhydride is the 4,4'-([1,1'-biphenyl]-4,4'- diylbis(oxy))bis(isobenzofuran-1,3-dione) (i.e., the dianhydride according to Formula (II)).
• the dianhydride according to Formula (II) may also be referred to as “3,3’-BPoDA” herein.
• the poly(etherimide) can optionally further comprise additional repeating units derived from polymerization of a dianhydride different from the dianhydrides according to Formula (I) and Formula (II).
• the dianhydride different from the dianhydride according to Formula (I) and Formula (II) can 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 total moles of dianhydride.
• the 22SHPP0074-WO-PCT (SS240080PCT) polyetherimide does not comprise repeating units derived from any dianhydride other than the dianhydride according to Formula (I) or Formula (II).
• the dianhydride different from the dianhydride according to Formula (I) or Formula (II) can be of the formula (III) or (IV) wherein T is -O- or a group of the formula -O-Z-O- wherein the divalent bonds of the -O- or the -O-Z-O- group are in the 3,3', 3,4', 4,3', or the 4,4' positions, and Z is an aromatic C 6-24 monocyclic or polycyclic group optionally substituted with 1 to 6 C 1-8 alkyl groups, 1-8 halogen atoms, or a combination thereof; and R 1 and R 2 are each independently a hydrogen, a C 1-8 alkyl group, a halogen, or a combination thereof, preferably
• Z can be a group derived from a dihydroxy compound of the formula (V) wherein 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 a C1-18 organic bridging group.
• the poly(etherimide) further comprises the second dianhydride of the formula (III), provided that the second dianhydride of the formula (III) is not the same as the dianhydride according to Formula (I) or Formula (II).
• the poly(etherimide) further comprises the second dianhydride of the formula (IV).
• the polyetherimide can exclude repeating units derived from formula (III), formula (IV), or both.
• the dianhydride is polymerized with a first diamine and a second diamine to provide the polyetherimide of the present disclosure.
• the first diamine comprises 9,9-bis(4- aminophenyl)fluorene, which may also be referred to as “BAF” herein and is shown in Formula (VI).
• the second diamine comprises diaminodiphenyl ether (also referred to herein as “DADE”), 4,4’-diaminodiphenyl sulfone (also referred to herein as “DDS”), meta-phenylene 22SHPP0074-WO-PCT (SS240080PCT) diamine (also referred to herein as “mPD”), or para-phenylene diamine (also referred to herein as “pPD”).
• DADE, DDS, mPD, and pPD are shown in Formulas (VII)-(X), respectively.
• the polyetherimide does not comprise repeating units derived from a fluorine substituted diamine.
• the polyetherimide does not include any fluorine substituents along the polymer backbone.
• the polyetherimide can exclude repeating units derived from a fluorine containing diamine such as bistrifluoromethylbenzidine (TFMB) (e.g., 2,2’- bistrifluoromethylbenzidine).
• TFMB bistrifluoromethylbenzidine
• polyetherimides excluding fluorine substituents can be desirable for regulatory reasons. For example, it can be desirable to provide a composition having less than 5000 ppm of fluorine, or less than 1000 ppm of fluorine, or less than 100 ppm of elemental fluorine.
• the polyetherimide comprises repeating units derived from the first diamine comprising 9,9-bis(4-aminophenyl)fluorene and the second diamine comprising diaminodiphenyl ether.
• the polyetherimide comprises the repeating units derived from the first diamine comprising 9,9-bis(4-aminophenyl)fluorene and the second diamine comprising 4,4’-diaminodiphenyl sulfone.
• the polyetherimide comprises the repeating units derived from the first diamine comprising 9,9-bis(4-aminophenyl)fluorene and the second diamine comprising meta-phenylene diamine. In an aspect, the polyetherimide comprises the repeating units derived from the first diamine comprising 9,9-bis(4- aminophenyl)fluorene and the second diamine comprising para-phenylene diamine.
• the polyetherimide comprises repeating units derived from the dianhydride comprising 4,4'-((propane-2,2-diylbis(4,1- phenylene))bis(oxy))bis(isobenzofuran-1,3-dione), the first diamine comprising 9,9-bis(4- aminophenyl)fluorene, and the second diamine comprising 4,4’-diaminodiphenyl ether.
• the polyetherimide comprises repeating units derived from the dianhydride comprising 4,4'-((propane-2,2-diylbis(4,1- 22SHPP0074-WO-PCT (SS240080PCT) phenylene))bis(oxy))bis(isobenzofuran-1,3-dione), the first diamine comprising 9,9-bis(4- aminophenyl)fluorene, and the second diamine comprising 4,4’-diaminodiphenyl sulfone.
• the polyetherimide comprises repeating units derived from the dianhydride comprising 4,4'-([1,1'-biphenyl]-4,4'-diylbis(oxy))bis(isobenzofuran-1,3-dione), the first diamine comprising 9,9-bis(4-aminophenyl)fluorene, and the second diamine comprising diaminodiphenyl ether.
• the polyetherimide comprises repeating units derived from the dianhydride comprising 4,4'-((propane-2,2-diylbis(4,1- phenylene))bis(oxy))bis(isobenzofuran-1,3-dione), the first diamine comprising 9,9-bis(4- aminophenyl)fluorene, and the second diamine comprising meta-phenylene diamine.
• the polyetherimide comprises repeating units derived from the dianhydride comprising 4,4'-((propane-2,2-diylbis(4,1- phenylene))bis(oxy))bis(isobenzofuran-1,3-dione), the first diamine comprising 9,9-bis(4- aminophenyl)fluorene, and the second diamine comprising para-phenylene diamine.
• the first diamine can be present in an amount of 10 mole percent to 98 mole percent, based on the total moles of the first diamine and the second diamine.
• 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, each based on the total moles of the first diamine and the second diamine.
• the first diamine comprising 9,9-bis(4-aminophenyl)fluorene can be present in an amount of at most 97 mole percent, or at most 95 mole percent, or at most 90 mole percent, or 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, each based on the total moles of the first diamine and the second diamine.
• the second diamine can be present in a complementary amount such the total the total moles of the first diamine and the second diamine total 100 mole percent.
• the second diamine can be present in an amount of 2 mole percent to 90 mole percent, 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, 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 22SHPP0074-WO-PCT (SS240080PCT) 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, each based on the total moles of the first diamine and the second diamine.
• the first diamine can be present in an amount of 60 mole percent to 98 mole percent, preferably 65 mole percent to 75 mole percent, or 75 mole percent to 85 mole percent
• the second diamine can be present in an amount of 2 mole percent to 40 mole percent, preferably 25 mole percent to 35 mole percent, or 15 mole percent to 25 mole percent, each based on the total moles of the first diamine and the second diamine.
• the polyetherimide can optionally further comprise at least one chain end derived from a chain stopper (also referred to as an endcapping agent). Chain stoppers can be employed during the polymerization reaction.
• the chain stopper limits molecular weight growth rate and thus can be used to control molecular weight in the polyetherimide.
• exemplary chain stoppers include certain mono amines (for example aniline), mono anhydrides (for example phthalic anhydride), mono-phenolic compounds and the like.
• the chain stopper can preferably be a monoamine chain stopper or a monoanhydride chain stopper, more preferably aniline or phthalic anhydride.
• Mw weight average molecular weight
• Chain stoppers can be present, for example, in an amount of 1 mole percent to 10 mole percent, based on the total moles of dianhydride, diamine, and chain stopper.
• the polyetherimide 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. [0030] The polyetherimide of the present disclose can exhibit one or more advantageous properties.
• the polyetherimide can exhibit a glass transition temperature of greater than 275°C, for example greater than 275 °C to 290 °C, as determined by differential scanning calorimetry.
• the polyetherimide can exhibit a melt flow rate of greater than 7 g/10 min, as determined at 367 °C under a 6.7 kg load.
• the polyetherimide can be transparent.
• the polyetherimide can exhibit a percent transmission of at least 80% at 850 nm.
• the polyetherimide can exhibit a combination of the foregoing properties.
• the polyetherimide can exhibit a melt flow rate of greater than 7 g/10 min, as determined at 367 °C under a 6.7 kg load and a transmission of at least 80% at 850 nm.
• the 22SHPP0074-WO-PCT (SS240080PCT) polyetherimide can exhibit a glass transition temperature of greater than 275 °C and a melt flow rate of greater than 7 g/10 min, as determined at 367°C under a 6.7 kg load.
• the polyetherimide can exhibit a glass transition temperature of greater than 275 °C and a transmission of at least 80% at 850 nm.
• the polyetherimide can exhibit a glass transition temperature of greater than 275 °C and a melt flow rate of greater than 7 g/10 min, as determined at 367 °C under a 6.7 kg load and a transmission of at least 80% at 850 nm. In an aspect, the polyetherimide can exhibit a yellowness index of less than 125. In an aspect, the polyetherimide can exhibit a glass transition temperature of greater than 275 °C, a melt flow rate of greater than 7 g/10 min, as determined at 367°C under a 6.7 kg load, and a yellowness index of less than 125.
• 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 of greater than 9 g/10 min, as determined at 367 °C under a 6.7 kg load; and a transmission of at least 80% at 850 nm.
• the polyetherimide can optionally exhibit a viscosity of greater than 200 Pa-s, as determined according to ASTM D3835 at 400 °C and 5000 s -1 .
• the polyetherimide can optionally exhibit a glass transition temperature of greater than 275°C, as determined by differential scanning calorimetry.
• the polyetherimide can optionally exhibit a yellowness index of less than 125.
• a method of making the polyetherimide represents another aspect of the present disclosure. The method of making the polyetherimide composition contacting the dianhydride, the first diamine and the second diamine under conditions effective to provide the polyetherimide.
• Conditions effective to provide the polyetherimide can include a temperature of 170 °C to 380 °C, and a solids content of 1 weight percent to 50 weight percent, preferably 20 weight percent to 40 weight percent, more preferably 25 weight percent to 35 weight percent.
• Polymerizations can be carried out for 2 hours to 24 hours, preferably 3 hours to 16 hours.
• the polymerization can be conducted at reduced, atmospheric, or high pressure.
• the method can optionally further comprise devolatilizing the polyetherimide at 360 °C to 390 °C for 1 minute to 30 minutes. Contacting the dianhydride and the first and second diamines can be in the presence of a solvent.
• Exemplary solvents can include ortho-dichlorobenzene, para- dichlorobenzene, meta-dichlorobenzene, meta-cresol, para-cresol, ortho-cresol, N- methylpyrrolidone, veratrole, chlorobenzene, xylene, 1,2,4-trichlorobenzene, 1,3,4- trichlorobenzene, ethyl benzoate, triglyme, benzonitrile, 3-nitrotoluene, 2-nitrotoluene, 1- 22SHPP0074-WO-PCT (SS240080PCT) nitrotoluene, 1,3-dimethyl-2-imidazolidinone, dimethyl acetamide, diphenyl ether, phenetole, sulfolane, or a combination thereof.
• the solvent comprises ortho-dichlorobenzene.
• the polyetherimide of the present disclosure can be useful in forming polymer compositions.
• a polymer composition comprising the polyetherimide represents another aspect of the present disclosure.
• the polymer composition can optionally comprise one or more thermoplastic polymers other than the polyetherimide.
• Such polymer compositions can include, for example, 1 weight percent to 99 weight of the polyetherimide according to the present disclosure and 1 weight percent to 99 weight percent of the second polymer, or 10 weight percent to 90 weight percent of the polyetherimide and 10 weight percent to 90 weight percent of the second polymer.
• second polymers include, but are not limited to, a 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, polymethacrylamide, cyclic olefin polymer, polyolefin, polyoxadiazole, polyoxymethylene, polyphthalide, polysilazane, polysiloxane, polystyrene, polysulfide, polysulfonamide, polysulfonate, polythioester, polytriazine, polyurea, polyurethane, vinyl polymer, or a combination thereof.
• the polymer composition can include various additives ordinarily incorporated into compositions of these types, with the proviso that any additive is selected so as to not significantly adversely affect the desired properties of the composition.
• additives include antioxidants, thermal stabilizers, light stabilizers, ultraviolet light (UV) absorbing additives, quenchers, plasticizers, lubricants, mold release agents, antistatic agents, visual effect additives such as dyes, pigments, and light effect additives, flame resistances, anti-drip agents, and radiation stabilizers.
• Particulate fillers and reinforcing fillers can also be present, and include mineral fillers, flaked 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, needle shaped, and lamellar talc, graphite, fibrillated fluoropolymers, polymer fibers and filaments, woven fibers, metal particles, inorganic fibers, single crystal fibers or “whiskers”, or the like. Combinations of additives can be used.
• the foregoing additives can be present individually in an amount from 0.005 weight percent to 10 weight percent, or combined in an amount from 0.005 weight percent to 20 weight percent, preferably 0.01 weight percent to 10 wt%, based on the total weight of the composition.
• 22SHPP0074-WO-PCT SS240080PCT
• articles that include the polyetherimide or the polymer composition comprising the polyetherimide.
• the polyetherimide 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, coining, and injection blow molding.
• the melt molding method can be injection molding.
• extrusion molding can be particularly suitable for the polyetherimides of the present disclosure.
• the polyetherimide can be formed into sheets or films by casting, blowing, or extruding. These can be further thermoformed into articles and structures that can be oriented from the melt or at a later stage in the processing of the compositions.
• the polyetherimide can be over-molded onto an article made from a different material or by a different process.
• the articles can also be formed using techniques such as compression molding or ram extruding.
• the articles can be further formed into other shapes by machining. Exemplary articles include a fiber, a film, a sheet, a foam, a filament, a molded article, an extruded article, or a powder.
• the properties of the polyetherimide of the present disclosure can be particularly suitable for forming thin-walled molded articles.
• the article can be an extruded film or an extruded sheet.
• the polyetherimide of the present disclosure can also be particularly suitable for use in optoelectronic applications.
• the polyetherimide can be used for optoelectronic articles such as transmitters, receivers, connectors, lenses, waveguides, and the like.
• the polyetherimide of the present disclosure is further illustrated by the following non-limiting examples. EXAMPLES [0038] Materials for the present examples are described in Table 1. No material used in the following examples was identified as having any fluorine-containing impurities as received.
• Table 1 Component Description 3,3’-BPADA 4,4'-((propane-2,2-diylbis(4,1-phenylene))bis(oxy))bis(isobenzofuran-1,3-dione), CAS Reg. No.: 52256-80-1 4,4’-BPADA 4,4 ⁇ -(4,4 ⁇ -Isopropylidenediphenoxy)bis(phthalic anhydride), CAS Reg. No.: 38103-06-9 3,3’-BPoDA 4,4'-([1,1'-biphenyl]-4,4'-diylbis(oxy))bis(isobenzofuran-1,3-dione), CAS Reg.
• Molten polymer was isolated by passing through an extruder to a water-cooled pelletizer. [0040] The resulting polymers were characterized according to the following tests and test methods. [0041] Molecular weight was determined by gel permeation chromatography in dichloromethane relative to polystyrene standards. Samples were dissolved in either dichloromethane or a 50:50 mixture of hexafluoroisopropanol and dichloromethane (HFIP/DCM) when dichloromethane alone was inadequate for full dissolution. [0042] Glass transition temperature (Tg) was determined under nitrogen using differential scanning calorimetry (DSC) according to ASTM D3418.
• DSC differential scanning calorimetry
• Viscosity change is a measurement of the change in viscosity of the polymer after being maintained at a specified elevated temperature for a specified time. Viscosity change as described herein is the change in melt viscosity after being held at 400 oC for 30 minutes in a parallel plate rheometer.
• the onset temperature is an extrapolated onset temperature as 22SHPP0074-WO-PCT (SS240080PCT) measured by the intersection of tangents according to ISO 11358-1. Weight loss percent is calculated from the initial mass and mass at 800 °C.
• Capillary rheometry (viscosity) was determined at 400 °C at 5000 s -1 according to ASTM D3835.
• 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.
• a solution yellowness index can be taken by the same method, except the polymer is dissolved in methylene chloride at a polymer concentration of 3.5 wt%, then measured to yellowness under the same ASTM standard. The materials were also visually analyzed by eye in sunlight to assess the basic color of the material. [0049] Film integrity was measured by forming a thin film ( ⁇ 0.05 mm) from isolated solids on a hydraulic press which could be set to a temperature of 380 °C. Samples were pressed until no voids remained across a 4 mm line. Samples were then folded in half in the void free section, forming a crease at the folded edge.
• thermoplastic material with a viable viscosity should be formable when pressed at these conditions, which are similar to the temperature of an injection molding machine.
• Desired properties include a high Tg (e.g., greater than 275 °C), 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 according to Examples 1-3, and 6-11 each meet the desired Tg. The polymers according to Examples 1, 2, 6, and 8-9 each meet the desired MFR.
• Examples 2, 7, and 9 each possess good IR transmittance at both 850 nm and 1150 nm.
• molding was attempted but unsuccessful (i.e., the composition could not be molded).
• property testing which require a molded sample (e.g., IR transmission, NII) did not result in any data 22SHPP0074-WO-PCT (SS240080PCT) being generated.
• comparative examples were observed to be deficient in at least one desired property.
• Comparative example 7 illustrates that using BPDA as the anhydride component did 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 weight percent) elemental fluorine intentionally added from the addition of TFMB into the backbone. Exact fluorine amounts could be determined by ion chromatography. [0052] It would be especially advantageous to provide a polymer composition having a combination of the aforementioned properties. From the data in Table 2, it can be seen that the polymer composition according to Example 2 can advantageously provide a Tg of 283 °C, a MFR of 11 g/10 minutes, and IR transmittance of 84% at 850 nm and 79% at 1150 nm.
• Table 4 shows optical properties for a molded sample of the polymer according to Example 2 as well as a blend of the polymers according to Examples 10 and 8 in a 1:3 weight 22SHPP0074-WO-PCT (SS240080PCT) ratio (referred to as Example 18 in Table 3).
• Example 18 the optical properties of a commercially available polyetherimide (obtained as ULTEM TM 1010 resin from SABIC) are also shown in Table 4.
• Example 2 Percent transmission was recorded at a thickness of 1 mm for Example 2 and the Example E18 (E9/E7 blend), and at 3.2 mm for ULTEM TM 1010 resin.
• the refractive index (RI) of each sample is also provided in Table 4. As shown in Table 4, the refractive index for E2 is similar to ULTEM TM 1010 resin datasheet value.
• the optical properties summarized in Table 4 indicate that the polymers disclosed herein may be particularly well suited for optical applications.
• Table 4 Wavelength E2 E17 ULTEM TM 1010 % transmission, 62.1% 40.9% 79% 550 nm % transmission, 83.9% 77.6% 86.5% 850 nm % transmission, 79.3% 77.5% 85.1% 1150 nm % transmission, 86% 83.3% 87.5% 1310 nm RI, 850 nm 1.639 1.658 1.639 [0055] Table 5 shows the results of optical property testing for the polymer according to the composition of Example 2.
• 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'-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, meta-phenylene diamine, or para-phenylene diamine.
• a dianhydride selected from 4,4'-((propane-2,2-diylbis(4,1- phenylene))bis(oxy))bis(isobenzofuran-1,3-dione); or 4,4'
• Aspect 2 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).
• Aspect 3 The polyetherimide of aspect 1 or 2, wherein the dianhydride is 4,4'- ([1,1'-biphenyl]-4,4'-diylbis(oxy))bis(isobenzofuran-1,3-dione).
• 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.
• 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.
• Aspect 6 The polyetherimide of any of aspects 1 to 5, wherein the polyetherimide has a weight average molecular weight of 30,000 g/mol to 65,000 g/mol, preferably 35,000 g/mol to 45,000 g/mol, as determined by gel permeation chromatography in dichloromethane relative to polystyrene standards.
• Aspect 7 The polyetherimide of any of aspects 1 to 6, wherein the polyetherimide exhibits a glass transition temperature of greater than 275°C, as determined by differential scanning calorimetry.
• Aspect 8 The polyetherimide of any of aspects 1 to 7, wherein the polyetherimide exhibits one or more of: a melt flow rate of greater than 7 g/10 min, as determined at 367 °C under a 6.7 kg load; or a transmission of at least 80% at 850 nm; or a yellowness index of less than 125, as determined 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.
• 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; 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 viscosity of greater than 200 Pa-s, as determined according to ASTM D3835 at 400 °C and 5000 s -1 ; and a melt flow rate of greater than 9 g/10 min, as determined at 367°C under a 6.7 kg load; and a transmission of at least 80% at 850 nm.
• the dianhydride is 4,4'- ((propane-2,2-di
• Aspect 10 The polyetherimide of aspect 9, wherein the polyetherimide exhibits a glass transition temperature of greater than 275 °C, preferably greater than 275 °C to 290 °C, as determined by differential scanning calorimetry.
• Aspect 11 The polyetherimide of any of claims 1 to 10, wherein the first diamine is present in an amount of 60 mole percent to 98 mole percent, and the second diamine 22SHPP0074-WO-PCT (SS240080PCT) is present in an amount of 2 mole percent to 40 mole percent, each based on the total moles of the first diamine and the second diamine.
• Aspect 12 A polymer composition comprising the polyetherimide of any of aspects 1 to 11.
• Aspect 12 An article comprising the polyetherimide of any of aspects 1 to 11 or the polymer composition of aspect 12.
• Aspect 13 The article of aspect 12, wherein the article is an optical article, preferably a lens or an optoelectronic component.
• Aspect 14 A method for the manufacture of the polyetherimide of any of aspects 1 to 10, the method comprising: combining the dianhydride, the first diamine, and the second diamine under conditions effective to provide the polyetherimide.
• the compositions, methods, and articles can alternatively comprise, consist of, or consist essentially of, any appropriate materials, steps, or components herein disclosed.
• compositions, methods, and articles can additionally, or alternatively, be formulated so as to be devoid, or substantially free, of any materials (or species), steps, or components, that are otherwise not necessary to the achievement of the function or objectives of the compositions, methods, and articles.
• All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other. “Combinations” is inclusive of 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.
• any position not substituted by any indicated group is understood to have its valency filled by a bond as indicated, or a hydrogen atom.
• a dash (“-") that is not between two letters or symbols is used to indicate a point of attachment for a substituent.
• -CHO is attached through carbon of the carbonyl group.
• hydrocarbyl whether used by itself, or as a prefix, suffix, or fragment of another term, refers to a residue that contains only carbon and hydrogen. The residue can be aliphatic or aromatic, straight-chain, cyclic, bicyclic, branched, saturated, or unsaturated.
• hydrocarbyl residue can also contain combinations of aliphatic, aromatic, straight chain, cyclic, bicyclic, branched, saturated, and unsaturated hydrocarbon moieties.
• hydrocarbyl residue when the hydrocarbyl residue is described as substituted, it may, optionally, contain heteroatoms over and above the carbon and hydrogen members of the substituent residue.
• the hydrocarbyl residue when specifically described as substituted, can also contain one or more carbonyl groups, amino groups, hydroxyl groups, or the like, or it can contain heteroatoms within the backbone of the hydrocarbyl residue.
• alkyl means 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, and n- and s-hexyl.
• Alkoxy means an alkyl group that is linked via an oxygen (i.e., alkyl-O-), for example methoxy, ethoxy, and sec-butyloxy groups.
• Alkylene means a straight or branched chain, saturated, divalent aliphatic hydrocarbon group (e.g., methylene (-CH2-) or, propylene (-(CH2)3- )).
• Cycloalkylene means a divalent cyclic alkylene group, -C n H 2n-x , wherein x is the number of hydrogens replaced by cyclization(s).
• Cycloalkenyl means 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 means an aromatic hydrocarbon group containing the specified number of carbon atoms, such as phenyl, tropone, indanyl, or naphthyl.
• Arylene means a divalent aryl group.
• Alkylarylene means an arylene group substituted with an alkyl group.
• Arylalkylene means an alkylene group substituted with an 22SHPP0074-WO-PCT (SS240080PCT) aryl group (e.g., benzyl).
• halo means a group or compound including one more of a fluoro, chloro, bromo, or iodo substituent. A combination of different halo atoms (e.g., bromo and fluoro), or only chloro atoms can be present.
• hetero means that the compound or group includes at least one ring member that is a heteroatom (e.g., 1, 2, or 3 heteroatom(s)), wherein the heteroatom(s) is each independently N, O, S, Si, or P.

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