Flame retardant thermoplastic compositions

Abstract

A thermoplastic composition comprising: a polyester,; a flame retardant composition comprising a non-fluorinated flame retardant, optionally, an auxiliary flame retardant, and optionally, an anti-drip agent; greater than or equal to 5 wt% of a polyetherimide; a reinforcing agent; optionally, an additive composition; and wherein the sum of the wt% of the polyester, the flame retardant composition, the polyetherimide, the reinforcing agent, and the optional additive composition total 100 wt%, wherein a sample of the composition exhibits a UL-94 rating of V-0 at a thickness of 0.8 mm, or 0.6 mm, more preferably wherein a sample of the composition exhibits a UL-94 rating of V-0 at a thickness of 0.4 mm, and wherein the thermoplastic composition is essentially fluorine-free.

Description

23SHPP0037-WO-PCT (SS180005PCT) FLAME RETARDANT THERMOPLASTIC COMPOSITIONS CROSS-REFERENCE TO RELATED APPLICATIONS This application is based on European Patent Application No.24156298.2, filed February 7, 2025, and claims the benefits thereof under 35 U.S.C.119, and incorporates the entire contents thereof by reference. BACKGROUND

[0001] This disclosure relates to thermoplastic compositions, and in particular to flame- retardant thermoplastic compositions, methods of manufacture, and uses thereof in thin-wall articles.

[0002] Thermoplastic compositions, such as those including poly(alkylene terephthalates), have valuable characteristics including strength, toughness, high gloss, and solvent resistance. The thermoplastic compositions therefore have utility as materials for a wide range of applications, from automotive parts to electric and electronic appliances. Because of their wide use, particularly in electronic applications, it is desirable for the thermoplastic compositions to have flame retardancy. Such properties may be particularly difficult to achieve in thin-wall applications. In addition, more stringent regulations are being put in place to reduce or eliminate the presence of halogens, in particular fluorine, in the final products.

[0003] There accordingly remains a need in the art for flame-retardant thermoplastic compositions suitable for thin-wall applications. It would be a further advantage if the compositions were essentially fluorine-free. SUMMARY

[0004] The above-described and other deficiencies of the art are met by a thermoplastic composition including: a polyester; a flame retardant composition comprising a non-fluorinated flame retardant, optionally, an auxiliary flame retardant, and optionally, an anti-drip agent; greater than or equal to 5 wt% of a polyetherimide; a reinforcing agent; and optionally, an additive composition; wherein the sum of the wt% of the polyester, the flame retardant composition, the polyetherimide, the reinforcing agent, and the optional additive composition total 100 wt%, wherein a sample of the composition exhibits a UL-94 rating of V-0 at a thickness of 0.4 mm, and wherein the thermoplastic composition is essentially fluorine-free.

[0005] In another aspect, a method of manufacture comprises combining the above- described components to form a thermoplastic composition.23SHPP0037-WO-PCT (SS180005PCT)

[0006] In yet another aspect, an article comprises the above-described thermoplastic composition.

[0007] In still another aspect, a method of manufacture of an article comprises molding, extruding, or shaping the above-described thermoplastic composition into an article.

[0008] The above described and other features are exemplified by the following detailed description, examples, and claims. DETAILED DESCRIPTION

[0009] Polyesters are thermoplastic polymers with many desirable properties but are inherently flammable. Current design trends are focused on thinner designs for purposes of slimness, weight reduction, and size reduction of the overall final product, as well as to for the purpose of more complex designs. However, polyesters tend to drip when exposed to a flame, and this behavior worsens as the wall thickness decreases. The UL 94 flammability test includes both short flame out times and no dripping of flaming particles as requirements for a V-0 or V-1 flame test rating. Conventional low halogen compositions often incorporate fluorine-based anti- drip agents either alone or in combination with a non-fluorinated flame retardant in order to pass the UL94 flame test. Given that more stringent regulations are being put in place to reduce or eliminate the addition of halogenated materials, for example, perfluoroalkyl and polyfluoroalkyl substances (PFAS), to the compositions used to make final products, there is a need in the art for thermoplastic compositions that may achieve a V-0 or V-1 flame test rating for thin-walled molded samples and / or thin films, while also minimizing and / or eliminating the addition of PFAS into the thermoplastic compositions used to make the molded samples and / or thin films.

[0010] The inventors hereof have discovered that reinforced, e.g., glass-filled, thermoplastic compositions including a polyester including a poly(alkylene arylate), a polyetherimide, and a flame retardant composition including a non-fluorinated flame retardant, optionally, an auxiliary flame retardant, and optionally, an anti-drip agent may provide improved flame retardance while eliminating the need for halogenated additives, such as fluorinated flame retardants and anti-drip agents. Surprisingly, unlike conventional compositions, fluorinated anti- drip agents may be omitted in the present thermoplastic compositions, thus eliminating added fluorine while providing improved flammability. Advantageously, the thermoplastic compositions may have a UL-94 flame test rating of V-0 at a thickness of 3.0 mm or thinner (i.e., 2.5 mm, 2.0 mm, 1.5 mm, 1.2 mm, 1.0 mm, 0.8 mm, 0.6 mm, or 0.4 mm) and be considered “essentially fluorine-free” as described in more detail below.23SHPP0037-WO-PCT (SS180005PCT)

[0011] As used herein, the phrase “essentially fluorine-free” can mean that the amount of calculated intentionally added fluorine (i.e., the amount of fluorine known to be present in the components used to manufacture the thermoplastic compositions) is 1500 parts per million by weight (ppm) or less, less than 1000 ppm, less than 500 ppm, less than 100 ppm, or less than 50 ppm. For example, if 0.5 wt% encapsulated polytetrafluoroethylene, (e.g., TSAN, which is 50 wt% PTFE, where PTFE estimated to have 76 wt% fluorine content), is added to a composition, the amount of calculated intentionally added fluorine due to the TSAN would be 1900 ppm. In some aspects, the thermoplastic compositions have zero added fluorine, i.e., no component used in the manufacture of the compositions includes fluorine. An amount of added fluorine (e.g., calculate intentionally added fluorine) can be calculated from the amount of fluorine in the components used to manufacture the compositions or can be determined using known elemental analysis techniques.

[0012] As used herein, the phrase “essentially fluorine-free” can further mean that the amount of fluorine present in the composition from any source (e.g., present in a component used to manufacture the thermoplastic composition, or introduced by contamination, for example cross-contamination during manufacture), is 1500 ppm or less, less than 1000 ppm, less than 500 ppm, less than 100 ppm, or less than 50 ppm or less than 20 ppm. It is to be understood that the present lowest detection limits of fluorine as determined in accordance with ASTM D7359-23 in the compositions is 20 ppm (20 mg / kg). Thus, the amount fluorine (from any source) present in the composition is bounded by this detection limit, and may be less than 20 ppm, such that the amount of fluorine in the compositions can be less than 20 ppm to 1500 ppm, less than 20 ppm to 1200 ppm, less than 20 ppm to 1000 ppm, less than 20 ppm to 500 ppm, less than 20 ppm to -400 ppm, less than 20 ppm to 380 ppm, less than 20 ppm to 300 ppm, less than 20 ppm to 200 ppm, less than 20 ppm to 100 ppm, less than 20 ppm to 50 ppm, or less than 20 ppm, each as determined in accordance with ASTM D7359-23.

[0013] In some aspects, the thermoplastic compositions may have a UL-94 flame test rating of V-0 at a thickness of 3.0 mm or thinner (i.e., 2.5 mm, 2.0 mm, 1.5 mm, 1.2 mm, 1.0 mm, 0.8 mm, 0.6 mm, or 0.4 mm) and be considered “essentially halogen-free” as defined by the International Electrochemical Commission, Restriction Use of Halogen standard IEC 61249- 2-21, or by the Underwriters Laboratories standard UL 746H. According to, IEC 61249-2-21, an “essentially halogen-free” composition includes 900 parts per million by weight (ppm) or less of each of chlorine and bromine and also include 1500 ppm or less of total bromine, chlorine, and fluorine content. According to UL 746H, an “essentially halogen-free” compositions includes 900 ppm or less of each of chlorine, bromine, and fluorine, and 1500 ppm or less of the total23SHPP0037-WO-PCT (SS180005PCT) chlorine, bromine, and fluorine. Each of the added (i.e., intentionally added) bromine, chlorine, and fluorine content may be calculated from the known bromine, chlorine, and fluorine content of the components used to manufacture the thermoplastic compositions or measured by known elemental analysis techniques. Alternatively, the bromine, chlorine, and fluorine content from any source may be measured using known elemental analysis techniques.

[0014] Conventional flame retardants may include or exclude halogens, but commonly used anti-drip agents include PTFE or PTFE-encapsulated styrene-acrylonitrile copolymers (e.g., TSAN) and thus include fluorine. Non-fluorinated flame retardants that are not brominated, chlorinated, or fluorinated have been used in conventional thermoplastic compositions, but an anti-drip agent is usually present in combination with the non-fluorinated flame retardant, causing the halogen content of the composition to exceed the 1500 ppm total halogen limit per IEC 61249-2-21 and UL 746H. Similarly, when flame retardants that are not brominated or chlorinated, but are fluorinated are used in combination with a fluorinated anti- drip agent, then the halogen content of the composition due to the presence of fluorine exceeds the 1500 ppm total halogen limit per IEC 61249-2-21 or UL 746H. Therefore, it would be a particular advantage if conventional anti-drip agents could be minimized or eliminated, so that the anti-drip agent does not contribute halogen content to the total halogen content of the compositions. Accordingly, a variety of non-fluorinated flame retardants that include or exclude halogens may be used in thermoplastic compositions so that the compositions may be considered “essentially halogen-free” per IEC 61249-2-21 or UL 746H.

[0015] The thermoplastic compositions include a polyester including a poly(alkylene arylate), a polyetherimide, a flame retardant composition including a non-fluorinated flame retardant, optionally, an auxiliary flame retardant, and optionally, an anti-drip agent, and a reinforcing agent.

[0016] The polyesters of the thermoplastic compositions may include aromatic polyesters, poly(alkylene esters) including poly(alkylene arylates), and poly(cycloalkylene diesters). Aromatic polyesters may have a polyester structure according to formula (7)wherein J is a divalent group derived from a dihydroxy compound (including a reactive derivative thereof), and J may be, for example, a C1-10 alkylene, a C6-20 cycloalkylene, a C5-20 arylene, or a polyoxyalkylene in which the alkylene groups contain 2 to 6 carbon atoms, preferably 2, 3, or 4 carbon atoms; and T is a divalent group derived from a dicarboxylic acid (including a reactive derivative thereof), and T may be, for example, a C2-20 alkylene, a C5-2023SHPP0037-WO-PCT (SS180005PCT) cycloalkylene, or a C6-20 arylene. Copolyesters containing a combination of different T or J groups may be used. The polyester units may be branched or linear.

[0017] In some aspects, J is a C2-30 alkylene group having a straight chain, branched chain, or cyclic (including polycyclic) structure, for example ethylene, n-propylene, i-proplyene, 1,4-butylene, 1,4-cyclohexylene, or 1,4-methylenecyclohexane. In another aspect, J is derived from a bisphenol of formula (3), e.g., bisphenol A. In another aspect, J is derived from an aromatic dihydroxy compound of formula (6), e.g, resorcinol.

[0018] Aromatic dicarboxylic acids that may be used to prepare the polyester units include isophthalic or terephthalic acid, 1,2-di(p-carboxyphenyl)ethane, 4,4'-dicarboxydiphenyl ether, 4,4'-bisbenzoic acid, or a combination thereof. Acids containing fused rings can also be present, such as in 1,4-, 1,5-, or 2,6-naphthalenedicarboxylic acids. Specific dicarboxylic acids include terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, or a combination thereof. A specific dicarboxylic acid comprises a combination of isophthalic acid and terephthalic acid wherein the weight ratio of isophthalic acid to terephthalic acid is 91:9 to 2:98.

[0019] Specific ester units include ethylene terephthalate, n-propylene terephthalate, n- butylene terephthalate, 1,4-cyclohexanedimethylene terephthalate, and ester units derived from isophthalic acid, terephthalic acid, and resorcinol (ITR)).

[0020] In some aspects, useful aromatic polyesters may include poly(isophthalate- terephthalate-resorcinol) esters, poly(isophthalate-terephthalate-bisphenol A) esters, poly[(isophthalate-terephthalate-resorcinol) ester-co-(isophthalate-terephthalate-bisphenol A)] ester, or a combination comprising at least one of these. Also contemplated are aromatic polyesters with a minor amount, e.g., 0.5 to 10 wt%, based on the total weight of the polyester, of units derived from an aliphatic diacid or an aliphatic polyol to make copolyesters. Poly(alkylene arylates) may have a polyester structure according to formula (7), wherein T comprises groups derived from aromatic dicarboxylates, cycloaliphatic dicarboxylic acids, or derivatives thereof. Examples of preferably useful T groups include 1,2-, 1,3-, and 1,4- phenylene; 1,4- and 1,5- naphthylenes; cis- or trans-1,4-cyclohexylene; or the like. Preferably, where T is 1,4-phenylene, the poly(alkylene arylate) is a poly(alkylene terephthalate). In addition, for poly(alkylene arylate), preferably useful alkylene groups J include, for example, ethylene, 1,4-butylene, and bis-(alkylene-disubstituted cyclohexane) including cis- or trans-1,4- (cyclohexylene)dimethylene. Examples of poly(alkylene terephthalates) include poly(ethylene terephthalate) (PET), poly(1,4-butylene terephthalate) (PBT), and poly(n-propylene terephthalate) (PPT). Also useful are poly(alkylene naphthoates), such as poly(ethylene23SHPP0037-WO-PCT (SS180005PCT) naphthanoate) (PEN), and poly(butylene naphthanoate) (PBN). A preferably useful poly(cycloalkylene diester) is poly(1,4-cyclohexanedimethylene terephthalate) (PCT). Combinations comprising at least one of the foregoing polyesters may also be used.

[0021] Copolymers comprising alkylene terephthalate repeating ester units with other ester groups may also be useful. Preferably useful ester units may include different alkylene terephthalate units, which may be present in the polymer chain as individual units, or as blocks of poly(alkylene terephthalates). Copolymers of this type include poly(cyclohexanedimethylene terephthalate)-co-poly(ethylene terephthalate), abbreviated as PETG where the polymer comprises greater than or equal to 50 mol% of poly(ethylene terephthalate), and abbreviated as PCTG where the polymer comprises greater than 50 mol% of poly(1,4-cyclohexanedimethylene terephthalate).

[0022] Poly(cycloalkylene diester)s may also include poly(alkylene cyclohexanedicarboxylate)s. Of these, a specific example is poly(1,4-cyclohexane-dimethanol- 1,4-cyclohexanedicarboxylate) (PCCD), having recurring units of formula 31)wherein, as described using formula (7), J is a 1,4-cyclohexanedimethylene group derived from 1,4-cyclohexanedimethanol, and T is a cyclohexane ring derived from cyclohexanedicarboxylate or a chemical equivalent thereof, and may comprise the cis-isomer, the trans-isomer, or a combination thereof.

[0023] A combination of two or more poly(alkylene arylates)s may be used to achieve the desired intrinsic viscosity. The combination may include a poly(alkylene arylate) having an intrinsic viscosity of 0.50-1.0 dL / g and a poly(alkylene arylate) having an intrinsic viscosity of 1.00-1.50 dL / g . In some aspects, the combination may include a poly(alkylene arylate) having an intrinsic viscosity of 0.7-0.8 dL / g and a poly(alkylene arylate) having an intrinsic viscosity of 1.15-1.50 dL / g . In some aspects the weight ratio of poly(alkylene arylate) having an intrinsic viscosity of 0.7-0.8 dL / g to poly(alkylene arylate) having an intrinsic viscosity of 1.00-1.50 dL / g is 1:9 to 9:1, 1:5 to 5:1, 1:4 to 4:1, 1:3 to 3:1, 1:2 to 2:1, 1:1.5 to 1.5:1, or 1:1. In the foregoing aspects, the poly(alkylene arylate) having an intrinsic viscosity of 1.00-1.50 dL / g may be present in an amount (wt%) less than the poly(alkylene arylate) having an intrinsic viscosity of 0.50-1.0 dL / g .

[0024] The polyesters may be obtained by interfacial polymerization or melt-process condensation as described above, by solution phase condensation, or by transesterification polymerization wherein, for example, a dialkyl ester such as dimethyl terephthalate may be23SHPP0037-WO-PCT (SS180005PCT) transesterified with ethylene glycol using acid catalysis, to generate poly(ethylene terephthalate). A branched polyester, in which a branching agent, for example, a glycol having three or more hydroxyl groups or a trifunctional or multifunctional carboxylic acid has been incorporated, may be used. Furthermore, it may be advantageous to have various concentrations of acid and hydroxyl end groups on the polyester, depending on the ultimate end use of the composition.

[0025] The polyester may be present in an amount ranging from 10-80 wt%, based on the total weight of the composition. Within that range, the polyester may be present in amount ranging from 20-80 wt%, 25-75 wt%, 30-75 wt%, 40-75 wt%, 45-75 wt%, 45-70 wt%, 45-65 wt%, 50-75 wt%, 50-70 wt%, or 50-65 wt%, each based on the total thermoplastic composition.

[0026] In addition to a polyester, the thermoplastic compositions include a polyetherimide. Polyetherimides comprise more than 1, for example 2 to 1000, or 5 to 500, or 10 to 100 structural units of formula (1)wherein each R is independently the same or different, and is a substituted or unsubstituted divalent organic group, such as a substituted or unsubstituted C6-20 aromatic hydrocarbon group, a substituted or unsubstituted straight or branched chain C4-20 alkylene group, a substituted or unsubstituted C3-8 cycloalkylene group, in particular a halogenated derivative any one of the foregoing. In some aspects R is divalent group of one or more of the following formulas (2)wherein Q1is -O-, -S-, -C(O)-, -SO2-, -SO-, -P(Rc)(=O)- wherein Rcis a C1-8 alkyl or C6-12 aryl, - CyH2y- wherein y is an integer from 1 to 5 or a halogenated derivative thereof, or -(C6H10)z- wherein z is an integer from 1 to 4. In some aspects R is m-phenylene, p-phenylene, or a diarylene sulfone, in particular bis(4,4’-phenylene)sulfone, bis(3,4’-phenylene)sulfone, bis(3,3’-23SHPP0037-WO-PCT (SS180005PCT) phenylene)sulfone, or a combination comprising at least one of the foregoing. In some aspects, at least 10 mole percent or at least 50 mole percent of the R groups contain sulfone groups, and in other aspects no R groups contain sulfone groups.

[0027] Further in formula (1), 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 C6-24 monocyclic or polycyclic moiety optionally substituted with 1 to 6 C1-8 alkyl groups, 1 to 8 halogen atoms, or a combination comprising at least one of the foregoing, provided that the valence of Z is not exceeded. Exemplary groups Z include groups of formula (3)wherein Raand Rbin formula (3) are each independently the same or different, and are a halogen atom or a monovalent C1-6 alkyl group, for example; p and q are each independently integers of 0 to 4; c is 0 to 4; and Xais a bridging group connecting the hydroxy-substituted aromatic groups, where the bridging group and the hydroxy substituent of each C6 arylene group are disposed ortho, meta, or para (specifically para) to each other on the C6 arylene group. The bridging group Xamay be a single bond, -O-, -S-, -S(O)-, -S(O)2-, -C(O)-, or a C1-18 organic bridging group. The C1-18 organic bridging group may be cyclic or acyclic, aromatic or non- aromatic, and can further comprise heteroatoms such as halogens, oxygen, nitrogen, sulfur, silicon, or phosphorus. The C1-18 organic group may be disposed such that the C6 arylene groups connected thereto are each connected to a common alkylidene carbon or to different carbons of the C1-18organic bridging group. A specific example of a group Z is a divalent group of formula (3a)wherein Q is -O-, -S-, -C(O)-, -SO2-, -SO-, -P(Rd)(=O)- wherein Rdis a C1-8alkyl or C6-12aryl, or -CyH2y- wherein y is an integer from 1 to 5 or a halogenated derivative thereof. In a specific aspect Z is a derived from bisphenol A, such that Q in formula (3a) is 2,2-isopropylidene.

[0028] In an aspect in formula (1), R is m-phenylene, p-phenylene, or a combination comprising at least one of the foregoing, and T is –O-Z-O- wherein Z is a divalent group of formula (3a). Alternatively, R is m-phenylene, p-phenylene, or a combination comprising at least one of the foregoing, and T is –O-Z-O wherein Z is a divalent group of formula (3a), and Q23SHPP0037-WO-PCT (SS180005PCT) is 2,2-isopropylidene. Such materials are available under the trade name ULTEM from SABIC. Alternatively, the polyetherimide may be a copolymer comprising additional structural polyetherimide units of formula (1) wherein at least 50 mole percent (mol%), for example up to 100 mol% of the R groups are bis(4,4’-phenylene)sulfone, bis(3,4’-phenylene)sulfone, bis(3,3’- phenylene)sulfone, or a combination thereof and the remaining R groups are p-phenylene, m- phenylene or a combination thereof; and Z is 2,2-(4-phenylene)isopropylidene, i.e., a bisphenol A moiety, an example of which is commercially available under the trade name EXTEM from SABIC.

[0029] In some aspects, the polyetherimide is a copolymer that optionally comprises additional structural imide units that are not polyetherimide units, for example imide units of formula (4)wherein R is as described in formula (1) and each V is the same or different, and is a substituted or unsubstituted C6-20 aromatic hydrocarbon group, for example a tetravalent linker of the formulaswherein W is a single bond, -O-, -S-, -C(O)-, -SO2-, -SO-, a C1-18 hydrocarbylene group, - P(Re)(=O)- wherein Reis a C1-8 alkyl or C6-12 aryl, or -CyH2y- wherein y is an integer from 1 to 5 or a halogenated derivative thereof. These additional structural imide units preferably comprise less than 20 mol% of the total number of units, and more preferably may be present in amounts of 0 to 10 mol% of the total number of units, or 0 to 5 mol% of the total number of units, or 0 to 2 mole % of the total number of units. In some aspects, no additional imide units are present in the polyetherimide.

[0030] The polyimide or the polyetherimide may 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 (5) or a chemical equivalent thereof, with an organic diamine of formula (6)H2N-R-NH2 (6)23SHPP0037-WO-PCT (SS180005PCT) wherein T and R are each defined as described above. Copolymers of the polyetherimides may be manufactured using a combination of an aromatic bis(ether anhydride) of formula (5) and an additional bis(anhydride) that is not a bis(ether anhydride), for example pyromellitic dianhydride or bis(3,4-dicarboxyphenyl) sulfone dianhydride.

[0031] Illustrative examples of aromatic bis(ether anhydride)s 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 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. A combination of different aromatic bis(ether anhydride)s may be used.

[0032] Examples of organic diamines include 1,4-butane diamine, 1,5-pentanediamine, 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-dimethylheptamethylenediamine, 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, 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-t-butyl) toluene, bis(p-amino-t- butylphenyl) ether, bis(p-methyl-o-aminophenyl) benzene, bis(p-methyl-o-aminopentyl)23SHPP0037-WO-PCT (SS180005PCT) benzene, 1, 3-diamino-4-isopropylbenzene, bis(4-aminophenyl) sulfide, bis-(4-aminophenyl) sulfone (also known as 4,4^-diaminodiphenyl sulfone (DDS)), and bis(4-aminophenyl) ether. Any regioisomer of the foregoing compounds may be used. C1-4 alkylated or poly(C1-4)alkylated derivatives of any of the foregoing may be used, for example a polymethylated 1,6- hexanediamine. Combinations of these compounds can also be used. In some aspects the organic diamine is m-phenylenediamine, p-phenylenediamine, 4,4^-diaminodiphenyl sulfone, 3,4^- diaminodiphenyl sulfone, 3,3^-diaminodiphenyl sulfone, or a combination comprising at least one of the foregoing.

[0033] The polyimides / polyetherimides can have a melt index of 0.1-10 grams per minute (g / min), as measured by American Society for Testing Materials (ASTM) D1238 at 340 to 370°C, using a 6.7 kilogram (kg) weight. In some aspects, the polyetherimide has a weight average molecular weight (Mw) of 1,000-150,000 grams / mole, as measured by gel permeation chromatography (GPC), using polystyrene standards. In some aspects the polyetherimide has an Mw of 10,000 -80,000 g / mole. Such polyetherimides typically have an intrinsic viscosity greater than 0.2 deciliters per gram (dL / g ), or 0.35 to 0.7 dL / g as measured in m-cresol at 25°C.

[0034] The polyetherimide may be present in amount of up to 15 wt% of the total composition. Within that range, the polyetherimide may be present in an amount of 1-15 wt%, 2-15 wt%, 2.5-15 wt%, 3-15 wt%, 3.5-15 wt%, 4-10 wt%, 4.5-15 wt%, 5-15 wt%, 1-12 wt%, 2- 12 wt%, 2.5-12 wt%, 3-12 wt%, 3.5-12 wt%, 4-12 wt%, 4.5-12 wt%, 5-12 wt%, 1-10 wt%, 2-10 wt%, 2.5-10 wt%, 3-10 wt%, 3.5-10 wt%, 4-10 wt%, 4.5-10 wt%, 5-10 wt%, 6-10 wt%, 6-12 wt% or 6-15 wt%, based on the total weight of the composition. In some aspects, the polyetherimide is present in an amount greater than 1 wt%, for example 1-15 wt%, or greater than or equal to 5%, for example 6-12 wt%, or greater than 5%, for example 6-12 wt%, each based of the total weight of the composition.

[0035] The thermoplastic compositions include a flame retardant composition including a non-fluorinated flame retardant, optionally, an auxiliary flame retardant, and optionally, an anti-drip agent. In some aspects, the thermoplastic compositions do not include a fluorinated flame retardant such as Rimar (potassium perfluorobutane sulfonate) salt.

[0036] In some aspects, the flame retardant can include halogens other than fluorine. In some aspects, the flame retardant composition includes halogens other than fluorine (e.g., bromine and chlorine), provided that the bromine and chlorine content are each 900 ppm or less and the total added bromine and chlorine content of the thermoplastic composition is 1500 ppm or less per IEC 61249-2-21 and UL 746H. Halogenated flame retardants can include halogenated compounds and polymers of formula (20):23SHPP0037-WO-PCT (SS180005PCT)wherein R is an alkylene, alkylidene, or cycloaliphatic linkage (e.g., methylene, ethylene, propylene, isopropylene, isopropylidene, butylene, isobutylene, amylene, cyclohexylene, cyclopentylidene, or the like), a linkage selected from oxygen ether, carbonyl, amine, a sulfur containing linkage (e.g., sulfide, sulfoxide, or sulfone), a phosphorus-containing linkage, or the like, or R can also consist of two or more alkylene or alkylidene linkages connected by such groups as aromatic, amino, ether, carbonyl, sulfide, sulfoxide, sulfone, a phosphorus-containing linkage, or the like; Ar and Ar' may be the same or different and are mono- or polycarbocyclic aromatic groups such as phenylene, biphenylene, terphenylene, naphthylene, or the like; Y is an organic, inorganic or organometallic radical such as halogen (e.g., chlorine, bromine, iodine, or fluorine), ether group of the general formula OE wherein E is a monovalent hydrocarbon radical similar to X, monovalent hydrocarbon groups of the type represented by R, or other substituents (e.g., nitro, cyano, or the like), the substituents being essentially inert provided there be at least one and preferably two halogen atoms per aryl nucleus; each X is the same or different, and is a monovalent hydrocarbon group such as alkyl (e.g., methyl, ethyl, propyl, isopropyl, butyl, decyl, or the like, aryl (e.g., phenyl, naphthyl, biphenyl, xylyl, tolyl, or the like), arylalkylene (e.g., benzyl, ethylenephenyl, or the like), cycloaliphatic (e.g., cyclopentyl, cyclohexyl, or the like), as well as monovalent hydrocarbon groups containing inert substituents therein; the letter d represents a whole number from 1 to a maximum equivalent to the number of replaceable hydrogens substituted on the aromatic rings including Ar or Ar'; the letter e represents a whole number from 0 to a maximum equivalent to the number of replaceable hydrogens on R; the letters a, b, and c represent whole numbers including 0, provided that when b is not 0, neither a nor c can be 0,or that either a or c, but not both, can be 0, or that where b is 0, the aromatic groups are joined by a direct carbon-carbon bond; the hydroxyl and Y substituents on the aromatic groups, Ar and Ar' may be varied in the ortho, meta or para positions on the aromatic rings and the groups may be in any possible geometric relationship with respect to one another.

[0037] Included within the scope of the above formula are bisphenols of which the following are representative: 2,2-bis-(3,5-dichlorophenyl)-propane; bis-(2-chlorophenyl)- methane; bis(2,6-dibromophenyl)-methane; 1,1-bis-(4-iodophenyl)-ethane; 1,2-bis-(2,6- dichlorophenyl)-ethane; 1,1-bis-(2-chloro-4-iodophenyl)ethane; 1,1-bis-(2-chloro-4- methylphenyl)-ethane; 1,1-bis-(3,5-dichlorophenyl)-ethane; 2,2-bis-(3-phenyl-4-bromophenyl)- ethane; 2,6-bis-(4,6-dichloronaphthyl)-propane; 2,2-bis-(2,6-dichlorophenyl)-pentane; 2,2-bis-23SHPP0037-WO-PCT (SS180005PCT) (3,5-dibromophenyl)-hexane; bis-(4-chlorophenyl)-phenyl-methane; bis-(3,5-dichlorophenyl)- cyclohexylmethane; bis-(3-nitro-4-bromophenyl)-methane; bis-(4-hydroxy-2,6-dichloro-3- methoxyphenyl)-methane; and 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane 2,2 bis-(3- bromo-4-hydroxyphenyl)-propane. Also included within the above structural formula are: 1,3- dichlorobenzene, 1,4-dibromobenzene, 1,3-dichloro-4-hydroxybenzene, and biphenyls such as 2,2'-dichlorobiphenyl, polybrominated 1,4-diphenoxybenzene, 2,4'-dibromobiphenyl, and 2,4'- dichlorobiphenyl as well as decabromo diphenyl oxide, or the like.

[0038] In some aspects, the non-fluorinated flame retardant is entirely non-halogenated.

[0039] The non-fluorinated flame retardant may include a phosphorus-containing flame retardant. The phosphorus-containing flame retardant may include a pyrophosphate, a polyphosphate, or a combination thereof. Pyrophosphates and polyphosphates may include metal pyrophosphates, metal polyphosphates, metal acid pyrophosphates, metal acid polyphosphates, or a combination thereof. The phosphorus-containing flame retardant may have the formula MzxHyPnO3n+1, wherein M is a metal, x is 1 to 12, y is 0 to 12, n is 2 to 10, z is 1-5, and the sum of (xz) + y is equal to n+2. M is a Group IA, IIA, IB, or IIB metal, for example sodium or potassium. Exemplary phosphorus-containing flame retardants of this type include, for example, pyrophosphates of the formula Na3HPO4, K2H2P2O7, Na3H2P2O10, KNaH2P2O7, Na2H2P2O7, sodium hexametaphosphate, Na8P6O19. The phosphorus-containing flame retardant that are pyrophosphates and polyphosphates may be hydrates and may be in powder form.

[0040] The phosphorus-containing flame retardant may include a metal di(C1-6 alkyl)phosphinate. As used herein, the term “metal di(C1-6 alkyl)phosphinate” refers to a salt comprising at least one metal cation and at least one di(C1-6 alkyl)phosphinate anion. In some aspects, the metal di(C1-6 alkyl)phosphinate has the formulawherein Raand Rbin the phosphinate are each independently C1-6alkyl; M is calcium, magnesium, aluminum, or zinc; and d is 2 or 3. Examples of Raand Rbin the phosphinate include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, and n-pentyl. In some aspects, Raand Rbin the phosphinate are ethyl, M is aluminum, and d is 3 (that is, the metal di(C1-6 alkyl)phosphinate is aluminum tris(diethylphosphinate)).23SHPP0037-WO-PCT (SS180005PCT)

[0041] In some aspects, the metal di(C1-6 alkyl)phosphinate is in particulate form. The metal di(C1-6 alkyl)phosphinate particles may have a median particle diameter (D50) less than or equal to 40 micrometers, or a D50 less than or equal to 30 micrometers, preferably a D50 less than or equal to 25 micrometers. The particles may have a minimum particle size of 0.1 micrometers or 0.5 micrometers. Additionally, the metal di(C1-6 alkyl)phosphinate may be combined with a polymer, such as a poly(arylene ether), a polyolefin, a polyamide, a block copolymer, or combination thereof, to form a masterbatch. The metal di(C1-6 alkyl)phosphinate masterbatch comprises the metal di(C1-6 alkyl)phosphinate in an amount greater than is present in the thermoplastic composition. Employing a masterbatch for the addition of the metal di(C1-6alkyl)phosphinate to the other components of the composition can facilitate addition and improve distribution of the metal di(C1-6alkyl)phosphinate.

[0042] In addition to the non-fluorinated flame retardant, the flame retardant composition may include an auxiliary flame retardant. In some aspects, the auxiliary flame retardant comprises a melamine having the formulawherein g is 1-10,000, and the ratio of f to g is 0.5:1 to 1.7:1, or 0.7:1 to 1.3:1, or 0.9:1 to 1.1:1. It will be understood that this formula includes species in which one or more protons are transferred from the phosphate group(s) to the melamine group(s). When g is 1, the melamine flame retardant is melamine phosphate (CAS Reg. No.20208-95-1). When g is 2, the melamine flame retardant is melamine pyrophosphate (CAS Reg. No.1554160-3). When g is, on average, greater than 2, the melamine flame retardant is a melamine polyphosphate (CAS Reg. No. 56386-64-2). In some aspects, the melamine flame retardant is melamine pyrophosphate, melamine polyphosphate, or a combination thereof. In some aspects in which the melamine flame retardant is melamine polyphosphate, g has an average value of greater than 2-10,000, or 5-1,000, or 10-500. In some aspects in which the melamine flame retardant is melamine polyphosphate, g has an average value of greater than 2-500. Methods for preparing melamine phosphate, melamine pyrophosphate, and melamine polyphosphate are known in the art, and all are commercially available. For example, melamine polyphosphates may be prepared by reacting polyphosphoric acid and melamine, as described, for example, in U.S. Pat. No. 6,025,419 to Kasowski et al., or by heating melamine pyrophosphate under nitrogen at 290°C to constant weight, as described in U.S. Patent No.6,015,510-Jacobson et al. In some aspects, the23SHPP0037-WO-PCT (SS180005PCT) melamine flame retardant comprises melamine cyanurate.

[0043] The melamine flame retardant may have a low volatility. For example, in some aspects, the melamine flame retardant exhibits less than 1 percent weight loss by thermogravimetric analysis when heated at a rate of 20 °C per minute from 25-280 °C, or 25-300 °C, or 25-320 °C.

[0044] The auxiliary flame retardant may include inorganic auxiliary flame retardants. Inorganic flame retardants may include metal hydroxides, metal oxides, polyphosphates, boron salts such as metal borates, inorganic antimony, tin, zinc, and molybdenum compounds, as well as red phosphorous. However, due to regulatory concerns, the auxiliary flame retardant is preferably substantially free of antimony, tin, and halogenated auxiliary flame retardants.

[0045] In some aspects, the auxiliary flame retardant includes a metal hydroxide, a metal borate, a pyrophosphate, a metal oxide, a metal oxide hydroxide, or a combination thereof. In some aspects, the auxiliary flame retardant includes a metal hydroxide. Exemplary metal hydroxides include, but are not limited to, magnesium hydroxide, aluminum hydroxide, zinc hydroxide, cobalt hydroxide, or a combination thereof. The metal hydroxide may be coated, for example, with stearic acid or another fatty acid. The auxiliary flame retardant may include a metal borate, such as zinc borate; a metal oxide hydroxide, such as aluminum oxide hydroxide also known as Boehmite and commercially available as SASOL; a metal oxide, such as magnesium oxide (e.g., ELASTOMAG 170), zinc oxide, or a combination thereof.

[0046] When the flame retardant composition includes phosphorus, the flame retardant is present in an amount effective to provide up to 6 wt% phosphorus, based on the total weight of the composition. Within this range, the flame retardant is present in an amount effective to provide 0.5-6 wt%, 1-6 wt%, 2-6 wt%, 2.5-6 wt%, or 3-6 wt% phosphorus, based on the total weight of the composition.

[0047] The thermoplastic compositions minimize or eliminate conventional anti-drip agents, in particular fluorinated anti-drip agents. Anti-drip agents include, for example, a fibril forming or non-fibril forming fluoropolymer such as polytetrafluoroethylene (PTFE). The anti- drip agent may be encapsulated by a rigid copolymer, for example styrene–acrylonitrile copolymer (SAN). PTFE encapsulated in SAN is known as TSAN. An TSAN comprises 50 wt% PTFE and 50 wt% SAN, based on the total weight of the encapsulated fluoropolymer. The SAN can comprise, for example, 75 wt% styrene and 25 wt% acrylonitrile based on the total weight of the copolymer. In some aspects, the fluorinated anti-drip agent is present in an amount effective to provide 0.15 wt% or less fluorine to the total composition. In some aspects, a fluorinated anti-drip agent is excluded from the thermoplastic compositions.23SHPP0037-WO-PCT (SS180005PCT)

[0048] The thermoplastic composition may include various additives (“an additive composition”) ordinarily incorporated into polymer compositions of this type, with the proviso that the additive(s) are selected so as to not significantly adversely affect the desired properties of the thermoplastic composition, in particular flame resistance, impact resistance and the melt volume rate. In some aspects, any additive is non-halogenated or non-fluorinated. Such additives may be mixed at a suitable time during the mixing of the components for forming the composition. Additives include antioxidants, heat stabilizers, light stabilizers, ultraviolet (UV) light stabilizers, plasticizers, lubricants, mold release agents, antistatic agents, colorants and organic dyes, surface effect additives, radiation stabilizers, and poly(ether-ester) block copolymers. A combination of additives may be used, for example a combination of a heat stabilizer, mold release agent, and ultraviolet light stabilizer. In general, the additives are used in the amounts generally known to be effective. For example, the total amount of the additives (other than any filler or reinforcing agents) may be 0.01-10 wt%, 0.01-5 wt%, 0.01-2 wt%, or 0.01-1 wt%, each based on the total weight of the thermoplastic composition.

[0049] In some aspects, the additive composition includes a poly(ether-ester) block copolymer, also known in the art as thermoplastic elastomers or thermoplastic ester elastomers (TPEE). Poly(ether-ester) block copolymers consist essentially of “soft block” long-chain ester units of formula (15)wherein G is a derived from a poly(C1-4alkylene oxide) glycol having a number-average molecular weight of 400 to 6000, and R20is derived from a C4-24 aliphatic or aromatic dicarboxylic acid, preferably an aromatic dicarboxylic acid; and “hard block” short-chain ester units of formula (16) O O C R20C O D O (16) wherein D is a C1-10alkylene or cycloalkylene derived from the corresponding diol having a molecular weight of less than or equal to 300; and R20is derived from a C4-24aliphatic, alicyclic, or aromatic dicarboxylic acid, preferably an aromatic dicarboxylic acid; with the proviso that the short-chain ester units constitute about 40% to about 90% by weight of the poly(ether-ester) block copolymer, and the long-chain ester units constitute about 10% to about 60% by weight of the poly(ether-ester) block copolymer.

[0050] A variety of poly(ether-ester) copolymers are commercially available, for example under the trademarks ARNITEL EM400 and ARNITEL EL630 poly(ether-ester)23SHPP0037-WO-PCT (SS180005PCT) copolymers from DSM; HYTREL 3078, HYTREL 4056, HYTREL 4556, and HYTREL 6356 poly(ether-ester) copolymers from DuPont; and ECDEL 9966 poly(ether-ester) copolymer from Eastman Chemical. In all cases, the soft block is derived from tetrahydrofuran. In the HYTREL 4556, HYTREL 6356, ARNITEL EM400, and ARNITEL EL630 poly(ether-ester) copolymers, the hard block is based on poly(butylene terephthalate) (PBT). In the HYTREL 4056 poly(ester- ether) copolymer, the hard block contains isophthalate units in addition to terephthalate units. In the ECDEL 9966 poly(ether-ester) copolymer, the hard block is based on poly(1,4-cyclohexane- dimethanol-1,4-cyclohexane dicarboxylate) (PCCD) units.

[0051] Colorants such as pigment or dye additives may be present in the additive composition. Useful pigments can include, for example, inorganic pigments such as metal oxides and mixed metal oxides such as zinc oxide, titanium dioxides, iron oxides, or the like; sulfides such as zinc sulfides, or the like; aluminates; sodium sulfo-silicates sulfates, chromates, or the like; carbon blacks; zinc ferrites; ultramarine blue; organic pigments such as azos, di-azos, quinacridones, perylenes, naphthalene tetracarboxylic acids, flavanthrones, isoindolinones, tetrachloroisoindolinones, anthraquinones, enthrones, dioxazines, phthalocyanines, and azo lakes; Pigment Red 101, Pigment Red 122, Pigment Red 149, Pigment Red 177, Pigment Red 179, Pigment Red 202, Pigment Violet 29, Pigment Blue 15, Pigment Blue 60, Pigment Green 7, Pigment Yellow 119, Pigment Yellow 147, Pigment Yellow 150, and Pigment Brown 24; or a combination thereof.

[0052] Dyes are generally organic materials and include coumarin dyes such as coumarin 460 (blue), coumarin 6 (green), nile red or the like; lanthanide complexes; hydrocarbon and substituted hydrocarbon dyes; polycyclic aromatic hydrocarbon dyes; scintillation dyes such as oxazole or oxadiazole dyes; aryl- or heteroaryl-substituted poly (C2-8) olefin dyes; carbocyanine dyes; indanthrone dyes; phthalocyanine dyes; oxazine dyes; carbostyryl dyes; napthalenetetracarboxylic acid dyes; porphyrin dyes; bis(styryl)biphenyl dyes; acridine dyes; anthraquinone dyes; cyanine dyes; methine dyes; arylmethane dyes; azo dyes; indigoid dyes, thioindigoid dyes, diazonium dyes; nitro dyes; quinone imine dyes; aminoketone dyes; tetrazolium dyes; thiazole dyes; perylene dyes, perinone dyes; bis-benzoxazolylthiophene (BBOT); triarylmethane dyes; xanthene dyes; thioxanthene dyes; naphthalimide dyes; lactone dyes; fluorophores such as anti-stokes shift dyes which absorb in the near infrared wavelength and emit in the visible wavelength, or the like; luminescent dyes such as 7-amino-4- methylcoumarin; 3-(2'-benzothiazolyl)-7-diethylaminocoumarin; 2-(4-biphenylyl)-5-(4-t- butylphenyl)-1,3,4-oxadiazole; 2,5-bis-(4-biphenylyl)-oxazole; 2,2'-dimethyl-p-quaterphenyl; 2,2-dimethyl-p-terphenyl; 3,5,3"",5""-tetra-t-butyl-p-quinquephenyl; 2,5-diphenylfuran; 2,5-23SHPP0037-WO-PCT (SS180005PCT) diphenyloxazole; 4,4'-diphenylstilbene; 4-dicyanomethylene-2-methyl-6-(p- dimethylaminostyryl)-4H-pyran; 1,1'-diethyl-2,2'-carbocyanine iodide; 3,3'-diethyl-4,4',5,5'- dibenzothiatricarbocyanine iodide; 7-dimethylamino-1-methyl-4-methoxy-8-azaquinolone-2; 7- dimethylamino-4-methylquinolone-2; 2-(4-(4-dimethylaminophenyl)-1,3-butadienyl)-3- ethylbenzothiazolium perchlorate; 3-diethylamino-7-diethyliminophenoxazonium perchlorate; 2- (1-naphthyl)-5-phenyloxazole; 2,2'-p-phenylen-bis(5-phenyloxazole); rhodamine 700; rhodamine 800; pyrene, chrysene, rubrene, coronene, or the like; or a combination thereof.

[0053] The thermoplastic compositions include a reinforcing agent. Reinforcing agents may include, for example, mica, clay, feldspar, quartz, quartzite, perlite, tripoli, diatomaceous earth, aluminum silicate (mullite), synthetic calcium silicate, fused silica, fumed silica, sand, boron-nitride powder, boron-silicate powder, calcium sulfate, calcium carbonates (such as chalk, limestone, marble, and synthetic precipitated calcium carbonates) talc (including fibrous, modular, needle shaped, and lamellar talc), wollastonite, hollow or solid glass spheres, silicate spheres, cenospheres, aluminosilicate or (armospheres), kaolin, whiskers of silicon carbide, alumina, boron carbide, iron, nickel, or copper, continuous and chopped carbon fibers or glass fibers, molybdenum sulfide, zinc sulfide, barium titanate, barium ferrite, barium sulfate, heavy spar, TiO2, aluminum oxide, magnesium oxide, particulate or fibrous aluminum, bronze, zinc, copper, or nickel, glass flakes, flaked silicon carbide, flaked aluminum diboride, flaked aluminum, steel flakes, natural fillers such as wood flour, fibrous cellulose, cotton, sisal, jute, starch , lignin, ground nut shells, or rice grain husks, reinforcing organic fibrous fillers such as poly(ether ketone), polyimide, polybenzoxazole, poly(phenylene sulfide), polyesters, polyethylene, aromatic polyamides, aromatic polyimides, polyetherimides, polytetrafluoroethylene, and poly(vinyl alcohol), as well a combination thereof. The fillers and reinforcing agents may be coated with a layer of metallic material to facilitate conductivity, or surface treated with silanes to improve adhesion and dispersion with the polymer matrix.

[0054] The reinforcing agent may include a reinforcing fiber (including continuous and chopped fibers) such as asbestos, carbon fibers, glass fibers, such as E, A, C, ECR, R, S, D, or NE glasses, or the like. In addition, the reinforcing fibers may be provided in the form of monofilament or multifilament fibers and may be used individually or in combination with other types of fiber, through, for example, co-weaving or core / sheath, side-by-side, orange-type or matrix and fibril constructions, or by other methods known to one skilled in the art of fiber manufacture. Co-woven structures include glass fiber-carbon fiber, carbon fiber-aromatic polyimide (aramid) fiber, and aromatic polyimide fiberglass fiber or the like. Preferably the reinforcing fiber includes carbon fibers, glass fibers, or a combination thereof. In some aspects,23SHPP0037-WO-PCT (SS180005PCT) only fibers are used as the reinforcing agent, and in some aspects, only glass fibers are used as the reinforcing agent.

[0055] The reinforcing fibers may be of any cross-sectional shape, for example round, square, ovoid, or irregular. The reinforcing fibers can have an average largest diameter from 1 micrometer to 1 millimeter, or from 1-500 micrometers. The reinforcing fibers may be supplied in the form of, for example, individual fibers, rovings, woven fibrous reinforcements, such as 0- 90 degree fabrics or the like; non-woven fibrous reinforcements such as continuous strand mat, chopped strand mat, tissues, papers, felts, or the like; or three-dimensional reinforcements such as braids.

[0056] The reinforcing agent may be present in an amount from 5-75 wt%, 5-65 wt%, 5- 55 wt%, 5-45 wt%, 5-30 wt%, 5-25 wt%, 10-75 wt%, 10-65 wt%, 10-55 wt%, 10-45 wt%, 10- 30 wt%, 10-25 wt%, 15-75 wt%, 15-65 wt%, 15-55 wt%, 15-45 wt%, 15-30 wt%, 15-25 wt%, 20-75 wt%, 20-65 wt%, 20-55 wt%, 20-45 wt%, 20-30 wt%, 20-25 wt%, based on the total weight of the thermoplastic composition, which sums to 100 wt%.

[0057] In some aspects, the thermoplastic compositions include a poly(alkylene arylate), preferably poly(1,4-butylene terephthalate), a polyetherimide, a non-fluorinated flame retardant including a metal di(C1-6alkyl)phosphinate, and a reinforcing agent including glass fibers.

[0058] In some aspects, the thermoplastic compositions include a poly(1,4-butylene terephthalate), a polyetherimide, a non-fluorinated flame retardant including a metal di(C1-6 alkyl)phosphinate, and a reinforcing agent including glass fibers.

[0059] In some aspects, the thermoplastic compositions include a poly(1,4-butylene terephthalate), 1-15 wt% polyetherimide, a non-fluorinated flame retardant including a metal di(C1-6 alkyl)phosphinate, and a reinforcing agent including glass fibers.

[0060] In some aspects, the thermoplastic compositions include a poly(1,4-butylene terephthalate), 1-15 wt% polyetherimide, a non-fluorinated flame retardant including a metal di(C1-6 alkyl)phosphinate, and a reinforcing agent including glass fibers, wherein the non- fluorinated flame retardant is present in amount effective to provide up to 6 wt% phosphorus, preferably 2-6 wt% phosphorus.

[0061] In some aspects, the thermoplastic compositions include a poly(1,4-butylene terephthalate) having an intrinsic viscosity of 0.5-1.0 dL / g and a poly(1,4-butylene terephthalate) having an intrinsic viscosity of 1.15-1.40 dL / g , a polyetherimide, a non- fluorinated flame retardant including a metal di(C1-6alkyl)phosphinate, and a reinforcing agent including glass fibers.23SHPP0037-WO-PCT (SS180005PCT)

[0062] In some aspects, the thermoplastic compositions include a poly(1,4-butylene terephthalate) having an intrinsic viscosity of 0.5-1.0 dL / g and a poly(1,4-butylene terephthalate) having an intrinsic viscosity of 1.15-1.40 dL / g , a polyetherimide, a non- fluorinated flame retardant including a metal di(C1-6 alkyl)phosphinate, and a reinforcing agent including glass fibers, wherein the wt% of poly(1,4-butylene terephthalate) having an intrinsic viscosity of 1.15-1.40 dL / g is less than the wt% of poly(1,4-butylene terephthalate) having an intrinsic viscosity of 0.5-1.0 dL / g .

[0063] In some aspects, the thermoplastic compositions include a poly(1,4-butylene terephthalate) having an intrinsic viscosity of 0.5-1.0 dL / g and a poly(1,4-butylene terephthalate) having an intrinsic viscosity of 1.15-1.40 dL / g , a polyetherimide, a non- fluorinated flame retardant including a metal di(C1-6alkyl)phosphinate, and a reinforcing agent including glass fibers, wherein the wt% of poly(1,4-butylene terephthalate) having an intrinsic viscosity of 1.15-1.40 dL / g is less than the wt% of poly(1,4-butylene terephthalate) having an intrinsic viscosity of 0.5-1.0 dL / g and wherein the non-fluorinated flame retardant is present in amount effective to provide up to 6 wt% phosphorus, preferably 2-6 wt% phosphorus.

[0064] The thermoplastic compositions may have ultra-low halogen content. As used herein, “ultra-low chlorine and / or bromine content” refers to materials produced without addition, e.g., intentional addition, of chlorine and / or bromine, or chlorine- and / or bromine- containing materials. It is understood however that in facilities that process multiple products cross contamination may occur, resulting in bromine and / or chlorine levels, typically on the parts per million by weight scale. With this understanding it may be readily appreciated that “ultra-low chlorine or bromine content” is defined as having a bromine or chlorine content of less than or equal to 100 parts per million by weight (ppm), less than or equal to 75 ppm, or less than or equal to 50 ppm. “Ultra-low chlorine and bromine content” means a total bromine and chlorine content of less than or equal to 100 parts per million by weight, or less than or equal to 75 ppm, or less than or equal to 50 ppm. When these definitions are applied to the non- fluorinated flame retardant each is based on the total weight of the non-fluorinated flame retardant. When these definitions are applied to the thermoplastic composition, each is based on the total parts by weight of the thermoplastic composition.

[0065] In another aspect, the thermoplastic composition may have an ultra-low chlorine, bromine, or fluorine content. As used herein, “ultra-low chlorine, bromine, or fluorine content” is defined as having a bromine, chlorine, or fluorine content of less than or equal to 100 ppm, less than or equal to 75 ppm, or less than or equal to 50 ppm, each based on the total parts by weight of the composition. As used herein, “ultra-low chlorine, bromine, and fluorine content” is23SHPP0037-WO-PCT (SS180005PCT) defined as having a bromine, chlorine, and fluorine content of less than or equal to 100 ppm, less than or equal to 75 ppm, or less than or equal to 50 ppm, each based on the total parts by weight of the composition.

[0066] The thermoplastic compositions may be manufactured by various methods. For example, powdered polymers, non-fluorinated flame retardant, and / or optional components are first blended, optionally with fillers in a HENSCHEL-Mixer high speed mixer. Other low shear processes, including but not limited to hand mixing, may also accomplish this blending. The blend is then fed into the throat of a twin-screw extruder via a hopper. Alternatively, at least one of the components may be incorporated into the composition by feeding directly into the extruder at the throat or downstream through a sidestuffer. Additives may also be compounded into a masterbatch with a desired polymeric polymer and fed into the extruder. The extruder is generally operated at a temperature higher than that necessary to cause the composition to flow. The extrudate is immediately quenched in a water bath and pelletized. The pellets so prepared may be one-fourth inch long or less as desired. Such pellets may be used for subsequent molding, shaping, or forming.

[0067] A sample of the thermoplastic composition may have a flame test rating of V-0, as measured according to UL-94 at a thickness of 0.8 millimeter or less, for example, 0.6 millimeter and / or 0.4 millimeter.

[0068] Shaped, formed, or molded articles including the thermoplastic compositions are also provided. The thermoplastic compositions may be molded into useful shaped articles by a variety of methods, such as injection molding, extrusion, rotational molding, blow molding and thermoforming. Some examples of articles include computer and business machine housings such as housings for monitors, handheld electronic device housings such as housings for cell phones, electrical connectors, and components of lighting fixtures, ornaments, home appliances, roofs, greenhouses, sun rooms, swimming pool enclosures, advanced driver assistance systems (ADAS) enclosures, or the like. In some aspects, the article is an extruded article, a molded article, pultruded article, a thermoformed article, a foamed article, a layer of a multi-layer article, a substrate for a coated article, or a substrate for a metallized article. In addition, the thermoplastic compositions may be used for such applications as a molded housing and other devices such as electrical circuit housing.

[0069] Thin films including the thermoplastic compositions are also provided. The thin film of the thermoplastic composition may be prepared by extrusion of the thermoplastic composition. The thin films may have improved thermal resistance. In some aspects, the thin films may be transparent.23SHPP0037-WO-PCT (SS180005PCT)

[0070] This disclosure is further illustrated by the following examples, which are non- limiting. EXAMPLES

[0071] The following components are used in the examples. Unless specifically indicated otherwise, the amount of each component is in wt%, based on the total weight of the composition.

[0072] The materials shown in Table 1 were used. Table 1. PBT-1 Poly(butylene terephthalate), CAS Reg. No.26062-94-2, having an intrinsic viscosity of 0.5-1.0 dL / g as measured at 30°C in a 1:1 w / w solution of phenol:1,1,2,2-tetrachloroethane, and 17 milliequivalents per kilogram SABIC (meq / kg) of COOH PBT-2 Poly(butylene terephthalate), CAS Reg. No.26062-94-2, having an intrinsic SABIC viscosity of 1.0-1.5 dL / g as measured at 30°C in a 1:1 w / w solution of phenol:1,1,2,2-tetrachloroethane, and having 38 meq / kg of COOH PEI Polyetherimide including ether-imide units derived from diamino phenylene SABIC and the bis-anhydride of BPA DEPAL Aluminum tris(diethyl phosphinate), CAS Reg. No.225789-38-8; obtained as Clariant EXOLIT OP1240; 24 wt% phosphorus MPP Melamine polyphosphate, CAS Reg. No.56386-64-2, obtained as MELAPUR BASF Corp 200; 24 wt% phosphorus ADD Poly(ether-ester) block copolymer, available as HYTREL 4056 DUPONT PETS Pentaerythritol tetrastearate, CAS Reg. No.115-83-3 FACI SpA. PHBPP Pentaerythritol 3-(4-hydroxy-3,5-di-tert-butylphenyl)propionate (1:4), CAS BASF Reg. No.6683-19-8; obtained as IRGANOX 1010 GF Chopped glass fibers having a diameter of 10 micrometers and a pre- PPG Industries compounded length of 3.2 millimeters; obtained as CHOPVANTAGE 3540

[0073] Sample preparation and testing methods are described below.

[0074] Samples were compounded on a 25 mm Werner Pfleiderer ZSK co-rotating twin- screw extruder with a vacuum vent. The temperature profile and other extruder settings are provided in Table 2. Table 2. Parameter – 25 mm ZSK Setting Die 2 holes Feed temperature 40 °C Zone 1 temperature 230-240 °C Zone 2 temperature 250-270 °C Zone 3-8 temperature 260-300 °C Die temperature 250-290 °C Screw speed 300 rpm Throughput 15-25 kg / h Vacuum 1 0.7 bar

[0075] The compounded strand was cooled in a water bath prior to pelletizing. The pellets were dried for two hours at 110-120 °C in a forced air-circulating oven prior to injection23SHPP0037-WO-PCT (SS180005PCT) molding. Sample parts were molded on an Engel molding machine. Molding settings are provided in Table 3. Table 3. Parameter – Engel Molding Machine Setting Pre-drying time 2-4 hours Pre-drying temperature 110-120 °C Hopper temperature 40 °C Zone 1 temperature 230-250 °C Zone 2 temperature 235-270 °C Zone 3 temperature 240-280 °C Nozzle temperature 255-275 °C Mold temperature 40-100 °C Screw speed 100 rpm

[0076] Flammability tests were performed on samples at a thickness of 3.0 mm or less (e.g., 2.0, 1.5 mm, 1.0 mm, and 0.8 mm) in accordance with the Underwriter’s Laboratory (UL) UL 94 standard. In some cases, a second set of 5 bars was tested to give an indication of the robustness of the rating. In this report the following definitions are used as shown in Table 4. Total flame-out-times for all bars (FOT = t1 + t2) were determined. Table 4. t1 and / or t2 5-bar cumulative FOT burning drips igniting cotton V-0 <10 <50 No V-1 <30 <250 No V-2 <30 <250 Yes N.R. (no rating) >30 >250 Table 5 below provides the compositions and properties for the following comparative examples and examples of the thermoplastic compositions. Table 5. Unit CE1 CE2 CE3 CE4 CE5 CE6 E1 E2 PBT-1 wt% 30.5 28.35 26.45 26.45 25.5 42.15 37.15 37.15 PBT-2 wt% 50.15 47.3 44.2 44.2 50.15 15 15 15 PEI wt% 5 10 5 5 10 DEPAL wt% 14 14 14 14 14 12.5 12.5 12.5 MPP wt% 5 5 5 5 5 PETS wt% 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 PHBPP wt% 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 ADD wt% 5 5 5 5 5 GF wt% 25 25 25 Total wt% 100 100 100 100 100 100 100 100 P wt% 3.4 4.6 3.4 3.4 4.6 4.2 4.2 4.2 UL-94 (1.6 mm) V-2 V-0 V-2 V-2 V-0 V-0 V-0 V-0 UL-94 (0.8 mm) V-2 V-2 V-2 V-2 V-2 V-1 V-0 V-0 UL-94 (0.6 mm) V-2 V-2 V-2 V-2 V-2 V-1 V-0 V-0 UL-94 (0.4 mm) V-2 V-2 V-2 V-2 V-2 V-2 V-2 V-023SHPP0037-WO-PCT (SS180005PCT)

[0077] Comparative Examples 1-5 do not include glass fibers and no anti-drip agent (e.g., TSAN). Comparative Example 1, which includes a non-fluorinated flame retardant (i.e., DEPAL), but no anti-drip agent (e.g., TSAN) failed to achieve a V-0 flame test rating at a low thickness (e.g., 0.8 mm and thinner). Comparative Example 2 includes a combination of non- fluorinated flame retardants (i.e., DEPAL and MPP), but still failed to achieve a V-0 flame test rating at a low thickness.

[0078] Comparative Examples 4-5 incorporate a polyetherimide, which failed to provide the desired flame test rating. Comparative Example 6 and Example 1-2 each include glass fibers. Comparative Example 6, which in addition to glass fibers includes a combination of non- fluorinated flame retardants (i.e., DEPAL and MPP) but does not include a polyetherimide, failed to provide the desired flame test rating. Examples 1-2 demonstrate that when a polyetherimide is present in a glass-filled composition including a non-fluorinated flame retardant, then a V-0 flame test rating at 0.8 mm and 0.6 mm was achieved. Comparison of Example 1 with Example 2 shows that greater than 5 wt% polyetherimide in the composition of Example 1 was needed to achieve a V-0 flame test rating at 0.4 mm. In particular, Example 1 shows that 5 wt% polyetherimide was insufficient and Example 2 shows that 10 wt% polyetherimide was sufficient to achieve a V-0 flame test rating.

[0079] This disclosure further encompasses the following aspects.

[0080] Aspect 1. A thermoplastic composition comprising: a polyester comprising a poly(alkylene arylate); a flame retardant composition comprising a non-fluorinated flame retardant, optionally, an auxiliary flame retardant, and optionally, an anti-drip agent; greater than or equal to 5 wt% of a polyetherimide based on the total weight of the composition, a reinforcing agent; optionally, an additive composition; and wherein the sum of the wt% of the polyester, the flame retardant composition, the polyetherimide, the reinforcing agent, and the optional additive composition total 100 wt%, wherein a sample of the composition exhibits a UL-94 rating of V-0 at a thickness of 0.8 mm, or 0.6 mm, or wherein a sample of the composition exhibits a UL-94 rating of V-0 at a thickness of 0.4 mm, wherein the thermoplastic composition is essentially fluorine-free.

[0081] Aspect 2. The thermoplastic composition of aspect 1 comprising: 10-80 wt% of the polyester comprising the poly(alkylene arylate); the flame retardant composition comprising a phosphorus-containing flame retardant present in an amount effective to provide up to 6 wt% phosphorus based on the total weight of the composition; 5-15 wt% of the polyetherimide; 5-75 wt% of the reinforcing agent; and 0.01-10 wt% of the additive composition; wherein the sum of the wt% of the polyester, the flame retardant composition, the polyetherimide, the reinforcing23SHPP0037-WO-PCT (SS180005PCT) agent and the optional additive composition total 100 wt%, and wherein a sample of the composition exhibits a UL-94 rating of V-0 at a thickness of 0.8 mm, preferably 0.6 mm.

[0082] Aspect 3. The thermoplastic composition of aspect 1 comprising: 10-80 wt% of the polyester comprising the poly(alkylene arylate); the flame retardant composition comprising a phosphorus-containing flame retardant present in an amount effective to provide 2-6 wt% phosphorus based on the total weight of the composition; greater than 5 to 15 wt% of the polyetherimide; 5-75 wt% of the reinforcing agent; and 0.01-10 wt% of the additive composition; wherein the sum of the wt% of the polyester, the flame retardant composition, the polyetherimide, the reinforcing agent, and the optional additive composition total 100 wt%, and wherein a sample of the composition exhibits a UL-94 rating of V-0 at a thickness of 0.4 mm.

[0083] Aspect 4. The thermoplastic composition of aspect 1 comprising: 20-70 wt%, or 30-60 wt%, of the polyester comprising poly(butylene arylate);the flame retardant composition comprising a phosphorus-containing flame retardant present in an amount effective to provide 2- 6 wt% phosphorus based on the total weight of the composition, and no fluorinated anti-drip agent; 6 to 12 wt% of the polyetherimide; 20-75 wt% of the reinforcing agent, wherein the reinforcing agent comprises glass fibers; and 0.01-10 wt% of the additive composition; wherein the sum of the wt% of the polyester, the flame retardant composition, the polyetherimide, the reinforcing agent, and the optional additive composition total 100 wt%, and wherein a sample of the composition exhibits a UL-94 rating of V-0 at a thickness of 0.4 mm.

[0084] Aspect 4a. The thermoplastic composition of any one of aspects 1 to 3, wherein the polyester further comprises a poly(cycloalkylene diester), a poly(alkylene arylate)-co- poly(cycloalkylene diester), or a combination thereof.

[0085] Aspect 4b. The thermoplastic composition of any one of aspects 1 to 4, wherein the poly(alkylene arylate) comprises: a poly(alkylene terephthalate), a poly(alkylene naphthoate), or a combination thereof, preferably wherein the poly(alkylene terephthalate) comprises poly(ethylene terephthalate) (PET), poly(1,4-butylene terephthalate) (PBT), poly(n- propylene terephthalate) (PPT), more preferably poly(1,4-butylene terephthalate), and preferably wherein the poly(alkylene naphthoate) comprises poly(ethylene naphthanoate) (PEN), and poly(butylene naphthanoate) (PBN), or a combination thereof.

[0086] Aspect 4c. The thermoplastic composition of any one of aspects 1 to 4, wherein the poly(alkylene arylate)-co- poly(cycloalkylene diester) comprises poly(cyclohexanedimethylene terephthalate)-co-poly(ethylene terephthalate).

[0087] Aspect 5d. The thermoplastic composition of any one of the preceding aspects, wherein the polyetherimide does not include a poly(etherimide-siloxane).23SHPP0037-WO-PCT (SS180005PCT)

[0088] Aspect 5. The thermoplastic composition of any one of the preceding aspects, wherein the non-fluorinated flame retardant comprises a phosphorus-containing flame retardant present in an amount effective to provide 2-6 wt% phosphorus, based on the total weight of the composition.

[0089] Aspect 5. The thermoplastic composition any one of the preceding aspects, wherein the polyetherimide does not include a poly(etherimide-siloxane) and wherein the thermoplastic composition comprises 500 ppm or less of added fluorine, or 500 ppm or less of fluorine.

[0090] Aspect 6. The thermoplastic composition any one of the preceding aspects excluding an anti-drip agent, preferably excluding a fluorinated anti-drip agent.

[0091] Aspect 7. The thermoplastic composition any one of the preceding aspects wherein: the added, e.g., the calculated added, bromine and chlorine content of the thermoplastic composition are each about 900 ppm or less and the added, e.g., the calculated total added, halogen content of the thermoplastic composition is about 1500 ppm or less; or the calculated added bromine, chlorine, and fluorine content of the thermoplastic composition are each about 900 ppm or less and the added, or the calculated total added bromine, chlorine, and fluorine content of the thermoplastic composition is about 1500 ppm or less.

[0092] Aspect 8. The thermoplastic composition of any one of the preceding aspects comprising: a poly(alkylene arylate), preferably poly(1,4-butylene terephthalate), and 100 ppm or less of added, or calculated added, fluorine.

[0093] Aspect 9. The thermoplastic composition of any one of the preceding aspects, wherein the polyester comprises: a poly(1,4-butylene terephthalate) comprising an intrinsic viscosity of 0.5 to 1.0 dL / g ; and a poly(1,4-butylene terephthalate) comprising an intrinsic viscosity of 1.15 to 1.40 dL / g , wherein the wt% of the poly(1,4-butylene terephthalate) comprising an intrinsic viscosity of 1.15 to 1.40 dL / g is less than the poly(1,4-butylene terephthalate) comprising an intrinsic viscosity of 0.5 to 1.0 dL / g .

[0094] Aspect 10. The thermoplastic composition of any one of the preceding aspects comprising greater than 5 wt% of a polyetherimide, wherein a sample of the composition exhibits a UL-94 rating of V-0 at a thickness of 0.4 mm.

[0095] Aspect 11. The thermoplastic composition of any one of the preceding aspects comprising 5-12 wt%, or 6-12 wt% of a polyetherimide, based on the total weight of the composition.

[0096] Aspect 12. The thermoplastic composition of any one of the preceding aspects, wherein the polyetherimide does not include a poly(etherimide-siloxane).23SHPP0037-WO-PCT (SS180005PCT)

[0097] Aspect 13. The thermoplastic composition of any one of the preceding aspects, wherein the polyetherimide does not comprise a poly(etherimide-siloxane).

[0098] Aspect 14. A method of making the thermoplastic composition of any one of the preceding aspects, the method comprising melt-mixing the components of the composition, and, optionally, extruding the composition.

[0099] Aspect 15. An article comprising the thermoplastic composition of any one of the preceding aspects.

[0100] Aspect 16. A method of manufacturing the article of aspect 15, comprising molding, casting, or extruding the composition to provide the article.

[0101] The compositions, methods, and articles may alternatively include, consist of, or consist essentially of, any appropriate materials, steps, or components herein disclosed. The compositions, methods, and articles may additionally, or alternatively, be formulated so as to be devoid, or substantially free, of any materials (or species), steps, or components, which are otherwise not necessary to the achievement of the function or objectives of the compositions, methods, and articles.

[0102] All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other (e.g., ranges of “up to 25 wt%, or, more specifically, 5 wt% to 20 wt%”, is inclusive of the endpoints and all intermediate values of the ranges of “5 wt% to 25 wt%,” etc.). “Combinations” is inclusive of blends, mixtures, alloys, reaction products, or the like. The terms “first,” “second,” or the like, do not denote any order, quantity, or importance, but rather are used to distinguish one element from another. The terms “a” and “an” and “the” do not denote a limitation of quantity and are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. “Or” means “and / or” unless clearly stated otherwise. Reference throughout the specification to “some aspects”, “an aspect”, and so forth, means that a particular element described in connection with the aspect is included in at least one aspect described herein, and may or may not be present in other aspects. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various aspects. A “combination thereof” is open and includes any combination including at least one of the listed components or properties optionally together with a like or equivalent component or property not listed.

[0103] Unless specified to the contrary herein, all test standards are the most recent standard in effect as of the filing date of this application, or, if priority is claimed, the filing date of the earliest priority application in which the test standard appears.23SHPP0037-WO-PCT (SS180005PCT)

[0104] Unless defined otherwise, technical and scientific terms used herein have the same meaning as is commonly understood by one of 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 the present application contradicts or conflicts with a term in the incorporated reference, the term from the present application takes precedence over the conflicting term from the incorporated reference.

[0105] Compounds are described using standard nomenclature. For example, 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. For example, -CHO is attached through carbon of the carbonyl group.

[0106] As used herein, the term “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 unless it is specifically identified as “substituted hydrocarbyl”. The hydrocarbyl residue may be aliphatic or aromatic, straight-chain, cyclic, bicyclic, branched, saturated, or unsaturated. It may also contain combinations of aliphatic, aromatic, straight chain, cyclic, bicyclic, branched, saturated, and unsaturated hydrocarbon moieties. When the hydrocarbyl residue is described as substituted, it may contain heteroatoms in addition to carbon and hydrogen.

[0107] The term "alkyl" means a branched or straight chain, unsaturated 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. “Alkenyl” means a straight or branched chain, monovalent hydrocarbon group having at least one carbon-carbon double bond (e.g., ethenyl (-HC=CH2)). “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, -CnH2n-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 aryl group (e.g., benzyl). The prefix "halo" means a group or compound including one more of a fluoro, chloro, bromo, or iodo substituent. A combination of different halo groups (e.g., bromo and fluoro), or23SHPP0037-WO-PCT (SS180005PCT) only chloro groups may be present. The prefix “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. “Substituted” means that the compound or group is substituted with at least one (e.g., 1, 2, 3, or 4) substituents that may each independently be a C1-9 alkoxy, a C1-9 haloalkoxy, a nitro (-NO2), a cyano (-CN), a C1-6 alkyl sulfonyl (-S(=O)2-alkyl), a C6-12 aryl sulfonyl (-S(=O)2-aryl)a thiol (-SH), a thiocyano (-SCN), a tosyl (CH3C6H4SO2-), a C3-12 cycloalkyl, a C2-12 alkenyl, a C5-12 cycloalkenyl, a C6-12 aryl, a C7-13 arylalkylene, a C4-12 heterocycloalkyl, and a C3-12 heteroaryl instead of hydrogen, provided that the substituted atom’s normal valence is not exceeded. The number of carbon atoms indicated in a group is exclusive of any substituents. For example -CH2CH2CN is a C2alkyl group substituted with a nitrile.

[0108] While particular embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are or may be presently unforeseen may arise to applicants or others skilled in the art. Accordingly, the appended claims as filed and as they may be amended are intended to embrace all such alternatives, modifications variations, improvements, and substantial equivalents.

Claims

23SHPP0037-WO-PCT (SS180005PCT) CLAIMS What is claimed is:

1. A thermoplastic composition comprising: a polyester comprising a poly(alkylene arylate); a flame retardant composition comprising a non-fluorinated flame retardant, optionally, an auxiliary flame retardant, and optionally, an anti-drip agent; greater than or equal to 5 wt% of a polyetherimide based on the total weight of the composition, a reinforcing agent; optionally, an additive composition; and wherein the sum of the wt% of the polyester, the flame retardant composition, the polyetherimide, the reinforcing agent, and the optional additive composition total 100 wt%, wherein a sample of the composition exhibits a UL-94 rating of V-0 at a thickness of 0.8 mm, or 0.6 mm, or wherein a sample of the composition exhibits a UL-94 rating of V-0 at a thickness of 0.4 mm, wherein the thermoplastic composition is essentially fluorine-free.

2. The thermoplastic composition of claim 1 comprising 10-80 wt% of the polyester comprising the poly(alkylene arylate); the flame retardant composition comprising a phosphorus-containing flame retardant present in an amount effective to provide up to 6 wt% phosphorus based on the total weight of the composition; 5-15 wt% of the polyetherimide; 5-75 wt% of the reinforcing agent; and 0.01-10 wt% of the additive composition; wherein the sum of the wt% of the polyester, the flame retardant composition, the polyetherimide, the reinforcing agent and the optional additive composition total 100 wt%, and wherein a sample of the composition exhibits a UL-94 rating of V-0 at a thickness of 0.8 mm, preferably 0.6 mm.

3. The thermoplastic composition of claim 1 comprising: 10-80 wt% of the polyester comprising the poly(alkylene arylate); the flame retardant composition comprising a phosphorus-containing flame retardant present in an amount effective to provide 2-6 wt% phosphorus based on the total weight of the composition;23SHPP0037-WO-PCT (SS180005PCT) greater than 5 to 15 wt% of the polyetherimide; 5-75 wt% of the reinforcing agent; and 0.01-10 wt% of the additive composition; wherein the sum of the wt% of the polyester, the flame retardant composition, the polyetherimide, the reinforcing agent, and the optional additive composition total 100 wt%, and wherein a sample of the composition exhibits a UL-94 rating of V-0 at a thickness of 0.4 mm.

4. The thermoplastic composition of claim 3, comprising: 30-70 wt% of the polyester comprising the poly(butylene arylate); the flame retardant composition comprising a phosphorus-containing flame retardant present in an amount effective to provide 2-6 wt% phosphorus based on the total weight of the composition, and no fluorinated anti-drip agent; 6 to 12 wt% of the polyetherimide; 20-75 wt% of the reinforcing agent, wherein the reinforcing agent comprises glass fibers; and 0.01-10 wt% of the additive composition; wherein the sum of the wt% of the polyester, the flame retardant composition, the polyetherimide, the reinforcing agent, and the optional additive composition total 100 wt%, and wherein a sample of the composition exhibits a UL-94 rating of V-0 at a thickness of 0.4 mm.

5. The thermoplastic composition of any one of the preceding claims, wherein the non- fluorinated flame retardant comprises a phosphorus-containing flame retardant present in an amount effective to provide 2-6 wt% phosphorus, based on the total weight of the composition.

6. The thermoplastic composition any one of the preceding claims, wherein the polyetherimide does not comprise a poly(etherimide-siloxane) and wherein the thermoplastic composition comprises 1500 ppm or less of added fluorine.

7. The thermoplastic composition any one of the preceding claims excluding an anti-drip agent, preferably excluding a fluorinated anti-drip agent.

8. The thermoplastic composition any one of the preceding claims wherein: the added bromine and chlorine content of the thermoplastic composition are each 900 ppm or less and the calculated total added halogen content of the thermoplastic composition is 1500 ppm or less; or23SHPP0037-WO-PCT (SS180005PCT) the added bromine, chlorine, and fluorine content of the thermoplastic composition are each 900 ppm or less and the calculated total added bromine, chlorine, and fluorine content of the thermoplastic composition is 1500 ppm or less.

9. The thermoplastic composition of any one of the preceding claims comprising: a poly(alkylene arylate), preferably poly(1,4-butylene terephthalate), and 100 ppm or less of added fluorine.

10. The thermoplastic composition of any one of the preceding claims, wherein the polyester comprises: a poly(1,4-butylene terephthalate) comprising an intrinsic viscosity of 0.5 to 1.0 dL / g ; and a poly(1,4-butylene terephthalate) comprising an intrinsic viscosity of 1.15 to 1.40 dL / g , wherein the wt% of the poly(1,4-butylene terephthalate) comprising an intrinsic viscosity of 1.15 to 1.40 dL / g is less than the poly(1,4-butylene terephthalate) comprising an intrinsic viscosity of 0.5 to 1.0 dL / g .

11. The thermoplastic composition of any one of the preceding claims comprising 6 to 12 wt% of a polyetherimide, based on the total weight of the composition.

12. The thermoplastic composition of any one of the preceding claims, wherein the polyetherimide does not comprise a poly(etherimide-siloxane).

13. A method of making the thermoplastic composition of any one of the preceding claims, the method comprising melt-mixing the components of the composition, and, optionally, extruding the composition.

14. An article comprising the thermoplastic composition of any one of claims 1 to 12.

15. A method of manufacturing the article of claim 14 comprising molding, casting, or extruding the composition to provide the article.

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