Flame retardant thermoplastic compositions

Abstract

A thermoplastic composition including: a polyester including a poly(alkylene arylate); optionally, a polyetherimide; a flame retardant composition comprising a dialkyl phosphinic acid salt, and optionally; optionally an auxiliary flame retardant comprising melamine polyphosphate, melamine cyanurate, melamine pyrophosphate, melamine phosphate, or a combination thereof; a mineral flame retardant synergist comprising a modified fibrillated magnesium silicate, a modified fibrillated aluminum silicate, or a combination thereof; optionally, glass fibers; and optionally, an additive composition; wherein the sum of the wt% of the polyester, the flame retardant composition, the mineral flame retardant synergist, the optional polyetherimide, the optional glass fibers, and the optional additive composition total 100 wt%, and wherein the thermoplastic composition comprises 1500 ppm or less of intentionally added fluorine, and a sample of the thermoplastic composition exhibits a UL 94 flame test rating of V-0 at a thickness of 1.5 mm.

Description

24SHPP0032-WO-PCT(SS180007PCT)FLAME RETARDANT THERMOPLASTIC COMPOSITIONSBACKGROUND

[0001] This disclosure relates to thermoplastic compositions, and in particular to flameretardant thermoplastic compositions, methods of manufacture, and uses thereof, particularly 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. Polyesters 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 can 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 including a poly (alkylene arylate); a poly etherimide or an auxiliary flame retardant comprising melamine polyphosphate, melamine cyanurate, melamine pyrophosphate, melamine phosphate, or a combination thereof; a flame retardant composition comprising a dialkyl phosphinic acid salt and optionally; a mineral flame retardant synergist comprising a modified fibrillated magnesium silicate, a modified fibrillated aluminum silicate, or a combination thereof; optionally, glass fibers; and optionally, an additive composition; wherein the sum of the wt% of the polyester, the flame retardant composition, the mineral flame retardant synergist, the optional polyetherimide, the optional glass fibers, and the optional additive composition total 100 wt%, and wherein the thermoplastic composition comprises 1500 ppm or less of intentionally added fluorine, and a sample of the thermoplastic composition exhibits a UL 94 flame test rating of V-0 at a thickness of 1.5 mm.

[0005] In another aspect, a method of manufacture includes combining the abovedescribed components to form the thermoplastic composition.24SHPP0032-WO-PCT(SS180007PCT)

[0006] In yet another aspect, an article includes the above-described thermoplastic composition. The article can be a thin-wall article.

[0007] In still another aspect, a method of manufacture of an article includes 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 resins 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 dripping can worsen 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-l flame test rating. Conventional low halogen compositions often incorporate fluorine-based antidrip agents either alone or in combination with a non-fluorinated flame retardant in order to pass the UL 94 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 can achieve a V-0 or V-l 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 thermoplastic compositions including a polyester comprising a poly(alkylene arylate); optionally, a polyetherimide; a flame retardant composition comprising a dialkyl phosphinic acid salt, and optionally, an auxiliary flame retardant comprising melamine polyphosphate, melamine cyanurate, melamine pyrophosphate, melamine phosphate, or a combination thereof; a mineral flame retardant synergist comprising a modified fibrillated magnesium silicate, a modified fibrillated aluminum silicate, or a combination thereof; optionally, glass fibers; and optionally, an additive composition can meet the desired flame retardancy while eliminating the need for halogenated additives, such as fluorinated flame retardants and anti-drip agents. Surprisingly, unlike conventional compositions, fluorinated anti-drip agents can be omitted in these thermoplastic compositions, thus eliminating added fluorine while providing improved flammability. Advantageously, the thermoplastic compositions can have a UL-94 flame test rating of V-0 at a thickness of 3.0 mm24SHPP0032-WO-PCT(SS180007PCT) or less, in particular 1.5 mm or 0.6 mm, and be considered “essentially fluorine-free”. As used herein, the phrase “essentially fluorine-free” means that the amount of calculated intentionally added fluorine present in the composition is 1500 parts per million (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 is added to a composition (e.g., TSAN, which is 50 wt% PTFE having 76 wt% fluorine content), the amount of calculated intentionally added fluorine would equal 1900 ppm. In an aspect, the thermoplastic described herein can have zero ppm of intentionally added fluorine.

[0011] In some aspects, the thermoplastic compositions can have a UL-94 flame test rating of V-0 at a thickness of 3.0 mm or thinner and be considered “essentially halogen-free” per IEC 61249-2-21 or UL 746H. As used herein, the phrase “essentially halogen-free” is as defined by IEC 61249-2-21 or UL 746H. According to International Electrochemical Commission, Restriction Use of Halogen (IEC 61249-2-21), a composition should include 900 ppm (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, a composition should include 900 ppm or less of each of chlorine, bromine, and fluorine and 1500 ppm or less of the total chlorine, bromine, and fluorine content. The bromine, chlorine, and fluorine content in ppm can be calculated from the composition or measured by elemental analysis techniques. Conventional flame retardants can include or exclude halogens, but commonly employed 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 antidrip 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 nonfluorinated flame retardants that include or exclude halogens can be used in thermoplastic compositions so that the compositions can be considered “essentially halogen-free” per IEC 61249-2-21 or UL 746H.24SHPP0032-WO-PCT(SS180007PCT)

[0012] As stated above, the thermoplastic compositions include a polyester including a poly (alkylene arylate). The polyesters of the thermoplastic compositions can include aromatic polyesters, poly(alkylene esters) including poly(alkylene arylates), and poly(cycloalkylene diesters). Aromatic polyesters can have a polyester structure according to formula (1) o o- c — T — c — o — J — o - Q) wherein J is a divalent group derived from a dihydroxy compound (including a reactive derivative thereof), and can be, for example, a Ci-io alkylene, a Ce-20 cycloalkylene, or a poly oxy alkylene 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 can be, for example, a C2-20 alkylene, a C5-20 cycloalkylene, a C6-20 arylene, or a combination thereof, provided that at least a portion of the J groups are arylene. Copolyesters containing a combination of different T or J groups can be used. The polyester units can be branched or linear.

[0013] In an aspect, 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.

[0014] Aromatic dicarboxylic acids that can 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 includes a combination of isophthalic acid and terephthalic acid wherein the weight ratio of isophthalic acid to terephthalic acid is 91:9 to 2:98.

[0015] Examples of poly( alkylene terephthalates) include poly(ethylene terephthalate) (PET), poly(l,4-butylene terephthalate) (PBT), and poly (n-propylene terephthalate) (PPT). Also useful are poly(alkylene naphthoates), such as poly(ethylene naphthanoate) (PEN), and poly(butylene naphthanoate) (PBN). A preferably useful poly(cycloalkylene diester) is poly(l,4- cyclohexanedimethylene terephthalate) (PCT). Combinations including at least one of the foregoing polyesters can also be used.24SHPP0032-WO-PCT(SS180007PCT)

[0016] Copolymers including alkylene terephthalate repeating ester units with other ester groups can also be used. Useful ester units can include different alkylene terephthalate units, which can 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 includes greater than or equal to 50 mol% of poly(ethylene terephthalate), and abbreviated as PCTG where the polymer includes greater than 50 mol% of poly(l,4-cyclohexanedimethylene terephthalate).

[0017] Poly(cycloalkylene diester)s can also include poly(alkylene cyclohexanedicarboxylate)s. Of these, a specific example is poly(l,4-cyclohexane-dimethanol- 1 ,4-cyclohexanedicarboxylate) (PCCD) having recurring units of formula (2)wherein, as described using formula (1), 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 can include the cis-isomer, the trans-isomer, or a combination thereof.

[0018] A combination of two or more poly(alkylene arylates)s can be used to achieve the desired intrinsic viscosity of the composition. The combination can 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 can 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 1.00-1.50 dl / g. In some aspects the weight ratio of poly(alkylene arylate) having an intrinsic viscosity of 1.00-1.5 dl / g to poly (alkylene arylate) having an intrinsic viscosity of 0.50-1.0 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- 1.5 dl / g can be present in an amount (weight percent (wt%)) similar to (i.e., within ± 10 wt%, or within ± 5 wt%, within ± 3 wt%) or greater than the poly(alkylene arylate) having an intrinsic viscosity of 0.50-1.0 dl / g.

[0019] The polyesters can 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 can be 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, can24SHPP0032-WO-PCT(SS180007PCT) be used. Furthermore, it can be desirable to have various concentrations of acid and hydroxyl end groups on the polyester, depending on the ultimate end use of the composition.

[0020] The polyester can be present in the thermoplastic composition an amount from 10-90 wt%, based on the total composition, i.e., based on the polyester, the flame retardant composition, the mineral flame retardant synergist, the optional polyetherimide (when present), and the optional additive composition (when present), which totals 100 wt%. Within that range, the polyester can be present in amount from 10-85 wt%, 20-85 wt%, 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 weight of the thermoplastic composition.

[0021] In addition to the polyester, the thermoplastic compositions can optionally include a polyetherimide composition. The polyetherimide composition includes a polyetherimide. In some aspects, the polyetherimide is not a polyetherimide siloxane, i.e., not a polyetherimide including greater than or equal to 3%, or greater than or equal to 10 wt%, to less than or equal to 50 wt% of siloxane repeating units.

[0022] Poly etherimides include more than 1, for example 2 to 1000, or 5 to 500, or 10 to 100 structural units of formula (3)wherein each R is independently the same or different, and is a substituted or unsubstituted divalent organic group, such as a substituted or unsubstituted Ce-20 aromatic hydrocarbon group, a substituted or unsubstituted straight or branched chain C4-20 alkylene group, a substituted or unsubstituted C3-8 cycloalkylene group, or a halogenated derivative of any of the foregoing. In some aspects R is divalent group of one or more of the following formulas (4)24SHPP0032-WO-PCT(SS180007PCT) wherein Q1is -0-, -S-, -C(0)-, -SO2-, -SO-, -P(Ra)(=O)- wherein Rais a Ci-s alkyl or C6-12 aryl, - CyH2y- wherein y is an integer from 1 to 5 or a halogenated derivative thereof, or -(CeHio)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’- phenylene)sulfone, or a combination including 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. In some aspects none of R or Q1includes a halogen.

[0023] Further in formula (3), 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 Ce-24 monocyclic or polycyclic moiety optionally substituted with 1 to 6 Ci-s alkyl groups, 1 to 8 halogen atoms, or a combination including at least one of the foregoing, provided that the valence of Z is not exceeded. Exemplary groups Z include groups of formula (5)wherein Raand Rbare 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 Ce arylene group are disposed ortho, meta, or para (specifically para) to each other on the Ce arylene group. The bridging group Xacan be a single bond, -O-, -S-, -S(O)-, -S(O)2-, -C(O)-, or a Ci-is organic bridging group. The Ci- 18 organic bridging group can be cyclic or acyclic, aromatic or non-aromatic, and can further include heteroatoms such as halogens, oxygen, nitrogen, sulfur, silicon, or phosphorus. The Ci-is organic group can be disposed such that the Ce arylene groups connected thereto are each connected to a common alkylidene carbon or to different carbons of the Ci-is organic bridging group. A specific example of a group Z is a divalent group of formula (5 a)wherein Q is -O-, -S-, -C(O)-, -SO2-, -SO-, -P(Ra)(=O)- wherein Rais a Ci-s alkyl or Ce-12 aryl, or -CyFEy- wherein y is an integer from 1 to 5 or a halogenated derivative thereof. In a specific24SHPP0032-WO-PCT(SS180007PCT) aspect Z is a derived from bisphenol A, such that Q in formula (5a) is 2,2-isopropylidene. In some aspects none of T, Z, or Q includes a halogen.

[0024] In an aspect in formula (3), R is m-phenylene, p-phenylene, or a combination including 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 including at least one of the foregoing, and T is -O-Z-O wherein Z is a divalent group of formula (3a) and Q is 2,2-isopropylidene. Such materials are available under the trade name ULTEM from SABIC. Alternatively, the polyetherimide can be a copolymer including additional structural polyetherimide units of formula (3) wherein at least 50 mole percent (mol%) of the R groups are bis(4,4’-phenylene)sulfone, bis(3,4’-phenylene)sulfone, bis(3,3’-phenylene)sulfone, or a combination including at least one of the foregoing and the remaining R groups are p- phenylene, m-phenylene or a combination including at least one of the foregoing; 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.

[0025] In some aspects, the poly etherimide is a copolymer that optionally includes additional structural imide units that are not polyetherimide units, for example imide units of formula (6)wherein R is as described in formula (3) and each V is the same or different, and is a substituted or unsubstituted Ce-20 aromatic hydrocarbon group, for example a tetravalent linker of the formulaswherein W is a single bond, -O-, -S-, -C(O)-, -SO2-, -SO-, a Ci-is hydrocarbylene group, - P(Ra)(=O)- wherein Rais a Ci-g 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 include less than 20 mol% of the total number of units, and more preferably can 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.24SHPP0032-WO-PCT(SS180007PCT)

[0026] The polyimide or the polyetherimide 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 (7) or a chemical equivalent thereof, with an organic diamine of formula (8)wherein T and R are each defined as described above. Copolymers of the polyetherimides can 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.

[0027] 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 can be used.

[0028] 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, l,2-bis(3-aminopropoxy) ethane, bis(3-aminopropyl) sulfide,24SHPP0032-WO-PCT(SS180007PCT)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-l,3-phenylene-diamine, 5-methyl-4,6-diethyl-l,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) 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 can be used. Ci-4 alkylated or poly(Ci-4)alkylated derivatives of any of the foregoing can 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 including at least one of the foregoing.

[0029] In some aspects the poly etherimide has an Mw of 10,000 to 80,000 g / mol. Such polyetherimides typically have an intrinsic viscosity greater than 0.2 deciliters per gram (dl / g), or, more specifically, 0.35 to 0.7 dl / g as measured in m-cresol at 25°C.

[0030] The polyetherimides can have a melt index of 0.1 to 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-siloxane copolymer can have a weight average molecular weight (Mw) of 1,000 to 150,000 g / mol as measured by gel permeation chromatography using polystyrene standards. In some aspects, the polyetherimide-siloxane copolymer has an Mwof 5,000 to 80,000 g / mol, or 55,000 to 75,000 g / mol, or 60,000 to 70,000 g / mol. 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.

[0031] In some aspects, the polyetherimides can have end groups including carboxylic anhydrides, aryl amines, or a combination thereof. For example, the polyetherimide can have both carboxylic anhydride and aryl amine end groups. In some aspects, improved melt stability can be obtained by a polyetherimide having a greater number of carboxylic anhydride end groups than aryl amine end groups. For example, improved melt stability can be obtained by a polyetherimide-siloxane copolymer having a greater number of carboxylic anhydride end groups than aryl amine end groups.24SHPP0032-WO-PCT(SS180007PCT)

[0032] The thermoplastic compositions include a flame retardant composition including a dialkyl phosphinic acid salt, and optionally, an auxiliary flame retardant comprising melamine polyphosphate, melamine cyanurate, melamine pyrophosphate, melamine phosphate, or a combination thereof. In some aspects, the thermoplastic compositions do not include fluorinated flame retardants such as Rimar (potassium perfluorobutane sulfonate) salt.

[0033] The dialkyl phosphinic acid salt is a compound of formula (9) or (10).(9) (10)In formulas (9) and (10), R1and R2are the same or different as each other and are a linear or branched alkyl group having 1-16 carbon atoms, or 1 to 10 carbon atoms, or 1 to 6 carbon atoms; R3is a linear or branched alkylene group having 1-10 carbon atoms, or an arylene, alkylarylene or arylalkylene group having 6-10 carbon atoms; each M is a metal, for example calcium, magnesium, aluminum or zinc, and n is an integer of 1 to 4, or 2 or 3. In some aspects, R1and R2in formulas (9) and (10) are the same or different as each other and have 1-6 carbon atoms. Examples of R1and R2include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, and n-pentyl.

[0034] The dialkyl phosphinic acid salts as that term is used herein include polymers of the phosphinic acid salts (9) or (10). In an aspect, R1and R2are ethyl, M is aluminum, and d is 3 (that is, the metal di(Ci-6 alkyl)phosphinate is aluminum tris(diethylphosphinate)). From the viewpoint of improving the mechanical properties, corrosiveness to metals, melt retention stability, flowability, and flame retardancy, the metal component can be aluminum, and the salt can be aluminum ethyl methylphosphinic acid salt or aluminum diethylphosphinic acid salt. Such phosphinic acid salts are available commercially as EXOLIT™ OP1230 and OP1240 supplied by Clariant. A combination comprising two or more dialkyl phosphinic acid salts can be used.

[0035] In an aspect, the metal di(Ci-6 alkyl)phosphinate is in particulate form. The metal di(Ci-6 alkyl)phosphinate particles can 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. Additionally, the metal di(Ci-6 alkyl)phosphinate can 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(Ci-6 alkyl)phosphinate masterbatch includes the metal di(Ci-6 alkyl)phosphinate in an amount greater than is present in the24SHPP0032-WO-PCT(SS180007PCT) thermoplastic composition. Employing a masterbatch for the addition of the metal di(Ci-6 alkyl)phosphinate to the other components of the composition can facilitate addition and improve distribution of the metal di(Ci-6 alkyl)phosphinate salt.

[0036] The amount of the dialkyl phosphinic acid salt (i.e., a salt of formula (9), formula(10), or a polymer thereof can be 1 to 35 wt %, or 3 to 30 wt %, or 5 to 25 wt %, based on the total weight of the thermoplastic composition.

[0037] An auxiliary flame retardant can optionally be present in the flame retardant composition, in particular melamine polyphosphate, melamine cyanurate, melamine pyrophosphate, melamine phosphate, or a combination thereof. In some aspects, melamine polyphosphate, melamine cyanurate, melamine pyrophosphate, melamine phosphate, or a combination thereof are present in the thermoplastic composition. When present, the amount of this auxiliary flame retardant agent can be 0.5 to 30 wt %, or 1 to 20 wt %, or 3 to 10 wt %, based on the total weight of the thermoplastic composition.

[0038] In some aspects, no flame retardant other than the metal dialkylphosphinate salt and the optional auxiliary flame retardant (melamine polyphosphate, melamine cyanurate, melamine pyrophosphate, melamine phosphate, or a combination thereof) are present in the thermoplastic composition. In other aspects, the flame retardant composition can optionally include one or more additional flame retardants, for example a flame retardant including a halogen other than fluorine. In some aspects, the flame retardant composition includes a flame retardant including a halogen other than fluorine (e.g., bromine or 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(11):wherein in formula (11) R is an alkylene, alkylidene, or cycloaliphatic linkage (e.g., methylene, ethylene, propylene, isopropylene, isopropylidene, butylene, isobutylene, amylene, cyclohexylene, cyclopentylidene, and the like), a linkage selected from oxygen ether, carbonyl, amine, a sulfur containing linkage (e.g., sulfide, sulfoxide, or sulfone), a phosphorus containing linkage, and 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, and the like; Ar and Ar' can be the same or different and are24SHPP0032-WO-PCT(SS180007PCT) mono- or polycarbocyclic aromatic groups such as phenylene, biphenylene, terphenylene, naphthylene, and 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, and the like, aryl ((e.g., phenyl, naphthyl, biphenyl, xylyl, tolyl, and the like), arylalkylene (e.g., as benzyl, ethylenephenyl, and the like), cycloaliphatic (e.g., cyclopentyl, cyclohexyl, and 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' can be varied in the ortho, meta or para positions on the aromatic rings and the groups can be in any possible geometric relationship with respect to one another.

[0039] 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; l,l-bis-(4-iodophenyl)-ethane; l,2-bis-(2,6- dichlorophenyl)-ethane; l,l-bis-(2-chloro-4-iodophenyl)ethane; l,l-bis-(2-chloro-4- methylphenyl)-ethane; l,l-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- (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- methoxyphenylj-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, l,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, and the like.

[0040] The flame retardant composition can optionally include inorganic flame retardants. Inorganic flame retardants can include metal hydroxides, metal oxides,24SHPP0032-WO-PCT(SS180007PCT) 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. In some aspects, the flame retardant composition can include 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 can be coated, for example, with a silane, or stearic acid or another fatty acid. The flame retardant composition can optionally 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.

[0041] When the flame retardant composition and the auxiliary flame retardant (if present) includes phosphorus, they are present in an amount effective to provide up to 6 wt% phosphorus, based on the total weight of the thermoplastic composition. Within this range, the flame retardant composition and the auxiliary flame retardant (if present) 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 thermoplastic composition.

[0042] The inventors hereof have found that use of a mineral flame retardant synergist comprising a modified fibrillated magnesium silicate, a modified fibrillated aluminum silicate, or a combination thereof, provides a combination of desirable physical and anti-drip properties. As used herein, “fibrillated” means that the magnesium silicate, aluminum silicate, or a combination thereof is, or has been treated to be, fibrillated, for example under shear stress or by another method. The fibrillated magnesium silicate, fibrillated aluminum silicate, or combination thereof can be referred to as “needle-shaped”, i.e., having a high length to diameter (L / D) such as 80 or higher, or 60 or higher, or 40 or higher, or 20 or higher, or 10 or higher. For example, the average L / D can be 2 to 80, or 5 50, or 10 to 40, or 10 to 30, or 20. The modified fibrillated magnesium silicate, modified fibrillated aluminum silicate, or a combination thereof can have a diameter of 1 to 500 nanometers (nm), or 1 to 300 nm, or 1 to 200 nm, or 1 to 100 nm, or 1 to 50 nm, or 5 to 200 nm, or 10 to 150 nm, or 10 to 100 nm. Without being bound by theory, the fibrillation provides a network of the nanofibers, which can increase the zero-shear viscosity, and can be ultimately responsible for the improved anti-drip properties of the thermoplastic compositions.24SHPP0032-WO-PCT(SS180007PCT)

[0043] Modified fibrillated magnesium silicate can be obtained from sepiolite. Sepiolite is a complex magnesium silicate mineral (a clay) with a fibrous morphology. The fibers are typically long and thin, providing a large surface area relative to its volume. Sepiolite can have a Mohs hardness of 2-2.5, and a relatively low density of about 2 g / cm3.

[0044] The mineral flame retardant synergist is a fibrillated, magnesium silicate or fibrillated aluminum silicate that has been modified, i.e., pre-treated. The treatment can be a surface treatment or other treatment. Without being bound by theory, the pre-treatment can be effective to provide desired properties such as improved compatibility or bonding with the polymer, which can provide improved , dispersion, mechanical properties, or the like. The pretreatment can be with organic or inorganic compounds including aluminum (e.g., aluminum salts), boron (e.g., boric acid or borate salts), nitrogen (e.g., long-chain trialkyl ammonium salts), phosphorus (e.g., phosphates, phosphonates, phosphites, phosphides, or the like), or silicon (e.g., silicates, silanes, silicones, and the like). As would be understood by one of ordinary skill in the art, such pre-treatments can include penetration beyond the surface, for example exfoliation, ceramification, and the like. Accordingly, the fibrillated (i.e., needle- shaped) magnesium silicate or fibrillated (i.e., needle-shaped) aluminum silicate can be pretreated to provide aluminum, nitrogen, phosphorus, silicon, or a combination thereof to the silicate. In an aspect, the fibrillated magnesium silicate or fibrillated aluminum silicate can be pre-treated by combining with glass particles. As stated above, the magnesium silicate or aluminum silicate may or may not be treated to provide the fibrillation (i.e., magnesium silicate or aluminum silicate may be naturally available in a fibrillated (needle-shaped form). Pretreatment can occur before or after fibrillation, if used, to provide the modified fibrillated magnesium silicate, modified fibrillated aluminum silicate, or combination thereof, before combining with the other components of the compositions.

[0045] The modified, fibrillated magnesium silicate, aluminum silicate, or a combination thereof can be adjusted to have a desired range of particle sizes that can be varied depending on the pre-treatment used, the thermoplastic composition used, the dispersion characteristics of the silicate, the method of dispersing the silicate, and the desired properties of the thermoplastic composition. For example, a useful particle size is one where dry sieving through a 45- micrometer screen leaves a maximum sieving residue of 10 wt%, or 5 wt%, or 3 wt%, or 1 wt%. Another useful particle size is one where dry sieving through a 25-micrometer screen leaves a maximum sieving residue of 10 wt%, or 5 wt%, or 3 wt%, or 1 wt%; or dry sieving through a 60-micrometer screen leaves a maximum sieving residue of 10 wt%, or 5 wt%, or 3 wt%, or 1 wt%.24SHPP0032-WO-PCT(SS180007PCT)

[0046] The amount of the modified fibrillated magnesium silicate, modified fibrillated aluminum silicate, or a combination thereof can be 0.5 to 30 wt %, or 1 to 20 wt %, or 3 to 10 wt %, based on the total weight of the thermoplastic 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 antidrip agent can be encapsulated by a rigid copolymer, for example styrene-acrylonitrile copolymer (SAN). PTFE encapsulated in SAN is known as TSAN. An TSAN includes 50 wt% PTFE and 50 wt% SAN, based on the total weight of the encapsulated fluoropolymer. The SAN can include, 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 antidrip agent is excluded from the thermoplastic compositions.

[0048] The thermoplastic composition can 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. Such additives can 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 can 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) can 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(Ci-4 alkylene oxide) glycol having a number-average molecular weight of 400 to 6000, and R20is derived from a C4-24 aliphatic or aromatic24SHPP0032-WO-PCT(SS180007PCT) dicarboxylic acid, preferably an aromatic dicarboxylic acid; and “hard block” short-chain ester units of formula (16) O O— C1 1-R 20-C1 1-O-D-O— (16) wherein D is a Ci-io alkylene or cycloalkylene derived from the corresponding diol having a molecular weight of less than or equal to 300; and R20is derived from a C4-24 aliphatic, 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) 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 polyesterether) 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(l,4-cyclohexane- dimethanol-l,4-cyclohexane dicarboxylate) (PCCD) units.

[0051] Colorants such as pigment or dye additives can 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;24SHPP0032-WO-PCT(SS180007PCT) 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)-l,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- diphenyloxazole; 4,4'-diphenylstilbene; 4-dicyanomethylene-2-methyl-6-(p- dimethylaminostyryl)-4H-pyran; l,r-diethyl-2,2'-carbocyanine iodide; 3,3'-diethyl-4,4',5,5'- dibenzothiatricarbocyanine iodide; 7-dimethylamino-l-methyl-4-methoxy-8-azaquinolone-2; 7- dimethylamino-4-methylquinolone-2; 2-(4-(4-dimethylaminophenyl)-l,3-butadienyl)-3- ethylbenzothiazolium perchlorate; 3-diethylamino-7-diethyliminophenoxazonium perchlorate; 2- (l-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 can optionally include a reinforcing agent.Reinforcing agents can include, for example, mica, clay, feldspar, quartz, quartzite, perlite, tripoli, diatomaceous earth, alumina, 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, 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, TiCh, 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,24SHPP0032-WO-PCT(SS180007PCT) polytetrafluoroethylene, and poly(vinyl alcohol), as well a combination thereof. The fillers and reinforcing agents can 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 can 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 can be provided in the form of monofilament or multifilament fibers and can 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.

[0055] The reinforcing fibers can 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 can 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 can be present 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 polyester comprising a poly(alkylene arylate), preferably poly(butylene terephthalate); optionally, a polyetherimide; a flame retardant composition comprising a dialkyl phosphinic acid salt, and optionally, an auxiliary flame retardant comprising melamine polyphosphate, melamine cyanurate, melamine pyrophosphate, melamine phosphate, or a combination thereof; a mineral flame retardant synergist comprising a modified fibrillated magnesium silicate, a modified fibrillated aluminum silicate, or a combination thereof; optionally, glass fibers; and optionally, an additive composition; wherein the thermoplastic composition comprises 1500 ppm or less of intentionally added fluorine, and a sample of the thermoplastic composition exhibits a UL 94 flame test rating of V-0 at a thickness of 0.8 mm. In these aspects, one or more of the following24SHPP0032-WO-PCT(SS180007PCT) can apply: the pre-treatment of the fibrillated, magnesium silicate provides aluminum, boron, nitrogen, phosphorus, silicon, or a combination thereof to a surface of the magnesium silicate; or the flame retardant composition is present in an amount effective to provide 3-6 wt% phosphorus, based on the total weight of the composition; or the optional polyetherimide is present but does not include a poly etherimide siloxane; or wherein the polyester comprises a poly(l,4-butylene terephthalate) comprising an intrinsic viscosity of 0.5 to 1.0 dl / g, and a poly(l,4-butylene terephthalate) comprising an intrinsic viscosity of 1.00 to 1.50 dl / g, optionally wherein a wt% of the poly(l,4-butylene terephthalate) having an intrinsic viscosity of 1.00 to 1.50 dl / g is similar to or greater than the poly(l,4-butylene terephthalate) having an intrinsic viscosity of 0.5 to 1.0 dl / g; or a combination thereof, wherein the intrinsic viscosity of poly(l,4- butylene terephthalate) is measured at 30 °C in a 1 :1 w / w solution of phenol: 1,1, 2,2- tetrachloroethane, and having 17 milliequivalents per kilogram (meq / kg) of COOH.

[0058] In some aspects, the thermoplastic compositions include the polyester comprising the poly(alkylene arylate); the polyetherimide; the flame retardant composition comprising the dialkyl phosphinic acid salt, and optionally, an auxiliary flame retardant comprising melamine polyphosphate, melamine cyanurate, melamine pyrophosphate, melamine phosphate, or a combination thereof; the mineral flame retardant synergist comprising the modified fibrillated magnesium silicate, the modified fibrillated aluminum silicate, or a combination thereof; and optionally, an additive composition; wherein the thermoplastic composition comprises 1500 ppm or less of intentionally added fluorine, and a sample of the thermoplastic composition exhibits a UL 94 flame test rating of V-0 at a thickness of 0.8 mm. In these aspects, one or more of the following can apply: the pre-treatment of the modified fibrillated, magnesium silicate provides aluminum, boron, nitrogen, phosphorus, silicon, or a combination thereof to a surface of the magnesium silicate; or the flame retardant composition is present in an amount effective to provide 3-6 wt% phosphorus, based on the total weight of the composition; or the poly etherimide is present but does not include a poly etherimide siloxane; or the polyester comprises a poly(l,4-butylene terephthalate) comprising an intrinsic viscosity of 0.5 to 1.0 dl / g, and a poly(l,4-butylene terephthalate) comprising an intrinsic viscosity of 1.00 to 1.50 dl / g, , optionally wherein a wt% of the poly( 1,4- butylene terephthalate) having an intrinsic viscosity of 1.00 to 1.50 dl / g is similar to or greater than the poly(l,4-butylene terephthalate) having an intrinsic viscosity of 0.5 to 1.0 dl / g; or a combination thereof.

[0059] In some aspects, the thermoplastic compositions include the polyester comprising the poly(alkylene arylate), preferably poly(l,4-butylene terephthalate); optionally, the poly etherimide; the flame retardant composition comprising the dialkyl phosphinic acid salt, and24SHPP0032-WO-PCT(SS180007PCT) the auxiliary flame retardant comprising melamine polyphosphate, melamine cyanurate, melamine pyrophosphate, melamine phosphate, or a combination thereof; the mineral flame retardant synergist comprising the modified fibrillated magnesium silicate, the modified fibrillated aluminum silicate, or a combination thereof; the glass fibers; and optionally, an additive composition; wherein the thermoplastic composition comprises 1500 ppm or less of intentionally added fluorine, and a sample of the thermoplastic composition exhibits a UL 94 flame test rating of V-0 at a thickness of 0.4 mm. In these aspects, one or more of the following can apply: the pre-treatment of the modified fibrillated, magnesium silicate provides aluminum, boron, nitrogen, phosphorus, silicon, or a combination thereof to a surface of the magnesium silicate; or the flame retardant composition is present in an amount effective to provide 3-6 wt% phosphorus, based on the total weight of the composition; or the optional poly etherimide is present but does not include a poly etherimide siloxane; or 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(l,4-butylene terephthalate) comprising an intrinsic viscosity of 1.00 to 1.50 dl / g, optionally wherein a wt% of the poly(l,4-butylene terephthalate) having an intrinsic viscosity of 1.00 to 1.50 dl / g is similar to or greater than the poly(l,4-butylene terephthalate) having an intrinsic viscosity of 0.5 to 1.0 dl / g; or a combination thereof.

[0060] In some aspects, the thermoplastic compositions include the polyester comprising a poly(l,4-butylene terephthalate) comprising an intrinsic viscosity of 1.00 to 1.50 dl / g, a poly(l,4-butylene terephthalate) comprising an intrinsic viscosity of 0.5 to 1.0 dl / g; up to 10 wt% of the poly etherimide; the flame retardant composition comprising the dialkyl phosphinic acid salt, and optionally, the auxiliary flame retardant comprising melamine polyphosphate, melamine cyanurate, melamine pyrophosphate, melamine phosphate, or a combination thereof, wherein the flame retardant composition is present in an amount effective to provide 2-6 wt% phosphorus; the mineral flame retardant synergist comprising the modified fibrillated magnesium silicate, the modified fibrillated aluminum silicate, or a combination thereof; and optionally, the additive composition; wherein the thermoplastic composition comprises 1500 ppm or less of intentionally added fluorine, and a sample of the thermoplastic composition exhibits a UL 94 flame test rating of V-0 at a thickness of 0.8 mm. In these aspects, one or more of the following can apply: the pre-treatment of the modified fibrillated, magnesium silicate provides aluminum, boron, nitrogen, phosphorus, silicon, or a combination thereof to a surface of the magnesium silicate; or the polyetherimide is present but does not include a polyetherimide siloxane; optionally wherein a wt% of the poly(l,4-butylene terephthalate) having an intrinsic24SHPP0032-WO-PCT(SS180007PCT) viscosity of 1.00 to 1.50 dl / g is similar to or greater than the poly(l,4-butylene terephthalate) having an intrinsic viscosity of 0.5 to 1.0 dl / g; or a combination thereof.

[0061] In some aspects, the thermoplastic compositions include a poly(l,4-butylene terephthalate) comprising an intrinsic viscosity of 0.5 to 1.0 dl / g; and a poly(l,4-butylene terephthalate) comprising an intrinsic viscosity of 1.00 to 1.50 dl / g, the flame retardant composition comprising a dialkyl phosphinic acid salt and an auxiliary flame retardant comprising melamine polyphosphate, melamine cyanurate, melamine pyrophosphate, melamine phosphate, or a combination thereof, wherein the flame retardant composition is present in an amount effective to provide 2-6 wt% phosphorus; the mineral flame retardant synergist comprising the modified fibrillated magnesium silicate, the modified fibrillated aluminum silicate, or a combination thereof; glass fibers; optionally, the additive composition; and wherein the thermoplastic composition comprises 1500 ppm or less of intentionally added fluorine, and a sample of the thermoplastic composition exhibits a UL 94 flame test rating of V-0 at a thickness of 0.4 mm. In these aspects, one or more of the following can apply: the pre-treatment of the fibrillated magnesium silicate provides aluminum, boron, nitrogen, phosphorus, silicon, or a combination thereof to a surface of the magnesium silicate; a wt% of the poly(l,4-butylene terephthalate) having an intrinsic viscosity of 1.00 to 1.50 dl / g is similar to or greater than the poly(l,4-butylene terephthalate) having an intrinsic viscosity of 0.5 to 1.0 dl / g; or a combination thereof.

[0062] In some aspects, the thermoplastic compositions include a poly(l,4-butylene terephthalate) comprising an intrinsic viscosity of 0.5 to 1.0 dl / g; and a poly(l,4-butylene terephthalate) comprising an intrinsic viscosity of 1.00 to 1.50 dl / g; up to 10 wt% of the poly etherimide; the flame retardant composition comprising the dialkyl phosphinic acid salt and the auxiliary flame retardant comprising melamine polyphosphate, melamine cyanurate, melamine pyrophosphate, melamine phosphate, or a combination thereof, wherein the flame retardant composition is present in an amount effective to provide 2-6 wt% phosphorus; a mineral flame retardant synergist comprising the modified fibrillated, magnesium silicate, the modified fibrillated aluminum silicate, or a combination thereof; glass fibers; and optionally, the additive composition; wherein the thermoplastic composition comprises 1500 ppm or less of intentionally added fluorine, and a sample of the thermoplastic composition exhibits a UL 94 flame test rating of V-0 at a thickness of 0.4 mm. In these aspects, one or more of the following can apply: the pretreatment of the modified fibrillated, magnesium silicate provides aluminum, boron, nitrogen, phosphorus, silicon, or a combination thereof to a surface of the magnesium silicate; or the flame retardant composition is present in an amount effective to provide 3-6 wt%24SHPP0032-WO-PCT(SS180007PCT) phosphorus, based on the total weight of the composition; the polyetherimide is present but does not include a polyetherimide siloxane; or a wt% of the poly(l,4-butylene terephthalate) having an intrinsic viscosity of 1.00 to 1.50 dl / g is similar to or greater than the poly(l,4-butylene terephthalate) having an intrinsic viscosity of 0.5 to 1.0 dl / g; or a combination thereof.

[0063] In any of the foregoing aspects, the thermoplastic compositions can have ultralow halogen content. As used herein, “ultra-low chlorine and / or bromine content” refers to materials produced without the intentional addition of chlorine or bromine or chlorine or bromine containing materials. It is understood however that in facilities that process multiple products a certain amount of cross contamination can occur resulting in bromine or chlorine levels typically on the ppm by weight scale. With this understanding it can be readily appreciated that “ultra-low chlorine or bromine content” can be defined as having a bromine or chlorine content of less than or equal to 100 ppm by weight (ppm), less than or equal to 75 ppm, or less than or equal to 50 ppm. In some aspects, “ultra-low chlorine and bromine content” means a total bromine and chlorine content of less than or equal to 100 ppm by weight, or less than or equal to 75 ppm, or less than or equal to 50 ppm. When this definition is applied to the non-fluorinated flame retardant it is based on the total weight of the non-fluorinated flame retardant. When this definition is applied to the thermoplastic composition it is based on the total parts by weight of the thermoplastic composition.

[0064] In another aspect, the thermoplastic composition can 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, based on the total parts by weight of the composition. Preferably, the thermoplastic composition has a combined 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, based on the total parts by weight of the composition.

[0065] The thermoplastic compositions can 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, can 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 can be incorporated into the composition by feeding directly into the extruder at the throat or downstream through a sidestuffer. Additives can 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.24SHPP0032-WO-PCT(SS180007PCT)The extrudate is immediately quenched in a water bath or using a belt and water sprays magnesium silicate and pelletized. The pellets so prepared can be one-fourth inch long or less as desired. Such pellets can be used for subsequent molding, shaping, or forming.

[0066] A sample of the thermoplastic composition can have a flame test rating of V-l or V-0, as measured according to UL-94 at a thickness of 0.8 millimeter or less, for example, 0.6 millimeter.

[0067] Shaped, formed, or molded articles including the thermoplastic compositions are also provided. The thermoplastic compositions can 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, sunrooms, swimming pool enclosures, advanced driver assistance systems (ADAS) enclosures, and the like. In an aspect, 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 can be used for such applications as a molded housing and other devices such as electrical circuit housing.

[0068] Thin films including the thermoplastic compositions are also provided. The thin film including the thermoplastic composition can be prepared by extrusion of the thermoplastic composition. The thin films can have improved thermal resistance. In some aspects, the thin films can be transparent.

[0069] This disclosure is further illustrated by the following examples, which are nonlimiting.EXAMPLES

[0070] 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.

[0071] The materials shown in Table 1 were used.Table 1.24SHPP0032-WO-PCT(SS180007PCT)

[0072] Samples were compounded on a Coperion ZSK 26 mm co-rotating twin-screw extruder with a vacuum vent. The temperature profile and other extruder settings are provided in Table 2.Table 2.

[0073] The compounded strand was cooled in a water bath prior to pelletizing. The pellets were dried for two hours at 100-120 °C in a forced air-circulating oven prior to injection molding. Sample parts were molded on an Engel molding machine. Molding settings are provided in Table 3.Table 3.24SHPP0032-WO-PCT(SS180007PCT)| Screw speed

[0074] Flammability tests were performed on samples melt-mixed and molded as decribed above at an indicated thickness (e.g., 1.5 mm, 0.75 mm, 0.6 mm, or 0.4 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 = tl + 12) were determined.Table 4.

[0075] Sample size and testing methods are described in Table 5.Table 5.

[0076] Table 6 shows compositions and properties for unfilled (non-glass filled) compositions that are comparative.Table 6.24SHPP0032-WO-PCT(SS180007PCT)

[0077] Comparative Examples CE1-CE4 do not include any clay additive. CE1 and CE2 include DEPAL, but no MPP. The flame test performance of CE1 was poor (i.e., “NR” or not rated). The addition of an anti-drip agent (i.e., TSAN) to the composition substantially improved the flame test performance (compare CE2 with CE1). However, TSAN is a fluorinated additive contributing added fluorine to the composition, which is undesirable. CE3 includes a combination of DEPAL and MPP, but does not include a clay additive or PEI and resulted in poor flame test performance. CE4 includes a combination of DEPAL and PEI, but does not include a clay additive or MPP and also resulted in poor flame test performance. CE5 includes a combination of DEPAL, MPP, and PEI, but does not include a clay additive, which also resulted in poor flame test performance. Therefore, in unfilled compositions, DEPAL / MPP, DEPAL / PEI and DEPAL / MPP / PEI are insufficient to improve the flame test performance (compare CE1 with CE3, CE4, and CE5).

[0078] Comparative Examples A-C (CE-A to CE-C) include DEPAL and a clay additive. CE-A, which included a phosphorus compound-coated clay additive (“CLAY-1”), failed to improve the flame test performance at a thickness of 0.75 mm (compare CE1 with CE- A). CE-B and CE-C, which include a clay additive surface treated with silicon-containing compound demonstrated an improvement in flame test performance (i.e., from NR to V-2) at a thickness of 0.75 mm (compare CE-B and CE-C with CE1).

[0079] The compositions of Table 7 include clay additives surface treated with silane in combination with either DEPAL / PEI (E7-E8) or DEPAL / PEI / MPP (E9-E13).Table 7.24SHPP0032-WO-PCT(SS180007PCT)

[0080] Examples 4-5 (E4-E5) include clay additives surface treated with a silicon- containing compound in combination with DEPAL / PEI, where no MPP was present. E4 demonstrated an improvement in flame test performance as compared with CE4 (see Table 5), resulting in a V-2 rating at both 1.0 mm and 0.75 mm, whereas CE4 had no rating at both 1.0 mm and 0.75 mm. E5 is the same as E4, except that a different clay additive was used (CLAY- 3). Despite this small difference, the flame test performance was adversely affected, resulting in no rating.

[0081] Examples 6-9 (E6-E9) include clay additives surface treated with a silicon- containing compound in combination with DEPAL, PEI, and MPP. E6, which includes the same loading of the same type of clay additive as E4, provided a substantial improvement in the flame test performance at both 1.0 and 0.75 mm thicknesses. The difference between E4 and E6 is the presence of MPP in E6. E7-E9 include DEPAL, PEI, and MPP, but the effect of the amount of the clay additive was explored. Reducing the loading of the clay additive from 5.5 wt% to 4 wt% did not affect the flame test performance at a thickness of 1.5 mm, but it did adversely affect the flame test performance at a 0.75 mm thickness, wherein E7 provided a V-2 rating at a 0.75 mm thickness, whereas E6 which included 5.5 wt% clay additive achieved a V-0 rating at the same thickness. Decreasing the loading of the clay additive to 2.5 wt% (see E8) resulted in a further24SHPP0032-WO-PCT(SS180007PCT) loss in flame test performance, resulting in a V-2 rating at a thickness of 1.5 mm, whereas E7 achieved a V-0 rating at a thickness of 1.5 mm.

[0082] Table 8 shows glass-filled compositions with a combination of DEPAL and MPP.Table 8.

[0083] Comparison of CE6 with CE7 shows a similar trend to that observed for E1-E2, wherein the presence of an anti-drip agent (TSAN) is needed to improve the flame test performance for compositions including DEPAL and MPP but omitting a clay additive and PEI. CE8 and CE9 include DEPAL, MPP, and PEI. CE8 provided a V-0 rating at 0.75 mm and thickness of 0.6 mm. CE9, which included TSAN, achieved a V-0 rating at 0.75 mm, 0.6 mm, and 0.4 mm thicknesses. However, as discussed, fluorine containing additives such as TSAN are undesirable. E10-E13 include DEPAL, MPP, as well as clay additives (but no PEI). E10, which included 5.5 wt% of a clay additive surface treated with a phosphorus-containing compound (CLAY-1) provided a flame test performance of V-l at 0.6 mm as compared with CE6, which had no rating at 0.6 mm. El 1 -El 3, which included a different clay additive that was surface treated with a silicon-containing compound, provided additional improvement in flame test24SHPP0032-WO-PCT(SS180007PCT) performance, resulting in V-0 flame test ratings at 0.6 mm and 0.4 mm, even at a loading as low as 2.5 wt%.

[0084] Table 9 shows glass-filled compositions having a combination of DEPAL, MPP, and clay additives.Table 9.

[0085] E14-E16 include DEPAL, MPP, 5 wt% PEI, and a clay additive surface treated with silane (CLAY-2), providing V-0 flame test ratings at 0.6 mm and 0.4 mm, even at a low loading of the clay additive (i.e., 2.5 wt%). E17-E18 explore the effect of decreasing the loading of PEI from 5 wt% to 2.5 wt% (compare E17 with E14 and El 8 with E15). The reduction of PEI had no adverse effect on the flame test performance. E19 includes DEPAL, MPP, and a clay additive surface treated with silane (CLAY-3). Comparison of E19 with El l shows similar flame test performance.

[0086] This disclosure further encompasses the following aspects.

[0087] Aspect 1. A thermoplastic composition including: a polyester including a poly(alkylene arylate); optionally, a poly etherimide; a flame retardant composition including a dialkyl phosphinic acid salt, optionally, an auxiliary flame retardant including melamine24SHPP0032-WO-PCT(SS180007PCT) polyphosphate, melamine cyanurate, melamine pyrophosphate, melamine phosphate, or a combination thereof; a mineral flame retardant synergist including a modified fibrillated magnesium silicate, a modified fibrillated aluminum silicate, or a combination thereof; optionally, glass fibers; and optionally, an additive composition; wherein the sum of the wt% of the polyester, the flame retardant composition, the mineral flame retardant synergist, the optional polyetherimide, the optional glass fibers, and the optional additive composition total 100 wt%, and wherein the thermoplastic composition includes 1500 ppm or less of intentionally added fluorine, and a sample of the thermoplastic composition exhibits a UL 94 flame test rating of V-0 at a thickness of 1.5 mm.

[0088] Aspect 2. The thermoplastic composition of aspect 1, the polyester including the poly (alkylene arylate); the polyetherimide; the flame retardant composition including the dialkyl phosphinic acid salt; optionally, the auxiliary flame retardant including melamine polyphosphate, melamine cyanurate, melamine pyrophosphate, melamine phosphate, or a combination thereof; the mineral flame retardant synergist including the modified fibrillated magnesium silicate, the modified fibrillated aluminum silicate, or a combination thereof; and optionally, an additive composition; wherein the sum of the wt% of the polyester, the flame retardant composition, the mineral flame retardant synergist, the polyetherimide, and the optional additive composition total 100 wt%, and wherein the thermoplastic composition includes 1500 ppm or less of intentionally added fluorine, and a sample of the thermoplastic composition exhibits a UL 94 flame test rating of V-0 at a thickness of 0.8 mm.

[0089] Aspect 3. The thermoplastic composition of aspect 1 including: the polyester including the poly(alkylene arylate) ;optionally, the polyetherimide; the flame retardant composition including the dialkyl phosphinic acid salt; the auxiliary flame retardant including melamine polyphosphate, melamine cyanurate, melamine pyrophosphate, melamine phosphate, or a combination thereof; the mineral flame retardant synergist including the modified fibrillated magnesium silicate, the modified fibrillated aluminum silicate, or a combination thereof; the glass fibers; and optionally, an additive composition; wherein the sum of the wt% of the polyester, the flame retardant composition, the mineral flame retardant synergist, the optional polyetherimide, the glass fibers, and the optional additive composition total 100 wt%, and wherein the thermoplastic composition includes 1500 ppm or less of intentionally added fluorine, and a sample of the thermoplastic composition exhibits a UL 94 flame test rating of V- 0 at a thickness of 0.6 mm.

[0090] Aspect 4. The thermoplastic composition of any aspect 1, or one of aspects 1 to 3, the polyester including a poly( 1,4- butylene terephthalate) including an intrinsic viscosity of 1.0024SHPP0032-WO-PCT(SS180007PCT) to 1.50 dl / g, a poly(l,4-butylene terephthalate) including an intrinsic viscosity of 0.5 to 1.0 dl / g; and up to 10 wt% of the polyetherimide; the flame retardant composition including the dialkyl phosphinic acid salt; and optionally, the auxiliary flame retardant including melamine polyphosphate, melamine cyanurate, melamine pyrophosphate, melamine phosphate, or a combination thereof, wherein the flame retardant composition and the optional the auxiliary flame retardant is present in an amount effective to provide 2-6 wt% phosphorus; the mineral flame retardant synergist including the modified fibrillated magnesium silicate, the modified fibrillated aluminum silicate, or a combination thereof; and optionally, the additive composition; wherein the sum of the wt% of the polyester, the flame retardant composition, the mineral flame retardant synergist, the polyetherimide, and the optional additive composition total 100 wt%, and wherein the thermoplastic composition includes 1500 ppm or less of intentionally added fluorine, and a sample of the thermoplastic composition exhibits a UL 94 flame test rating of V- 0 at a thickness of 0.8 mm.

[0091] Aspect 5. The thermoplastic composition of aspect 4, or any one of aspects 1 to 3, wherein a wt% of the poly(l,4-butylene terephthalate) having an intrinsic viscosity of 1.00 to 1.50 dl / g is similar to or greater than the poly(l,4-butylene terephthalate) having an intrinsic viscosity of 0.5 to 1.0 dl / g.

[0092] Aspect 6. The thermoplastic composition of aspect 1, or any one of aspects 1 to 5, including: a poly(l,4-butylene terephthalate) including an intrinsic viscosity of 0.5 to 1.0 dl / g; and a poly(l,4-butylene terephthalate) including an intrinsic viscosity of 1.00 to 1.50 dl / g, the flame retardant composition including a dialkyl phosphinic acid salt and the auxiliary flame retardant including melamine polyphosphate, melamine cyanurate, melamine pyrophosphate, melamine phosphate, or a combination thereof, is present in an amount effective to provide 2-6 wt% phosphorus; the mineral flame retardant synergist including the modified fibrillated magnesium silicate, the modified fibrillated aluminum silicate, or a combination thereof; glass fibers; optionally, the additive composition; and wherein the sum of the wt% of the polyester, the flame retardant composition, the mineral flame retardant synergist, the optional polyetherimide, the glass fibers, and the optional additive composition total 100 wt%, and wherein the thermoplastic composition includes 1500 ppm or less of intentionally added fluorine, and a sample of the thermoplastic composition exhibits a UL 94 flame test rating of V- 0 at a thickness of 0.4 mm.

[0093] Aspect 7. The thermoplastic composition of aspect 1, or any one of aspects 1 to 6 including: a poly(l,4-butylene terephthalate) including an intrinsic viscosity of 0.5 to 1.0 dl / g; and a poly(l,4-butylene terephthalate) including an intrinsic viscosity of 1.00 to 1.50 dl / g,24SHPP0032-WO-PCT(SS180007PCT) wherein the wt% of the poly(l,4-butylene terephthalate) including an intrinsic viscosity of 1.00 to 1.50 dl / g is greater than the poly(l,4-butylene terephthalate) including an intrinsic viscosity of 0.5 to 1.0 dl / g; up to 10 wt% of the poly etherimide; the flame retardant composition including the dialkyl phosphinic acid salt and the auxiliary flame retardant including melamine polyphosphate, melamine cyanurate, melamine pyrophosphate, melamine phosphate, or a combination thereof is present in an amount effective to provide 2-6 wt% phosphorus; a mineral flame retardant synergist including the modified fibrillated magnesium silicate, the modified fibrillated aluminum silicate, or a combination thereof; glass fibers; and optionally, the additive composition; wherein the sum of the wt% of the polyester, the flame retardant composition, the mineral flame retardant synergist, the optional polyetherimide, the glass fibers, and the optional additive composition total 100 wt%, and wherein the thermoplastic composition includes 1500 ppm or less of intentionally added fluorine, and a sample of the thermoplastic composition exhibits a UL 94 flame test rating of V-0 at a thickness of 0.4 mm.

[0094] Aspect 8. The thermoplastic composition of any one of the preceding aspects, wherein the pre-treatment of the modified fibrillated magnesium silicate provides aluminum, boron, nitrogen, phosphorus, silicon, or a combination thereof to a surface of the magnesium silicate.

[0095] Aspect 9. The thermoplastic composition of aspect 2 or aspect 4, wherein the composition includes no glass fibers and 5 to 10 wt% of a fibrillated silicon-treated magnesium silicate, a fibrillated silicon-treated aluminum silicate, or a combination thereof, and the sample of the composition exhibits a UL 94 flame test rating of V-0 at a thickness of 0.8 mm; or the composition includes 0.5 to 10 wt% of the glass fibers and 0.5 to 10 wt% of a fibrillated silicon- treated magnesium silicate, a fibrillated silicon-treated aluminum silicate, or a combination thereof, and the sample of the composition exhibits a UL 94 flame test rating of V-0 at a thickness of 0.8 mm.

[0096] Aspect 10. The thermoplastic composition of aspects 3, 6, or 7, wherein the polyester includes no less than 34 wt.% of poly(l,4-butylene terephthalate) having an intrinsic viscosity of 0.5 to 1.0 dl / g) and no less than 14 wt.% of poly(l,4-butylene terephthalate) having an intrinsic viscosity of 1.00 to 1.50 dl / g, up to 10 wt.% of the polyetherimide, a fibrillated silicon-treated magnesium silicate, a fibrillated silicon-treated aluminum silicate, or a combination thereof, and the sample exhibits a UL 94 flame test rating of V-0 at a thickness of 0.8 mm or a sample of the thermoplastic composition exhibits a UL 94 flame test rating of V-0 at 0.4 mm.24SHPP0032-WO-PCT(SS180007PCT)

[0097] Aspect 11. The thermoplastic composition of any one of the preceding aspects, wherein the flame retardant composition is present in an amount effective to provide 3-6 wt% phosphorus, based on the total weight of the composition.

[0098] Aspect 12. The thermoplastic composition of any one of the preceding aspects wherein: the calculated 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; or the calculated 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.

[0099] Aspect 13. A method of making the thermoplastic composition of any of aspects 1 to 12, the method including melt-mixing the components of the composition, and, optionally, extruding the melt-mixed composition.

[0100] Aspect 14. An article including the thermoplastic composition of any of aspects 1 to 12.

[0101] Aspect 15. A method of manufacturing the article of aspect 14 including molding, casting, or extruding the composition to provide the article.

[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, and the like. The terms “first,” “second,” and the like, do not denote any order, quantity, or importance, but rather are used to distinguish one element from another. The terms “a” 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 can 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.24SHPP0032-WO-PCT(SS180007PCT)

[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 dashthat 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 can be aliphatic or aromatic, straight-chain, cyclic, bicyclic, branched, saturated, or unsaturated. It can 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 can 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), or24SHPP0032-WO-PCT(SS180007PCT) only chloro groups can 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 can 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 C2 alkyl group substituted with a nitrile.

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

Claims

24SHPP0032-WO-PCT(SS180007PCT)CLAIMSWhat is claimed is:

1. A thermoplastic composition comprising: a polyester comprising a poly(alkylene arylate); at least one of a polyetherimide or an auxiliary flame retardant, wherein the auxiliary flame retardant comprises melamine polyphosphate, melamine cyanurate, melamine pyrophosphate, melamine phosphate, or a combination thereof; a flame retardant composition comprising a dialkyl phosphinic acid salt; a mineral flame retardant synergist comprising a modified fibrillated magnesium silicate, a modified fibrillated aluminum silicate, or a combination thereof; optionally, glass fibers; and optionally, an additive composition; wherein the sum of the wt% of the polyester, the flame retardant composition, the mineral flame retardant synergist, the optional polyetherimide, the optional glass fibers, and the optional additive composition total 100 wt%, and wherein the thermoplastic composition comprises 1500 ppm or less of intentionally added fluorine, and a sample of the thermoplastic composition exhibits a UL 94 flame test rating of V-0 at a thickness of 1.5 mm.

2. The thermoplastic composition of claim 1 comprising: the polyester comprising the poly (alkylene arylate); the polyetherimide; optionally, the auxiliary flame retardant comprising melamine polyphosphate, melamine cyanurate, melamine pyrophosphate, melamine phosphate, or a combination thereof; the flame retardant composition comprising the dialkyl phosphinic acid salt; optionally, an additive composition; wherein the sum of the wt% of the polyester, the flame retardant composition, the mineral flame retardant synergist, the polyetherimide, and the optional additive composition total 100 wt%, and wherein the thermoplastic composition comprises 1500 ppm or less of intentionally added fluorine, and a sample of the thermoplastic composition exhibits a UL 94 flame test rating of V-0 at a thickness of 0.8 mm.

3. The thermoplastic composition of claim 1 comprising: the polyester comprising the poly (alkylene arylate);24SHPP0032-WO-PCT(SS180007PCT) optionally, the poly etherimide; the auxiliary flame retardant comprising melamine polyphosphate, melamine cyanurate, melamine pyrophosphate, melamine phosphate, or a combination thereof; the flame retardant composition comprising the dialkyl phosphinic acid salt; the mineral flame retardant synergist comprising the modified fibrillated magnesium silicate, the modified fibrillated aluminum silicate, or a combination thereof; the glass fibers; and optionally, an additive composition; wherein the sum of the wt% of the polyester, the flame retardant composition, the mineral flame retardant synergist, the optional polyetherimide, the glass fibers, and the optional additive composition total 100 wt%, and wherein the thermoplastic composition comprises 1500 ppm or less of intentionally added fluorine, and a sample of the thermoplastic composition exhibits a UL 94 flame test rating of V-0 at a thickness of 0.6 mm.

4. The thermoplastic composition of any one of claims 1 to 3, the polyester comprising a poly(l,4-butylene terephthalate) comprising an intrinsic viscosity of 1.00 to 1.50 dl / g_as measured at 30°C in a 1:1 w / w solution of phenol: 1,1, 2, 2-tetrachloroethane, and having 17 milliequivalents per kilogram (meq / kg) of COOH, a poly(l,4-butylene terephthalate) comprising an intrinsic viscosity of 0.5 to 1.0 dl / g as measured at 30°C in a 1:1 w / w solution of phenol: 1,1, 2, 2-tetrachloroethane, and having 17 milliequivalents per kilogram (meq / kg) of COOH; and up to 10 wt% of the poly etherimide; the flame retardant composition comprising the dialkyl phosphinic acid salt; optionally, the auxiliary flame retardant comprising melamine polyphosphate, melamine cyanurate, melamine pyrophosphate, melamine phosphate, or a combination thereof, wherein the flame retardant composition and the optional auxiliary flame retardant is present in an amount effective to provide 2-6 wt% phosphorus; the mineral flame retardant synergist comprising the modified fibrillated magnesium silicate, the modified fibrillated aluminum silicate, or a combination thereof; and optionally, the additive composition;24SHPP0032-WO-PCT(SS180007PCT) wherein the sum of the wt% of the polyester, the flame retardant composition, the mineral flame retardant synergist, the polyetherimide, and the optional additive composition total 100 wt%, and wherein the thermoplastic composition comprises 1500 ppm or less of intentionally added fluorine, and a sample of the thermoplastic composition exhibits a UL 94 flame test rating of V-0 at a thickness of 0.8 mm.

5. The thermoplastic composition of any one of claims 1 to 3, wherein the a wt% of the poly(l,4-butylene terephthalate) having an intrinsic viscosity of 1.00 to 1.50 dl / g is similar to or greater than the poly(l,4-butylene terephthalate) having an intrinsic viscosity of 0.5 to 1.0 dl / g, wherein the intrinsic viscosity of poly(l,4-butylene terephthalate) is measured at 30 °C in a 1:1 w / w solution of phenol: 1,1, 2, 2-tetrachloroethane, and having 17 milliequivalents per kilogram (meq / kg) of COOH.

6. The thermoplastic composition of any one of claims 1 to 5, comprising: a poly(l,4-butylene terephthalate) comprising an intrinsic viscosity of 0.5 to 1.0 dl / g; and a poly(l,4-butylene terephthalate) comprising an intrinsic viscosity of 1.00 to 1.50 dl / g, wherein the intrinsic viscosity of poly(l,4-butylene terephthalate) is measured at 30 °C in a 1:1 w / w solution of phenol: 1,1, 2, 2-tetrachloroethane, and having 17 milliequivalents per kilogram (meq / kg) of COOH; the flame retardant composition comprising a dialkyl phosphinic acid salt and the optional auxiliary flame retardant comprising melamine polyphosphate, melamine cyanurate, melamine pyrophosphate, melamine phosphate, or a combination thereof is present in an amount effective to provide 2-6 wt% phosphorus; the mineral flame retardant synergist comprising the modified fibrillated magnesium silicate, the modified fibrillated aluminum silicate, or a combination thereof; glass fibers; optionally, the additive composition; and wherein the sum of the wt% of the polyester, the flame retardant composition, the mineral flame retardant synergist, the optional polyetherimide, the glass fibers, and the optional additive composition total 100 wt%, and wherein the thermoplastic composition comprises 1500 ppm or less of intentionally added fluorine, and a sample of the thermoplastic composition exhibits a UL 94 flame test rating of V-0 at a thickness of 0.4 mm.24SHPP0032-WO-PCT(SS180007PCT)7. The thermoplastic composition of any one of claims 1 to 6, comprising: the poly(l,4-butylene terephthalate) comprising an intrinsic viscosity of 0.5 to 1.0 dl / g; and a poly(l,4-butylene terephthalate) comprising an intrinsic viscosity of 1.00 to 1.50 dl / g, wherein the wt% of the poly(l,4-butylene terephthalate) comprising an intrinsic viscosity of 1.00 to 1.50 dl / g is greater than the poly(l,4-butylene terephthalate) comprising an intrinsic viscosity of 0.5 to 1.0 dl / g, wherein the intrinsic viscosity of poly(l,4-butylene terephthalate) is measured at 30 °C in a 1:1 w / w solution of phenol: 1,1, 2, 2-tetrachloroethane, and having 17 milliequivalents per kilogram (meq / kg) of COOH; up to 10 wt% of the poly etherimide; the flame retardant composition comprising the dialkyl phosphinic acid salt and the optional auxiliary flame retardant comprising melamine polyphosphate, melamine cyanurate, melamine pyrophosphate, melamine phosphate, or a combination thereof are present in an amount effective to provide 2-6 wt% phosphorus; a mineral flame retardant synergist comprising the modified fibrillated magnesium silicate, the modified fibrillated aluminum silicate, or a combination thereof; glass fibers; and optionally, the additive composition; wherein the sum of the wt% of the polyester, the flame retardant composition, the mineral flame retardant synergist, the optional polyetherimide, the glass fibers, and the optional additive composition total 100 wt%, and wherein the thermoplastic composition comprises 1500 ppm or less of intentionally added fluorine, and a sample of the thermoplastic composition exhibits a UL 94 flame test rating of V-0 at a thickness of 0.4 mm.

8. The thermoplastic composition of any one of the preceding claims, wherein the pre-treatment of the modified fibrillated magnesium silicate provides aluminum, boron, nitrogen, phosphorus, silicon, or a combination thereof to a surface of the magnesium silicate.

9. The thermoplastic composition of claim 2 or claim 4, wherein the composition includes no glass fibers and 5 to 10 wt% of a fibrillated silicon-treated magnesium silicate, a fibrillated silicon-treated aluminum silicate, or a combination thereof, and the sample of the composition exhibits a UL 94 flame test rating of V-0 at a thickness of 0.8 mm; or the composition includes 0.5 to 10 wt% of the glass fibers and 0.5 to 10 wt% of a fibrillated silicon-treated magnesium silicate, a fibrillated silicon-treated aluminum silicate, or a24SHPP0032-WO-PCT(SS180007PCT) combination thereof, and the sample of the composition exhibits a UL 94 flame test rating of V- 0 at a thickness of 0.8 mm.

10. The thermoplastic composition of claims 3, 6, or 7, wherein the polyester comprises no less than 34 wt.% of poly(l,4-butylene terephthalate) having an intrinsic viscosity of 0.5 to 1.0 dl / g and no less than 14 wt.% of poly(l,4-butylene terephthalate) having an intrinsic viscosity of 1.00 to 1.50 dl / g, wherein the intrinsic viscosity of poly(l,4-butylene terephthalate) is measured at 30 °C in a 1:1 w / w solution of phenol: 1,1, 2,2- tetrachloroethane, and having 17 milliequivalents per kilogram (meq / kg) of COOH, up to 10 wt.% of the poly etherimide, a fibrillated silicon-treated magnesium silicate, a fibrillated silicon-treated aluminum silicate, or a combination thereof, and the sample exhibits a UL 94 flame test rating of V-0 at a thickness of 0.8 mm11. The thermoplastic composition of any one of the preceding claims, wherein the flame retardant composition and the auxiliary flame retardant is present in an amount effective to provide 3-6 wt% phosphorus, based on the total weight of the composition.

12. The thermoplastic composition of any one of the preceding claims wherein: the calculated 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; or the calculated 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.

13. A method of making the thermoplastic composition of any of claims 1 to 12, the method comprising melt-mixing the components of the composition, and, optionally, extruding the melt-mixed composition.

14. An article comprising the thermoplastic composition of any 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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