Flame retardant, thermally stabilized polyetherimide

Abstract

The polyetherimide composition comprises a polyetherimide and an organophosphorus stabilizer present in an amount effective to provide from greater than 0.01 ppm to less than 20 ppm, preferably from greater than 0.01 ppm to less than 10 ppm, and more preferably from greater than 0.01 ppm to less than 4.8 ppm of phosphorus, based on the total weight of the polyetherimide composition, wherein the organophosphorus stabilizer has a molecular weight of 300 to 2,000 daltons and a phosphorus content of 1 to 15 wt %, and a molded sample of the polyetherimide composition has a UL 94 V0 rating at a thickness of 1.5 mm.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of European Patent Application No. 19220229.9, filed December 31, 2019, which is incorporated herein by reference in its entirety. [Background technology]

[0002] Polyetherimides are amorphous, transparent, high-performance polymers with glass transition temperatures (Tg) above 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, telecommunications, aerospace, electrical / electronics, transportation, and healthcare. Due to their widespread use, particularly in electrical and consumer electronics applications, there is a continuing need for polyetherimide compositions that meet a V-0 flammability rating in the Underwriter's Laboratory Bulletin 94, 1.5 mm vertical flame test, "Tests for Flammability of Plastic Materials, UL 94," which is often required for these applications. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2000 / 12604 [Patent Document 2] European Patent Application Publication No. 0325719 [Patent Document 3] U.S. Patent Application Publication No. 2006-281840 Summary of the Invention [Problem to be solved by the invention]

[0004] Polyetherimides are inherently flame retardant. However, certain additives used to tailor other properties of polyetherimides can affect and potentially produce inconsistent results in UL94 flammability tests. Therefore, there is a continuing need for polyetherimide compositions that have a robust UL94 V0-rating at 1.5 mm sample thickness. [Means for solving the problem]

[0005] The polyetherimide composition comprises a polyetherimide and an organophosphorus stabilizer present in an amount effective to provide from greater than 0.01 ppm to less than 20 ppm, preferably from greater than 0.01 ppm to less than 10 ppm, more preferably from greater than 0.01 ppm to less than 4.8 ppm phosphorus, based on the total weight of the polyetherimide composition, the organophosphorus stabilizer having a molecular weight of 300 to 2,000 daltons and a phosphorus content of 1 to 15 wt %, and a molded sample of the polyetherimide composition has a UL94 V0 rating at a thickness of 1.5 mm.

[0006] Also disclosed is a thermoplastic composition comprising the above-described polyetherimide composition.

[0007] The description of the drawings is provided by way of example and is not meant to be limiting. [Brief explanation of the drawings]

[0008] [Figure 1] 1 is a graph showing the storage modulus (Pa·s) of various polyetherimide compositions as a function of temperature, T (° C.). DETAILED DESCRIPTION OF THE INVENTION

[0009] These and other features are illustrated by the following detailed description and examples.

[0010] Detailed Description Heat stabilizers can be added during the production of polyetherimides to improve their melt stability and heat resistance. Heat stabilizers can also help minimize changes in the yellowness index during secondary melt processing operations, such as injection molding and extrusion. However, the inventors have found that higher stabilizer levels, especially when used in low molecular weight polyetherimides, can increase the likelihood of polyetherimide dripping during UL flame testing, potentially leading to inconsistent test results. The inventors have further discovered that when used in amounts greater than zero but less than 100 ppm, organophosphorus stabilizers do not adversely affect the UL-94 V0 performance of polyetherimides. Thus, polyetherimide compositions can be provided that simultaneously have improved melt stability and robust UL-94 V0 performance.

[0011] As used herein, the organophosphorus stabilizer can be an organophosphite, an organophosphonite, an organophosphinite, or a combination comprising at least one of the foregoing. The organophosphorus stabilizer can have a molecular weight of 300 to 2,000 grams / mole (Daltons or Da) or 500 to 1,500 Da, and a phosphorus content of 1 to 12 wt % or 3 to 10 wt %.

[0012] Certain organophosphate stabilizers are represented by formula (1), (2), or (3): [ka] (1) Organic Phosphite [ka] (2), or Organic Phosphonite [ka] (3) Organic phosphinite.

[0013] In chemical formulas (1)-(3), R 1, R 2 , and R 3 each independently represents a substituted or unsubstituted C 1-40 Alkyl, or substituted or unsubstituted C 6-30 aryl, with the optional proviso that R 1 , R 2 , and R 3 provided that at least two of the following are taken together to form a substituted or unsubstituted fused heteroaliphatic ring. Substituents for the alkyl group include N-containing moieties, halogens, substituted or unsubstituted aryls, ether moieties, ester moieties, phosphite-containing moieties, phosphonite-containing moieties, or a combination comprising at least one of the foregoing. Substituents for the aryl group include C 1-40 alkyl, N-containing moiety, halogen, phosphite-containing moiety, phosphonite-containing moiety, or a combination comprising at least one of the foregoing.

[0014] When the organophosphorus stabilizer is an organic phosphite, R 1 , R 2 , and R 3 Each of the 10-30 Aryl, e.g., C 10-30 It can be alkylarylene, preferably R 1 , R 2 , and R 3 Each of the C 12-30 It is an alkylarylene.

[0015] The organophosphorus stabilizer can also be an organophosphite of formula (4): [ka] (4) where R is a substituted or unsubstituted C 6-30 Aryl, preferably substituted C 10-30 It is aryl.

[0016] In one embodiment, the organophosphorus stabilizer is selected from the group consisting of tris(2,4-di-tert-butylphenyl)phosphite (IRGAFOS168), tris-(nonylphenyl)phosphite (TNPP), tetrakis(2,4-di-tert-butylphenyl)[1,1′-biphenyl]-4,4′-diylbis(phosphonite) (PEPQ), bis(2,4-dicumylphenyl)pentaerythritol diphosphite, tris(nonylphenyl)phosphite (DOVERPHOS S-9228), bis(2,4-di-tert-butylphenyl)pentraerythritol diphosphite (ULTRANOX 626), 2,2',2"-nitrilo[triethyl-tris[3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl]]phosphite (IRGAPHOS 12), or a combination comprising at least one of the foregoing, preferably the organophosphorus stabilizer comprises tris(2,4-di-tert-butylphenyl)phosphite.

[0017] The structures of certain organophosphate stabilizers are shown in chemical formulas (5)-(10): [ka] (5) [ka] (6) [ka] (7) [ka] (8) [ka] (9), or [ka] (10).

[0018] Optionally, an organophosphorus stabilizer can be used together with the hindered phenol heat stabilizer. The hindered phenol heat stabilizer can have a molecular weight of greater than 300 Da to less than 2,000 Da. In such embodiments, the molecular weight of the hindered phenol heat stabilizer can help retain the hindered phenol moieties in the polymer melt at high processing temperatures, such as, for example, temperatures of 200°C or higher. The number of hydroxyl groups in the hindered phenol heat stabilizer can be 2 to 6 or 2 to 4 per hindered phenol molecule. In some embodiments, the polyetherimide composition can be free of a hindered phenol heat stabilizer.

[0019] Examples of hindered phenolic heat stabilizers include (oxalylbis(azanediyl))bis(ethane-2,1-diyl)bis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate) (NAUGARDXL-1), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene (IRGANOX1330), and pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) (IRGAN OXF174), N,N'-1,6-hexanediylbis[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropanamide] (IRGANOX1098), 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione (CYANOX1790), 2',3-bis[[3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyl]]proponiohydrazine (IRGANOX MD1024), butylated reaction products of p-cresol and dicyclopentadiene (WINGSTAY L), or a combination comprising at least one of the foregoing.

[0020] The structures of certain hindered phenol heat stabilizers are represented by formulas (11)-(17): [ka] (11), [ka] (12), [ka] (13), [ka] (14), [ka] (15), [ka] (16), or [ka] (17).

[0021] As used herein, polyetherimide or poly(etherimide) refers to a homopolymer or copolymer containing more than one, e.g., from 2 to 1000, or from 5 to 500, or from 10 to 100, structural units of formula (18). [ka] (18) wherein each R is independently the same or different and is a substituted or unsubstituted divalent organic group, such as a substituted or unsubstituted C 6-20 Aromatic hydrocarbon groups, substituted or unsubstituted, straight or branched chain C 4-20 Alkylene group, substituted or unsubstituted C 3-8 and cycloalkylene groups, particularly halogenated derivatives of any of the foregoing. In some embodiments, R is one or more divalent groups of formula (19): [ka] (19) In the formula, Q1 -O-, -S-, -C(O)-, -SO2-, -SO-, -P(R a )(=O)-(wherein, R a is C 1-8 Alkyl or C 6-12 aryl), -C y H 2y - (wherein y is an integer from 1 to 5) or a halogenated derivative thereof (including a perfluoroalkylene group), or -(CH 10 ) z - (wherein z is an integer from 1 to 4). In some embodiments, R is m-phenylene, p-phenylene, or diarylene sulfone, particularly bis(4,4'-phenylene) sulfone, bis(3,4'-phenylene) sulfone, bis(3,3'-phenylene) sulfone, or a combination comprising at least one of the foregoing. In some embodiments, at least 10 mole percent or at least 50 mole percent of the R groups comprise sulfone groups, e.g., particularly bis(4,4'-phenylene) sulfone, bis(3,4'-phenylene) sulfone, bis(3,3'-phenylene) sulfone, and the remainder of the R groups, if present, are m-phenylene or p-phenylene. In some embodiments, none of the R groups comprise a sulfone group. In some embodiments, R is m-phenylene, p-phenylene, or a combination thereof.

[0022] Further, in formula (18), T is -O- or a group of formula -OZO-, where the divalent bond of the -O- or -OZO- group is at the 3,3', 3,4', 4,3', or 4,4' positions of the aromatic ring bearing the imide moiety, and Z is optionally 1 to 6 C 1-8 Aromatic C substituted with alkyl groups, 1 to 8 halogen atoms, or a combination containing at least one of the foregoing 6-24 It may be a monocyclic or polycyclic moiety, provided that the valence of Z does not exceed that of Z. Exemplary Z groups include groups of formula (20): [ka] (20) In the formula, R aand R b are each independently the same or different and are, for example, a halogen atom or a monovalent C 1-6 is an alkyl group, p and q are each independently an integer from 0 to 4, c is from 0 to 4, and X a is a bridging group connecting the hydroxy-substituted aromatic groups, where the bridging group and the hydroxy substituents of each C6 arylene group are positioned ortho, meta, or para (specifically para) to each other on the C6 arylene group. a is a single bond, -O-, -S-, -S(O)-, -S(O)2-, -C(O)-, or C 1-18 It can be an organic bridging group. 1-18 The organic bridging group can be cyclic or acyclic, aromatic or non-aromatic, and can further contain heteroatoms such as halogens, oxygen, nitrogen, sulfur, silicon, or phosphorus. 1-18 The organic group is such that each of the C6 arylene groups connected thereto is C 1-18 They can be arranged to be linked to a common alkylidene carbon or to different carbons of the organic bridging group. An exemplary Z group is a divalent group of formula (20a): [ka] (20a) In the formula, Q is -O-, -S-, -C(O)-, -SO2-, -SO-, -P(R a )(=O)-(wherein, R a is C 1-8 Alkyl or C 6-12 aryl), or -C y H 2y - (wherein y is an integer from 1 to 5) or a halogenated derivative thereof (including a perfluoroalkylene group). In certain embodiments, Z is derived from bisphenol A, such that Q in formula (20a) is 2,2-isopropylidene.

[0023] In one embodiment, in Formula (18), R is m-phenylene, p-phenylene, or a combination comprising at least one of the foregoing; T is -OZO-; and Z is a divalent radical of Formula (20a). Alternatively, R is m-phenylene, p-phenylene, or a combination comprising at least one of the foregoing; T is -OZO; and Z is a divalent radical of Formula (20a); and Q is 2,2-isopropylidene.

[0024] In another embodiment, the poly(etherimide) is a poly(etherimide) sulfone having more than one structural unit of formula (18), e.g., from 2 to 1000, or from 5 to 500, or from 10 to 100, wherein at least 10 mole percent or at least 50 mole percent of the R groups comprise sulfone groups. In one embodiment, at least 10 mole percent or at least 50 mole percent of the R groups comprise sulfone groups, particularly bis(4,4'-phenylene)sulfone, bis(3,4'-phenylene)sulfone, bis(3,3'-phenylene)sulfone, or a combination comprising at least one of the foregoing, and the remainder of the R groups, if present, are m-phenylene or p-phenylene. T is as defined herein, preferably -OZO-, where Z is a divalent radical of formula (20a), e.g., 2,2-(4-phenylene)isopropylidene, i.e., a bisphenol A moiety.

[0025] Poly(etherimides) can be prepared by any of the methods known to those skilled in the art, including the reaction of an aromatic bis(ether anhydride) of formula (21), or its chemical equivalent, with an organic diamine of formula (22). [ka] (twenty one) H2N-R-NH2(22) where T and R are defined as described above. Copolymers of poly(etherimide) can be made using a combination of the aromatic bis(ether anhydride) of formula (21) and an additional bis(anhydride) that is not a bis(ether anhydride), such as pyromellitic dianhydride or bis(3,4-dicarboxyphenyl)sulfone dianhydride. An organophosphorus stabilizer can be added during the process of making the poly(etherimide).

[0026] Illustrative examples of aromatic bis(ether anhydrides) include 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (also known as bisphenol A dianhydride or BPADA), 3,3-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl ether dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)benzophenone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride, 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl ether dianhydride, 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(2,3 -dicarboxyphenoxy)benzophenone dianhydride, 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl sulfone dianhydride, 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl-2,2-propane dianhydride, 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl ether dianhydride, 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl ether dianhydride Examples of aromatic bis(ether anhydrides) include 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)benzophenone dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, and 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride. Combinations of different aromatic bis(ether anhydrides) may be used.

[0027] Examples of organic diamines include 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,12-dodecanediamine, 1,18-octadecanediamine, 3-methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 4-methylnonamethylenediamine, 5-methylnonamethylenediamine, 2,5-dimethylhexamethylenediamine, 2,5-dimethylhept ... Butamethylenediamine, 2,2-dimethylpropylenediamine, N-methyl-bis(3-aminopropyl)amine, 3-methoxyhexamethylenediamine, 1,2-bis(3-aminopropoxy)ethane, bis(3-aminopropyl)sulfide, 1,4-cyclohexanediamine, bis-(4-aminocyclohexyl)methane, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, m-xylylenediamine Amine, p-xylylenediamine, 2-methyl-4,6-diethyl-1,3-phenylene-diamine, 5-methyl-4,6-diethyl-1,3-phenylene-diamine, benzidine, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 1,5-diaminonaphthalene, bis(4-aminophenyl)methane, bis(2-chloro-4-amino-3,5-diethylphenyl)methane, bis(4-aminophenyl)propane, 2,4-bis(p-amino Examples of suitable isomers of the compounds include bis(4-aminophenyl)sulfide, bis(4-aminophenyl)sulfone (also known as 4,4'-diaminodiphenylsulfone (DDS)), and bis(4-aminophenyl)ether. Any positional isomer of the compounds described above may be used. Any of the above C 1-4 Alkylation or poly(C 1-4) Alkylated derivatives, such as polymethylated 1,6-hexanediamine, can be used. Combinations of these compounds can also be used. In some embodiments, the organic diamine is m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, or a combination comprising at least one of the foregoing.

[0028] The poly(etherimide) can have a hydroxyl end group content of less than 1,000 ppm, less than 500 ppm, or less than 100 ppm by weight of the poly(etherimide).

[0029] The poly(etherimide) can have a melt index of 0.5 to 2.3 grams per minute (g / min), as measured by American Society for Testing and Materials (ASTM) D1238 at 337°C using a 6.7 kilogram (kg) weight. Preferably, the poly(etherimide) has a melt index of 1.5 to 2.3 g / min or 1.7 to 2.1 g / min, more preferably 1.7 to 2.0 g / min or 1.8 to 2.0 g / min, as measured by ASTM D1238 at 337°C using a 6.7 kg weight.

[0030] The poly(etherimide) has a weight average molecular weight (Mw) of 1,000 to 50,000 grams per mole (Daltons) as measured by gel permeation chromatography (GC) using polystyrene standards. Preferably, the poly(etherimide) has a Mw of 10,000 to 50,000 Daltons, 40,000 to 50,000 Daltons, or 46,000 to 48,000 Daltons as measured by gel permeation chromatography using polystyrene standards. The poly(etherimide) can be endcapped with an endcapping agent such as phthalic anhydride or aniline.

[0031] Preferably, the poly(etherimide) has a glass transition temperature (Tg) of from 130 to 320° C., preferably from 210 to 320° C., and more preferably from 215 to 312° C., as determined by differential scanning calorimetry (DSC) using a 20° C. / min heating rate per ASTM D3418. Examples of poly(etherimide)s having such glass transition temperatures include the poly(etherimide) sulfones described herein.

[0032] The organophosphorus stabilizer can be present in an amount effective to provide from greater than 0.01 ppm to less than 20 ppm, preferably from greater than 0.01 ppm to less than 10 ppm, and more preferably from greater than 0.01 ppm to less than 4.8 ppm of phosphorus, based on the total weight of the polyetherimide composition. In one embodiment, the organophosphorus stabilizer is present in an amount effective to provide from greater than 0.04 ppm to less than 20 ppm, preferably from greater than 0.04 ppm to less than 10 ppm, and more preferably from greater than 0.04 ppm to less than 4.8 ppm of phosphorus, based on the total weight of the polyetherimide composition. The amount of stabilizer is determined by gas chromatography (GC) or high-performance liquid chromatography (HPLC), depending on the particular organophosphorus stabilizer used. When the stabilizer is tris(2,4-di-tert-butylphenyl) phosphite, gas chromatography is used to determine the amount of stabilizer. Because the stabilizer may be decomposed, evaporated, or otherwise consumed during the process of making the polyetherimide composition, the initial amount of organophosphorus compound used to make the polyetherimide composition may be greater than 100 ppm, for example, 200 to 5000 ppm.

[0033] When the organophosphorus stabilizer is tris(2,4-di-tert-butylphenyl)phosphite, the polyetherimide composition may have a phosphorus content, by weight, based on the total weight of the polyetherimide composition, of greater than 0.01 ppm to less than 4.8 ppm, or greater than 0.04 ppm to less than 4.8 ppm. For other organophosphorus stabilizers, the phosphorus content may be less than 20 ppm, less than 10 ppm, or less than 4.8 ppm, but greater than 0.01 ppm or greater than 0.04 ppm, based on the total weight of the polyetherimide composition.

[0034] The polyetherimide can be present in an amount greater than 98 wt%, preferably greater than 99 wt%, based on the total weight of the polyetherimide composition. In addition to the organophosphorus stabilizer and optional hindered phenol stabilizer, the polyetherimide composition can also contain additives such as mold release agents. The polyetherimide composition can be free of other thermoplastic polymers. For example, the polyetherimide composition can be free of thermoplastic polymers such as polyester, polycarbonate, or both.

[0035] The polyetherimide composition can be essentially free of certain metals or metal ions. In one embodiment, the polyetherimide composition contains less than 20 ppm or less than 10 ppm by weight of each of the following metals or ions: Na, Fe, Co, Ni, Mo, Ca, and Mg. The polyetherimide composition can also contain less than 20 ppm or less than 10 ppm by weight of transition metals or ions thereof, such as Cr, Mn, Ti, and Zn.

[0036] The polyetherimide composition has good flame retardancy. Molded samples of the polyetherimide composition have a UL94 V0 rating at a thickness of 1.5 mm. Additionally, molded samples of the composition can have a first-time pass probability of at least 0.9 in a UL94 V0 test at a thickness of 1.5 mm, and preferably, molded samples of the composition have a first-time pass probability of at least 0.95 in a UL94 V0 test at a thickness of 1.5 mm.

[0037] The polyetherimide compositions can be thermally stabilized and have excellent resistance to thermal degradation.

[0038] The polyetherimide composition may have a yellowness index of less than 100, less than 90, or less than 80 as measured according to ASTM D1925 using 3.2 mm thick injection molded specimens / parts.

[0039] The polyetherimide composition has a storage modulus of 65 Pa or greater, eg, 65 to 200 Pa, as determined on extruded pellets of the polyetherimide composition according to ASTM D4440-15 at 23°C.

[0040] The polyetherimide composition can be in the form of pellets or powder (fines).

[0041] Polyetherimide compositions can be formulated with various additives to provide thermoplastic compositions, provided that the additives are selected so as not to significantly adversely affect the desired properties of the composition. Exemplary additives include catalysts, impact modifiers, fillers, antioxidants, light stabilizers, ultraviolet (UV) absorbing additives, quenchers, plasticizers, lubricants, mold release agents, antistatic agents, visual effect additives such as dyes, pigments, and lighting effect additives, flame retardants, drip repellents, and radiation stabilizers. The additives (other than any fillers) are generally present in an amount of 0.005 to 20 wt %, specifically 0.01 to 10 wt %, based on the total weight of the thermoplastic composition.

[0042] In some embodiments, the thermoplastic composition can further comprise at least one additional polymer. Examples of such additional polymers include PPSU (polyphenylene sulfone), polyetherimide, PSU (polysulfone), PPE (polyphenylene ether), PFA (perfluoroalkoxyalkane), MFA (copolymer of tetrafluoroethylene TFE and perfluorinated vinyl ether PFVE), FEP (fluorinated ethylene propylene polymer), PPS (poly(phenylene sulfide), PTFE (polytetrafluoroethylene), PA (polyamide), PBI (polybenzimidizole), PAI (poly(amide-imide)), poly(ether sulfone), ), poly(arylsulfones), polyphenylenes, polybenzoxazoles, polybenzthiazoles, and blends and copolymers thereof. When present, the polymers are used in amounts of greater than 0 to 20 wt %, specifically 0.1 to 15 wt %, and more specifically 0.5 to 10 wt %, all based on the total weight of the polyetherimide composition. In some embodiments, no polymers other than the polyetherimides described herein are present in the thermoplastic composition. In some embodiments, no polyesters or polycarbonates are present in the polyetherimide composition.

[0043] Polyetherimides and thermoplastic compositions can be formed into articles by several methods, such as shaping, extrusion (including profile extrusion), thermoforming, and molding, such as injection molding, compression molding, gas-assisted molding, structural foam molding, and blow molding. In some embodiments, a method of forming an article includes shaping, extruding, blow molding, or injection molding the polyetherimide or thermoplastic composition to form the article. Polyetherimides and thermoplastic compositions can also be formed into articles using thermoplastic processes, such as film extrusion, sheet extrusion, melt casting, blown film extrusion, and calendering. Coextrusion and lamination processes can be used to form composite multilayer films or sheets. The article can be a sheet, film, multilayer sheet, multilayer film, molded part, extruded profile, coated part, pellet, powder, foam, fiber, fibrid, flake fiber, or a combination comprising at least one of the foregoing.

[0044] These and other features are illustrated by the following examples, in which, unless otherwise specified, the percentages (%) of ingredients are weight percents based on the total weight of the composition. [Example]

[0045] material Various batches of polyetherimide were prepared by polymerizing 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride and meta-phenylenediamine using phthalic anhydride or aniline as end-capping agents. An organophosphorus stabilizer, i.e., tris(2,4-di-tert-butylphenyl)phosphite, was added during the polyetherimide preparation process.

[0046] Sample Exam Melt index was measured according to ASTM D1238 at 337°C using a 6.7 kilogram (kg) weight.

[0047] Yellowness Index (YI) was measured according to ASTM D1925 using 3.2 mm thick injection molded specimens / parts.

[0048] The amount of stabilizer in the samples was determined by gas chromatography.

[0049] The storage modulus was determined using a dynamic oscillatory temperature sweep method (melt rheology). Experiments were performed using an ARES strain-controlled rheometer. The temperature sweep method was used to determine the viscosity or modulus of the material as a function of temperature. The temperature was varied from 300 to 480°C using a heating rate of 10°C / min.

[0050] Storage modulus was determined according to ISO 6721-10 and ASTM D4440-01. Dynamic mechanical analysis (melt rheology) was performed on pellets or injection molded specimens / parts.

[0051] The storage modulus of polyetherimide initially decreases as a function of temperature, and once the transition temperature (the temperature at which thermal decomposition and crosslinking begin) is reached, the storage modulus increases significantly. The onset temperature of the storage modulus change, T onset was obtained by carrying out a temperature sweep of 10°C / min in an air atmosphere in a rheometer.

[0052] Flammability testing was performed according to the procedures in Underwriters Laboratory Bulletin 94 (ISBN 0-7629-0082-2), 5th Edition, October 29, 1996 (incorporating revisions through December 12, 2003), entitled "Tests for Flammability of Plastic Materials for Parts in Devices and Appliances." Several ratings are applicable based on burn rate, extinguishment time, ability to resist dripping, and whether dripping is observed or the cotton ignites. According to this procedure, materials can be classified as UL94HB, V0, V1, V2, 5VA, or 5VB at a given sample thickness. Specimens were aged for 48 hours at 23°C and 50% RH before testing.

[0053] Data was collected from many samples (typically 20 bars) and then analyzed by calculating the mean flame out time (FOT), standard deviation of flame out time, and total number of drips (# drips), and using statistical methods to convert the data into a first-time pass probability, or "p(FTP)," that a particular sample formulation will achieve a "pass" rating in the five-bar conventional UL94 V0 test. P(FTP) is as close to 1 as possible, e.g., greater than 0.9, and more preferably greater than 0.95, for maximum flame retardant performance in the UL test. A 90% probability of first-time pass (i.e., a p(FTP) of 0.9) is considered acceptable performance. Values ​​significantly below 0.9 are considered unacceptable.

[0054] Examples 1-15 Exemplary polyetherimide compositions of the present disclosure (Ex1 through Ex11), along with control or comparative compositions (CEx12 through CEx15), were tested for melt flow index, yellowness index, stabilizer content, storage modulus, onset temperature (the temperature at which modulus increases due to crosslinking and a concomitant increase in Mw of the polyetherimide polymer), and flame retardancy. The results are shown in Table 1. The compositions comprise tris(2,4-di-tert-butylphenyl) phosphite (stabilizer) in the amounts shown in Table 1, and a phthalic anhydride end-capped polyetherimide having a weight average molecular weight of 46,000 to 48,000 daltons as determined by GPC using polystyrene standards.

[0055] [Table 1]

[0056] The data show the effect of the amount of organophosphorus stabilizer on the flame retardant performance of polyetherimide compositions. When the amount of organophosphorus stabilizer is less than 100 ppm, the polyetherimide compositions (Ex1-Ex12) all have a first-time pass probability of at least 0.9 for UL 94 V0 testing at a sample thickness of 1.5 mm. In contrast, when the amount of organophosphorus stabilizer is greater than 100 ppm, the polyetherimide compositions (CEx13-CEx15) have a first-time pass probability of less than 0.6.

[0057] When exposed to a flame during the UL-94 V0 flame test, the flame heats the bar above the glass transition temperature (Tg) of the material, causing the material to melt, elongate, and ultimately drip. Without wishing to be bound by theory, it is believed that the probability of dripping is reduced if the polyetherimide has a shear viscosity or melt strength greater than zero, or if the polyetherimide undergoes pyrolytic crosslinking.

[0058] A faster onset temperature indicates that the polyetherimide is less thermally stable and therefore more likely to crosslink at a lower temperature, thereby reducing the probability of dripping. As shown in Table 1, compositions with a pFTP >0.95 have onset temperatures of 405°C or less, and compositions with a pFTP <0.9 have onset temperatures of 410°C or more.

[0059] The storage modulus, measured by a dynamic oscillatory temperature sweep method at a specific temperature, e.g., 150° above the glass transition temperature, correlates with the flame retardant performance of the composition. As shown in Table 1, the storage modulus of the compositions of the present disclosure is 65 Pa or greater, while the storage modulus of the comparative compositions is 56 Pa or less. Thus, the onset temperature and the storage modulus at a specific temperature, e.g., 425°C, can be used as screening tools to predict the flame retardant performance of polyetherimide compositions.

[0060] Examples 16-19 Temperature sweep studies were performed on polyetherimides end-capped with phthalic anhydride or aniline and stabilized with or without 110 to 140 ppm tris(2,4-di-tert-butylphenyl) phosphite. The temperature sweep curves are shown in Figure 1. As can be seen, there are no major differences in the rheological / dripping behavior of polyetherimides with different end groups.

[0061] Comparative Examples 20 and 21 Various polyetherimides with weight-average molecular weights ranging from 53,000 to 56,000 daltons, as determined by gel permeation chromatography using polystyrene standards, were prepared by polymerizing 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride and meta-phenylenediamine using phthalic anhydride or aniline as end-capping agents. An organophosphorus stabilizer, i.e., tris(2,4-di-tert-butylphenyl)phosphite, was added during the polyetherimide manufacturing process. One set of compositions contained stabilizer in an amount greater than 0 to less than 100 ppm, while another set contained stabilizer in an amount greater than 100 ppm but less than 200 ppm. The flame retardancy of the compositions was evaluated. The results show that, regardless of the amount of stabilizer used, the compositions reliably passed the UL 94 V0 rating with a sample thickness of 1.5 mm. In other words, the results suggest that when the weight average molecular weight of the polyetherimide, as measured by GPC using polystyrene standards, exceeds 50,000 daltons, the amount of organophosphorus stabilizer no longer affects the flame retardant performance of the polyetherimide.

[0062] Various aspects of the disclosure are set forth below.

[0063] Embodiment 1. A polyetherimide composition comprising: a polyetherimide; and an organophosphorus stabilizer present in an amount effective to provide from greater than 0.01 ppm to less than 20 ppm, preferably from greater than 0.01 ppm to less than 10 ppm, and more preferably from greater than 0.01 ppm to less than 4.8 ppm, of phosphorus, based on the total weight of the polyetherimide composition, wherein the organophosphorus stabilizer has a molecular weight of 300 to 2,000 daltons and a phosphorus content of 1 to 15 wt %, and wherein a molded sample of the polyetherimide composition has a UL 94 V0 rating at a thickness of 1.5 mm.

[0064] Embodiment 2. The polyetherimide composition of embodiment 1, wherein a molded sample of the polyetherimide composition has a first-time probability of passing a UL94 V0 test at a thickness of 1.5 mm of at least 0.9, and preferably a molded sample of the polyetherimide composition has a first-time probability of passing a UL94 V0 test at a thickness of 1.5 mm of at least 0.95.

[0065] Embodiment 3. The polyetherimide composition of any one or more of embodiments 1-2, wherein the organophosphorus stabilizer is present in an amount effective to provide from greater than 0.04 ppm to less than 20 ppm, preferably from greater than 0.04 ppm to less than 10 ppm, and more preferably from greater than 0.04 ppm to less than 4.8 ppm, of phosphorus, based on the total weight of the polyetherimide composition.

[0066] Aspect 4. The organophosphorus stabilizer has the formula [ka] , [ka] ,or [ka] , and In the formula, R 1 , R 2 , and R 3 each independently represents a substituted or unsubstituted C 1-40 Alkyl, or substituted or unsubstituted C 6-30 aryl, with the optional proviso that R 1 , R 2 , and R 3 The polyetherimide composition of any one of embodiments 1 through 3, provided that at least two of:

[0067] Embodiment 5. The polyetherimide composition of any one or more of Embodiments 1 through 4, wherein the organophosphorus stabilizer comprises tris(2,4-di-tert-butylphenyl)phosphite, tris-(nonylphenyl)phosphite, tetrakis(2,4-di-tert-butylphenyl)[1,1'-biphenyl]-4,4'-diylbis(phosphonite), bis(2,4-dicumylphenyl)pentaerythritol diphosphite, tris(nonylphenyl)phosphite, bis(2,4-di-tert-butylphenyl)pentraerythritol diphosphite, 2,2',2"-nitrilo[triethyl-tris[3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl]]phosphite, or a combination comprising at least one of the foregoing; preferably, the organophosphorus stabilizer comprises tris(2,4-di-tert-butylphenyl).

[0068] Embodiment 6. The polyetherimide composition of any one or more of embodiments 1 through 5, wherein the polyetherimide has a weight average molecular weight of from 1,000 to 50,000 daltons, preferably from 40,000 to 50,000 daltons, and more preferably from 46,000 to 48,000 daltons, as measured by gel permeation chromatography using polystyrene standards.

[0069] Embodiment 7. The polyetherimide composition of any one or more of embodiments 1 through 6, wherein the polyetherimide has a melt index of 0.5 to 2.3 grams per minute, preferably 1.5 to 2.3 grams per minute, as measured by ASTM D1238 at 337°C using a 6.7 kilogram weight.

[0070] Embodiment 8. The poly(etherimide) comprises structural units of the formula: [ka] wherein each R is independently a substituted or unsubstituted divalent organic group, and T is -O- or a group of formula -OZO-, where the divalent bonds of the -O- or -OZO- group are in the 3,3', 3,4', 4,3', or 4,4' positions, and Z is optionally 1 to 6 C 1-8 Aromatic C substituted with alkyl groups, 1 to 8 halogen atoms, or a combination containing at least one of the foregoing 6-24 The polyetherimide composition of any one or more of embodiments 1 through 7, wherein the moiety is a single ring or a multiple ring.

[0071] Aspect 9. R is one or more divalent groups of the formula [ka] In the formula, Q 1 -O-, -S-, -C(O)-, -SO2-, -SO-, -P(R a )(=O)-(wherein, R a is C 1-8 Alkyl or C 6-12 aryl), -C y H 2y - (wherein y is an integer from 1 to 5) or a halogenated derivative thereof, or -(CH 10 ) z wherein z is an integer from 1 to 4, preferably m-phenylene, p-phenylene, or diarylene sulfone; and Z is 2,2-(4-phenylene)isopropylidene.

[0072] Embodiment 10. The polyetherimide composition of any one or more of embodiments 1 through 9, wherein the polyetherimide has a hydroxyl end group content of less than 1,000 ppm, preferably less than 500 ppm, and more preferably less than 100 ppm.

[0073] Embodiment 11. The polyetherimide composition of any one or more of embodiments 1 through 10, further comprising a hindered phenol heat stabilizer having a molecular weight of 400 to 2,000 daltons.

[0074] Embodiment 12. The polyetherimide composition of any one or more of embodiments 1 through 11, wherein the polyetherimide is present in an amount greater than 98 wt.% or greater than 99 wt.%, based on the total weight of the composition.

[0075] Embodiment 13. The polyetherimide is present in an amount greater than 98 wt%, preferably greater than 99 wt%, based on the total weight of the composition, and comprises structural units of the formula: [ka] , wherein R is m-phenylene, T is an OZO- group, Z is 2,2-(4-phenylene)isopropylidene, the polyetherimide is end-capped with phthalic anhydride or aniline and has a weight average molecular weight of 40,000 to 50,000 daltons as determined by gel permeation chromatography using polystyrene standards, and the organophosphorus stabilizer is tris(2,4-di-tert-butylphenyl)phosphite, tetrakis(2,4-di-tert-butylphenyl)[1,1'- 13. The polyetherimide composition of any one or more of embodiments 1 through 12, wherein the organophosphorus stabilizer comprises tris(2,4-di-tert-butylphenyl)phosphite, bis(2,4-di-tert-butylphenyl)-4,4′-diylbis(phosphonite), bis(2,4-dicumylphenyl)pentaerythritol diphosphite, tris(nonylphenyl)phosphite, or a combination thereof, and preferably the organophosphorus stabilizer comprises tris(2,4-di-tert-butylphenyl)phosphite, and is present in an amount effective to provide greater than 0.04 ppm to less than 4.8 ppm phosphorus, based on the total weight of the polyetherimide composition.

[0076] Embodiment 14. The polyetherimide composition of any one or more of embodiments 1 through 13, wherein no polyester or polycarbonate is present in the polyetherimide composition.

[0077] Embodiment 15. The polyetherimide composition of any one or more of Embodiments 1 through 14, wherein the composition does not contain a hindered phenol heat stabilizer.

[0078] Embodiment 16. A thermoplastic composition comprising the polyetherimide composition of any one or more of Embodiments 1 through 15.

[0079] Embodiment 17. An article comprising the polyetherimide composition of any one or more of embodiments 1 through 15 or the thermoplastic composition of embodiment 16.

[0080] Compounds are described using standard nomenclature. For example, any position not substituted by any indicated group is understood to have its valence filled by the indicated bond or hydrogen atom. A dash ("-") that is not between two letters or symbols is used to indicate the point of attachment for a substituent. For example, -CHO is attached through the carbon of a carbonyl group.

[0081] As used herein, the terms "hydrocarbyl" and "hydrocarbon" broadly refer to substituents containing carbon and hydrogen, optionally together with one to three heteroatoms, such as oxygen, nitrogen, halogen, silicon, sulfur, or combinations thereof; "alkyl" refers to a straight or branched chain, saturated monovalent hydrocarbon radical; "alkylene" refers to a straight or branched chain, saturated, divalent hydrocarbon radical; "aryl" refers to an aromatic monovalent radical containing only carbon in one or more aromatic rings; "arylene" refers to an aromatic divalent radical containing only carbon in one or more aromatic rings; "alkylarylene" refers to an aryl group substituted with an alkyl group as defined above; 4-methylphenyl is an exemplary alkylarylene group; "arylalkylene" refers to an alkyl group substituted with an aryl group as defined above; and benzyl is an exemplary arylalkylene group.

[0082] Unless otherwise specified, each of the foregoing groups can be unsubstituted or substituted, provided that the substitution does not significantly adversely affect the synthesis, stability, or use of the compound. As used herein, the term "substituted" means that at least one hydrogen on the specified atom or group has been replaced with another group, provided that the standard valence of the specified atom is not exceeded. When a substituent is oxo (i.e., =0), two hydrogens on that atom are replaced. Combinations of substituents and / or variables are permissible, provided that the substitution does not significantly adversely affect the synthesis or use of the compound. Groups that can be present in a substituted position include (-NO2), cyano (-CN), halogen, thiocyano (-SCN), C 2-6 Alkanoyl (e.g., acyl (H3CC(=O)-), carboxamido, C 1-6 Or C 1-3 Alkyl, cycloalkyl, alkenyl, and alkynyl, C 1-6 Or C 1-3 Alkoxy, C 6-10 Aryloxy, e.g., phenoxy, C 1-6 Alkylthio, C 1-6 Or C 1-3 Alkylsulfinyl, C 1-6 Or C 1-3 Alkylsulfonyl, C with at least one aromatic ring 6-12 Aryl (e.g., phenyl, biphenyl, naphthyl, etc., where each ring is substituted or unsubstituted aromatic), C having 1 to 3 separate or fused rings and 6 to 18 ring carbon atoms 7-19 Included are arylalkylene or arylalkoxy having from 1 to 3 separate or fused rings and from 6 to 18 ring carbon atoms. The stated number of carbon atoms includes any optional substituents.

[0083] All references cited herein are incorporated by reference in their entirety. While exemplary embodiments have been set forth for illustrative purposes, the foregoing description should not be deemed to limit the scope of the present specification. Accordingly, various modifications, adaptations, and alternatives may occur to those skilled in the art without departing from the spirit and scope of the present specification. The use of the word "comprises" allows for the inclusion of other components, but also describes situations where no other components are present, or where the composition consists essentially of or consists of the listed components.

Claims

1. 1. A polyetherimide composition comprising: Polyetherimide, an organophosphorus stabilizer present in an amount effective to provide greater than 0.01 ppm to less than 4.8 ppm phosphorus, based on the total weight of the polyetherimide composition, from 1 ppm to 82 ppm, said organophosphorus stabilizer having a molecular weight of 300 to 2,000 daltons and a phosphorus content of 1 to 15 wt %, Including, the organophosphorus stabilizer comprises tris(2,4-di-tert-butylphenyl)phosphite; A polyetherimide composition, wherein a molded sample of said polyetherimide composition has a UL 94 V0 rating at a thickness of 1.5 mm.

2. 10. The polyetherimide composition of claim 1, wherein a molded sample of the polyetherimide composition has a first-time pass probability of a UL94 V0 test of at least 0.9 at a thickness of 1.5 mm.

3. 3. The polyetherimide composition of claim 1, wherein the organophosphorus stabilizer is present in an amount effective to provide greater than 0.04 ppm to less than 4.8 ppm phosphorus, based on the total weight of the polyetherimide composition.

4. 4. The polyetherimide composition of claim 1, wherein the polyetherimide has a weight average molecular weight of from 1,000 to 50,000 daltons as measured by gel permeation chromatography using polystyrene standards.

5. 5. The polyetherimide composition of claim 1, wherein the polyetherimide has a melt index of 0.5 to 2.3 grams per minute as measured by ASTM D1238 at 337°C using a 6.7 kilogram weight.

6. The polyetherimide comprises structural units of the formula: 【Chemistry 1】 During the ceremony, each R is independently a substituted or unsubstituted divalent organic group; and T is -O- or a group of formula -O-Z-O-, wherein the divalent bonds of said -O- or said -O-Z-O- group are in the 3,3', 3,4', 4,3', or 4,4' positions, and Z is optionally 1 to 6 C １－８ an aromatic C substituted with an alkyl group, 1 to 8 halogen atoms, or a combination comprising at least one of the foregoing; ６－２４ 6. The polyetherimide composition of claim 1, wherein the moiety is a monocyclic or polycyclic moiety.

7. R is one or more divalent groups of the following chemical formula: 【Chemistry 2】 During the ceremony, Q １ -O-, -S-, -C(O)-, -SO ２ -, -SO-, -P(R ａ )(=O)-(wherein, R ａ is C １－８ Alkyl or C ６－１２ aryl), —C ｙ H ２ｙ -(wherein y is an integer from 1 to 5) or a halogenated derivative thereof, or -(C ６ H １０ ) ｚ where z is an integer from 1 to 4, preferably m-phenylene, p-phenylene, or diarylylene sulfone; and The polyetherimide composition of any one or more of claims 1 to 6, wherein Z is 2,2-(4-phenylene)isopropylidene.

8. 8. The polyetherimide composition of claim 1, wherein the polyetherimide has a hydroxyl end group content of less than 1,000 ppm.

9. 9. The polyetherimide composition of claim 1, further comprising a hindered phenol heat stabilizer having a molecular weight of 400 to 2,000 daltons.

10. 10. The polyetherimide composition of claim 1, wherein the polyetherimide is present in an amount greater than 98 wt. % or greater than 99 wt. %, based on the total weight of the composition.

11. The polyetherimide is present in an amount greater than 98 wt %, preferably greater than 99 wt %, based on the total weight of the composition, and comprises structural units of the formula: 【Transformation 3】 、 During the ceremony, R is m-phenylene, T is an O-Z-O- group, and Z is 2,2-(4-phenylene)isopropylidene; the polyetherimide is end-capped with phthalic anhydride or aniline and has a weight average molecular weight of 40,000 to 50,000 daltons as determined by gel permeation chromatography using polystyrene standards; and 11. The polyetherimide composition of claim 1, wherein the organophosphorus stabilizer further comprises tetrakis(2,4-di-tert-butylphenyl)[1,1′-biphenyl]-4,4′-diylbis(phosphonite), bis(2,4-dicumylphenyl)pentaerythritol diphosphite, tris(nonylphenyl)phosphite, or a combination thereof.

12. 12. The polyetherimide composition of claim 1, wherein no polyester or polycarbonate is present in the polyetherimide composition.

13. 13. The polyetherimide composition of claim 1, wherein the composition is free of a hindered phenol heat stabilizer.

14. A thermoplastic composition comprising the polyetherimide composition of any one or more of claims 1 to 13.

15. 15. An article comprising the polyetherimide composition of any one or more of claims 1 to 13 or the thermoplastic composition of claim 14.

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