Polycarbonate copolymer compositions for interior parts of rail vehicles

Abstract

A polycarbonate composition comprising: a polycarbonate including a homopolycarbonate, a poly(ester-carbonate-siloxane), a poly(aliphatic ester-carbonate), a poly(ester-carbonate-siloxane), a brominated polycarbonate, a poly(ester-carbonate), or a combination thereof, and optionally, a poly(phthalate-carbonate); a poly(carbonate-siloxane) present in an amount effective to provide 1-10 wt% total siloxane, based on the total weight of the composition; 11-25 wt% of a reinforcing composition comprising 10-24 wt% glass fiber and 1-10 wt% mineral filler including talc, kaolin, calcium carbonate, wollastonite, or a combination thereof; optionally, an organic phosphorus flame retardant in an amount effective to provide up to 1.5 wt% phosphorus; optionally, up to 10 wt% of an additive composition, wherein each amount is based on the total weight of the polycarbonate composition, the sum of each amount is 100 wt%.

Description

[0001] Citations of relevant applications

[0002] This application claims priority and benefit to European Patent Application No. 21162286.5, filed on March 12, 2021, the contents of which are incorporated herein by reference in their entirety. Technical Field

[0003] This disclosure relates to compositions for train interior components, and particularly seat components and cladding, having low smoke density and low heat release. Background Technology

[0004] The harmonized fire standard for rail applications (EN-45545) sets forth stringent requirements on the permissible heat release, smoke density, toxicity, and flame spread characteristics of materials used in rail applications within the European Union.

[0005] As set forth in the requirements of EN-45545, “hazard levels” (HL1 to HL3) have been specified, reflecting the degree of probability of personal injury due to fire. The levels are based on dwell time and are related to the operating and design category. HL1 is the lowest hazard level and is generally applicable to vehicles operating under relatively safe conditions (easy evacuation of the vehicle). HL3 is the highest hazard level and represents the most dangerous operating / design category (difficult and / or time-consuming evacuation of the vehicle, e.g., in underground rail vehicles).

[0006] EN-45545 classifies products into 26 sets of requirements (R1-R26). R1 ​​covers horizontal and vertical inner surfaces, and R6 covers passenger seat shells and covers. For each product type, different test requirements are defined for the hazard level.

[0007] Table 1A shows the test methods for various hazard levels in the European Railway standard EN-45545 (2013) for R6 applications, as well as the values ​​for smoke density and maximum heat release rate.

[0008] Table 1A

[0009]

[0010]

[0011] For R1 applications, Table 1B shows the test methods for various hazard levels in the European Orbital Standard EN-45545 (2013), as well as smoke density, maximum heat release rate values, and critical heat flux at extinguishment.

[0012] Table 1B

[0013]

[0014] Polycarbonates can be used to manufacture articles and components for a wide range of applications, from automotive parts to electronic appliances. Due to their extensive use, particularly in rail interiors, there is a demand for polycarbonate compositions that meet or exceed the requirements set forth in EN-45545.

[0015] However, manufacturing articles that meet these standards and possess good mechanical properties (including high stiffness, high strength, good impact resistance, and good processability) is particularly challenging. Therefore, there remains a need for polycarbonate compositions with a combination of low smoke, low heat release, low toxicity, and low flame spread. Further advantages would be the ability to prepare polycarbonate compositions at low material costs, with ease of manufacture, and while achieving the desired mechanical properties. Summary of the Invention

[0016] The above and other deficiencies in the art are satisfied by a polycarbonate composition comprising: a polycarbonate comprising homopolymer or a combination of homopolymer and brominated polycarbonate; a poly(carbonate-siloxane) having a siloxane content of 30-70 wt% based on the total weight of the poly(carbonate-siloxane), and present in an amount effectively providing 1-10 wt% of total siloxane based on the total weight of the composition; 11-25 wt% of a reinforcing composition comprising 10-24 wt% glass fiber and 1-10 wt% mineral filler comprising talc, kaolin, calcium carbonate, wollastonite, or combinations thereof; optionally, an organophosphorus flame retardant effectively providing up to 1.5 wt% phosphorus; and optionally, up to 10 wt% of an additive composition, wherein the amounts are based on the total weight of the polycarbonate composition and the sum of the amounts is 100 wt%.

[0017] The above and other deficiencies in the art are satisfied by a polycarbonate composition comprising: poly(ester-carbonate-siloxane), poly(aliphatic ester-carbonate), poly(ester-carbonate-siloxane), brominated polycarbonate, poly(ester-carbonate), poly(phthalate-carbonate), or combinations thereof, and optionally, all polycarbonate; poly(carbonate-siloxane) present in an amount of 1-10 wt% total siloxane based on the total weight of the composition; 11-25 wt% of a reinforcing composition comprising 10-24 wt% glass fiber and 1-10 wt% mineral filler comprising talc, kaolin, calcium carbonate, wollastonite, or combinations thereof; optionally, an organophosphorus flame retardant in an amount of up to 1.5 wt% phosphorus; and optionally, up to 10 wt% of an additive composition, wherein the amounts are based on the total weight of the polycarbonate composition and the sum of the amounts is 100 wt%.

[0018] In another aspect, the manufacturing method includes combining the above-mentioned components to form a polycarbonate composition.

[0019] In another aspect, the article comprises the above-described polycarbonate composition.

[0020] In another aspect, the method of manufacturing the article includes molding, extruding, or forming the above-described polycarbonate composition into an article.

[0021] The above and other features are illustrated by the following detailed description, embodiments, and claims. Detailed Implementation

[0022] The inventors of this invention have discovered polycarbonate compositions that can be used for track internals, having low smoke density characteristics (e.g., DS-4 as measured according to ISO 5659-2), low heat release characteristics (e.g., MAHRE as measured according to ISO 5660-1), and optionally, improved critical heat flux (CFE) upon extinction (e.g., as measured according to ISO 5658-2).

[0023] Manufacturing internal track materials that meet stringent smoke density, heat release, and / or flame spread standards, among other material requirements, while also providing low material costs, ease of manufacture, and good mechanical properties, is extremely challenging. Advantageously, the inventors have discovered that compositions comprising poly(carbonate-siloxane), a polycarbonate other than poly(carbonate-siloxane), and a reinforcing composition comprising mineral fillers and glass fibers provide the desired smoke density and heat release characteristics, while also providing good stiffness and impact resistance. This is a surprising and unexpected discovery, as the development of materials that robustly meet the EN45545 requirements for R1 or R6 under moderate loads using only glass fibers or only mineral fillers has proven challenging in the past. High loads of inorganic fillers (such as glass or minerals) typically result in improved fire resistance, but at the expense of impact resistance, processability, and colorability. However, the inventors have found that, under relatively low loads, the combination of glass fibers and mineral fillers results in robust smoke density and heat release that meet the R6-HL2 requirements, allowing for good maintenance of impact resistance and aesthetics.

[0024] Among its particularly advantageous features, the polycarbonate composition can have a strength of 50 kW / m² on a 3 mm thick sheet according to ISO 5659-2. 2 A measured DS-4 value of 300 or less indicates a low smoke density, measured according to ISO 5660-1 on a 3mm thick plate at 50 kW / m³. 2 Measured 90kJ / m 2 Or even lower maximum average heat release (MAHRE), with high stiffness, high strength, and maintaining sufficient practical impact resistance. Optionally, the composition may have 20 kW / m² measured according to ISO 5658-2 on a 3 mm thick part. 2 Or a larger critical heat flux (CFE) upon extinction.

[0025] The polycarbonate composition comprises a polycarbonate including (1) homopolymer carbonate or a combination of homopolymer carbonate and brominated polycarbonate, or (2) poly(ester-carbonate-siloxane), poly(aliphatic ester-carbonate), poly(ester-carbonate-siloxane), brominated polycarbonate, poly(ester-carbonate), poly(phthalate-carbonate), or a combination thereof, and optionally, homopolymer carbonate; poly(carbonate-siloxane); and a reinforcing composition comprising a combination of glass fibers and mineral fillers. The various components of the polycarbonate composition are described in detail below.

[0026] As used herein, “polycarbonate” refers to a polymer having repeating carbonate units of formula (1):

[0027]

[0028] Among them, R 1 At least 60% of the total number of groups contains an aromatic moiety, and the remainder is aliphatic, alicyclic, or aromatic. In one aspect, each R 1 It is C 6-30 Aromatic groups, that is, containing at least one aromatic moiety. R 1 It can be derived from HO-R 1 -OH, especially aromatic dihydroxy compounds of formula (2):

[0029] HO-A 1 -Y 1 -A 2 -OH(2)

[0030] Among them, A 1 and A 2 Each is a monocyclic divalent aromatic group, and Y 1 Is it a single bond or has A 1 With A 2 A bridging base consisting of one or more separate atoms. In one aspect, an atom will connect A... 1 With A 2 Separate. Preferably, each R 1 Bisphenols that can be derived from formula (3):

[0031]

[0032] Among them, R a and R b Each is independently a halogen, C 1-12 alkoxy, or C 1-12 Alkyl groups, and p and q are each independent integers from 0 to 4. It should be understood that when p or q is less than 4, the valence of each carbon in the ring is filled with hydrogen. Also in equation (3), X a It is a bridging group that connects two hydroxyl-substituted aromatic groups, wherein the bridging group and the hydroxyl substituents of each C6 arylene are arranged ortho, meta, or para (preferably para) on the C6 arylene. In one aspect, the bridging group X a It is a single bond, -O-, -S-, -S(O)-, -S(O)2-, -C(O)-, or C 1-60 Organic bridging groups. Organic bridging groups can be cyclic or acyclic, aromatic or non-aromatic, and may further contain heteroatoms such as halogens, oxygen, nitrogen, sulfur, silicon, or phosphorus. They can be arranged... 1-60 The organic group causes each of the C6 arylene groups attached to it to be attached to a common alkylidene carbon or to a C6 arylene group. 1-60Different carbons in an organic bridging group. In one respect, p and q are each 1, and R a and R b Each is C 1-3 Alkyl groups, preferably methyl groups, are arranged in a meta position on the hydroxyl groups of each arylene group.

[0033] Formula HO-R 1 Other useful dihydroxy compounds of -OH include aromatic dihydroxy compounds of formula (6):

[0034]

[0035] Among them, each R h Independently, it is a halogen atom, C 1-10 Hydrocarbon groups such as C 1-10 Alkyl, halogen-substituted C 1-10 Alkyl, C 6-10 Aryl or halogen-substituted C 6-10 Aryl group, and n is 0 to 4. Halogens are usually bromine.

[0036] Some illustrative examples of specific dihydroxy compounds include the following: 4,4'-dihydroxybiphenyl, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)diphenylmethane, bis(4-hydroxyphenyl)-1-naphthylmethane, 1,2-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2-(4-hydroxyphenyl)-2-(3-hydroxyphenyl)propane, bis(4-hydroxyphenyl)phenylmethane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 1,1-bis(hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)isobutylene, 1,1-bis(4-hydroxyphenyl)cyclopentane, Cyclododecane, trans-2,3-bis(4-hydroxyphenyl)-2-butene, 2,2-bis(4-hydroxyphenyl)adamantane, α,α'-bis(4-hydroxyphenyl)toluene, bis(4-hydroxyphenyl)acetonitrile, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3-ethyl-4-hydroxyphenyl)propane, 2,2-bis(3-n-propyl-4-hydroxyphenyl)propane, 2,2-bis(3-isopropyl-4-hydroxyphenyl)propane, 2,2-bis(3-sec-butyl-4-hydroxyphenyl)propane, 2,2-bis(3-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 2,2-bis(3-allyl-4-hydroxyphenyl)propane, 2, 2-Di(3-methoxy-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 1,1-dichloro-2,2-bis(4-hydroxyphenyl)ethylene, 1,1-dibromo-2,2-bis(4-hydroxyphenyl)ethylene, 1,1-dichloro-2,2-bis(5-phenoxy-4-hydroxyphenyl)ethylene, 4,4'-dihydroxybenzophenone, 3,3-bis(4-hydroxyphenyl)-2-butanone, 1,6-bis(4-hydroxyphenyl)-1,6-hexanedione, ethylene glycol bis(4-hydroxyphenyl) ether, bis(4-hydroxyphenyl) ether, bis(4-hydroxyphenyl) sulfide, bis(4-hydroxyphenyl) sulfoxide, bis(4-hydroxyphenyl) sulfone, 9,9-bis(4-hydroxyphenyl)fluorene, 2,7-dihydroxypyrene 6,6'-Dihydroxy-3,3,3',3'-Tetramethylspiro(bis)indane ("spirodiindane bisphenol"), 3,3-bis(4-hydroxyphenyl)phthalimide, 2,6-dihydroxydibenzo-p-dioxin, 2,6-dihydroxythiaanthracene, 2,7-dihydroxyphenthia, 2,7-dihydroxy-9,10-dimethylphenazine, 3,6-dihydroxydibenzofuran, 3,6-dihydroxydibenzothiophene, and 2,7-dihydroxycarbazole, resorcinol, substituted resorcinol compounds such as 5-methylresorcinol, 5-ethylresorcinol, 5-propylresorcinol, 5-butylresorcinol, 5-tert-butylresorcinol, 5-phenylresorcinol, 5-cumylresorcinol, 2,4,5,6-tetrafluororesorcinol, 2,4,5,6-Tetrabromoresorcinol, etc.; catechol; hydroquinone; substituted hydroquinones such as 2-methylhydroquinone, 2-ethylhydroquinone, 2-propylhydroquinone, 2-butylhydroquinone, 2-tert-butylhydroquinone, 2-phenylhydroquinone, 2-cumylhydroquinone, 2,3,5,6-tetramethylhydroquinone, 2,3,5,6-tetratert-butylhydroquinone, 2,3,5,6-tetrafluorohydroquinone, 2,3,5,6-tetrabromohydroquinone, etc., or combinations thereof.

[0037] Polycarbonate can have an intrinsic viscosity of 0.3 to 1.5 dL / gm, preferably 0.45 to 1.0 dL / gm, as determined in chloroform at 25°C. Polycarbonate can have a weight-average molecular weight (Mw) of 10,000 to 200,000 Daltons, preferably 20,000 to 100,000 Daltons, as measured by gel permeation chromatography (GPC) using a cross-linked styrene-divinylbenzene column and calculated for polycarbonate. GPC samples are prepared at a concentration of 1 mg / ml and eluted at a flow rate of 1.5 ml / min.

[0038] The polycarbonate composition may comprise homopolymer polycarbonate (wherein each R in the polymer is a homopolymer polycarbonate) 1 (They are the same). In one aspect, the homopolymer in the polycarbonate composition is derived from bisphenol of formula (2), preferably bisphenol A, wherein each A in formula (2) 1 and A 2 p-phenylene and Y 1 It is isopropylidene.

[0039] In some aspects, the polycarbonate is a bisphenol A homopolymer. The bisphenol A homopolymer may have a melt flow rate of 3-50 / 10 min at 300°C and a load of 1.2 kg, and a Mw of 17,000-40,000 g / mol, preferably 20,000-30,000 g / mol, more preferably 21,000-23,0000, each as measured as described above. In some aspects, the polycarbonate includes linear bisphenol A homopolymer. In some aspects, polycarbonate includes linear bisphenol A polycarbonate homopolymers having a weight-average molecular weight of 26,000 to 40,000 g / mol, preferably 27,000 to 35,000 g / mol, as determined by gel permeation chromatography using polystyrene standards and calculated for polycarbonate; or linear bisphenol A polycarbonate homopolymers having a weight-average molecular weight of 15,000 to 25,000 g / mol, preferably 17,000 to 25,000 g / mol, as determined by gel permeation chromatography using polystyrene standards and calculated for polycarbonate; or combinations thereof.

[0040] Homopolymer polycarbonate may be present, for example, in amounts of 10-89 wt%, 20-75 wt%, or 30-60 wt%, each based on the total weight of the polycarbonate composition.

[0041] "Polycarbonate" includes homopolymer polycarbonate (where each R in the polymer is a homopolymer polycarbonate). 1 (They are the same) and contain different R in carbonates. 1 A copolymer of some (“copolycarbonate”) and a copolymer comprising carbonate units and other types of polymer units such as ester units or siloxane units.

[0042] A certain polycarbonate in a polycarbonate composition may include an aromatic poly(ester-carbonate). In addition to the repeating carbonate unit of formula (1), such a polycarbonate further comprises repeating ester units of formula (3):

[0043]

[0044] Wherein, J is a divalent group derived from an aromatic dihydroxy compound (including its reactive derivatives), such as bisphenols of formula (2), for example, bisphenol A; and T is a divalent group derived from an aromatic dicarboxylic acid (including its reactive derivatives), preferably isophthalic acid or terephthalic acid, wherein the weight ratio of isophthalic acid to terephthalic acid is 91:9 to 2:98. Copolyesters containing combinations of different T or J groups can be used. The polyester units can be branched or linear.

[0045] In one respect, J is derived from bisphenols of formula (2), such as bisphenol A. In another respect, J is derived from aromatic dihydroxy compounds, such as resorcinol. A portion of group J, for example up to 20 mol%, may be C having a straight-chain, branched, or cyclic (including polycyclic) structure. 2-30 Alkylene, such as ethylene, n-propylene, isopropylene, 1,4-butylene, 1,4-cyclohexylene, or 1,4-methylenecyclohexane. Preferably, all J groups are aromatic.

[0046] Aromatic dicarboxylic acids that can be used to prepare polyester units include isophthalic acid or terephthalic acid, 1,2-bis(p-carboxyphenyl)ethane, 4,4'-dicarboxydiphenyl ether, 4,4'-dibenzoic acid, or combinations thereof. Acids containing fused rings, such as 1,4-, 1,5-, or 2,6-naphthalenedicarboxylic acids, may also be present. Specific dicarboxylic acids include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, or combinations thereof. Specific dicarboxylic acids include combinations of isophthalic acid and terephthalic acid, wherein the weight ratio of isophthalic acid to terephthalic acid is 91:9 to 2:98. A portion of the group T, for example up to 20 mol%, may be aliphatic, for example, derived from 1,4-cyclohexanedicarboxylic acid. Preferably, all T groups are aromatic.

[0047] The molar ratio of ester units to carbonate units in polycarbonate can vary widely, for example, from 1:99 to 99:1, preferably from 10:90 to 90:10, more preferably from 25:75 to 75:25, or from 2:98 to 15:85, depending on the desired properties of the final composition.

[0048] A certain polycarbonate in the polycarbonate composition may include a specific poly(ester-carbonate) that comprises bisphenol A carbonate units and bisphenol A isophthalate / bisphenol A terephthalate units, i.e., poly(bisphenol A carbonate)-co-(bisphenol A phthalate) of formula (4a):

[0049]

[0050] Where x and y represent the weight percentages of bisphenol A carbonate units and bisphenol A isophthalate / bisphenol A terephthalate units, respectively. Typically, the units exist as blocks. In one aspect, the weight ratio of carbonate units x to ester units y in polycarbonate is 1:99 to 50:50, or 5:95 to 25:75, or 10:90 to 45:55. Copolymers of formula (5) comprising 35-45 wt% carbonate units and 55-65 wt% ester units, wherein the ester units have a molar ratio of isophthalate to terephthalate of 45:55 to 55:45, are commonly referred to as poly(carbonate-ester). A copolymer comprising 15-25 wt% carbonate units and 75-85 wt% ester units, wherein the ester units have a molar ratio of isophthalic acid ester to terephthalic acid ester from 98:2 to 88:12, commonly referred to as poly(phthalic acid ester-carbonate), and may optionally be present in addition to certain polycarbonates in the polycarbonate composition.

[0051] In another aspect, the high-heat poly(ester-carbonate) is a poly(carbonate-co-monoarylate) of formula (4b), which comprises an aromatic carbonate unit (1) and repeating monoarylate ester units.

[0052]

[0053] Among them, R 1 As defined in equation (1), and each R h Independently, it is a halogen atom, C 1-10 Hydrocarbon groups such as C 1-10 Alkyl, halogen-substituted C 1-10 Alkyl, C 6-10 Aryl or halogen-substituted C 6-10 Aryl, and n is 0-4. Preferably, each R h C is independent1-4 Alkyl group, and n is 0-3, 0-1, or 0. The molar ratio of carbonate unit x to ester unit z can be from 99:1 to 1:99, or from 98:2 to 2:98, or from 90:10 to 10:90. In one aspect, the molar ratio of x:z is from 50:50 to 99:1, or from 1:99 to 50:50.

[0054] In one aspect, the heat-resistant poly(ester-carbonate) comprises aromatic ester units and monoaromatic ester units derived from the reaction of a combination of isophthalic acid and terephthalic acid (or reactive derivatives thereof) with resorcinol (or reactive derivatives thereof) to provide resorcinol resorcinol phthalate / resorcinol terephthalate (“ITR” ester units). Based on the total molar number of ester units in the polycarbonate, the ITR ester units may be present in the heat-resistant poly(ester-carbonate) in an amount greater than or equal to 95 mol%, preferably greater than or equal to 99 mol%, and even more preferably greater than or equal to 99.5 mol%. Preferred heat-resistant poly(ester-carbonate) comprises bisphenol A carbonate units and ITR ester units derived from terephthalic acid, isophthalic acid, and resorcinol, i.e., poly(bisphenol A carbonate-co-resorcinol resorcinol phthalate / resorcinol terephthalate) of formula (c):

[0055]

[0056] The molar ratio of x:z is from 98:2 to 2:98, or from 90:10 to 10:90. In one aspect, the molar ratio of x:z is from 50:50 to 99:1, or from 1:99 to 50:50. Based on the total molar number of ester units in the copolymer, the ITR ester units may be present in the poly(bisphenol A carbonate-co-resorcinol resorcinol phthalate-resorcinol terephthalate) in an amount greater than or equal to 95 mol%, preferably greater than or equal to 99 mol%, and even more preferably greater than or equal to 99.5 mol%. Based on the total molar number of units in the copolymer, other carbonate units, other ester units, or combinations thereof may be present in a total amount of 1 to 20 mol%, such as the monoaryl carbonate units of formula (5) and the bisphenol ester units of formula (3a):

[0057]

[0058] In the above formula, R h Each is C independently 1-10 Hydrocarbon group, n is 0-4, R a and R b Each is C independently 1-12 Alkyl groups, p and q are each independent integers from 0 to 4, and X aIt is a single bond, -O-, -S-, -S(O)-, -S(O)2-, -C(O)-, or the formula -C(R) c (R) d )- of C 1-13 Alkyl groups (where R) c and R d Each is independently either hydrogen or C 1-12 alkyl) or formula -C (=R) e )- group (where R e It is divalent C 1-12 (Hydrocarbon group). The bisphenol ester unit can be the bisphenol A phthalate unit of formula (3b):

[0059]

[0060] In one aspect, poly(bisphenol A carbonate-co-resorcinol resorcinol phthalate / resorcinol terephthalate) (4c) comprises 1-90 mol% of bisphenol A carbonate units, 10-99 mol% of isophthalic acid-terephthalic acid-resorcinol ester units, and optionally 1-60 mol% of resorcinol carbonate units, isophthalic acid-terephthalic acid-bisphenol A phthalate units, or combinations thereof. In another aspect, poly(bisphenol A carbonate-co-resorcinol resorcinol phthalate / resorcinol terephthalate) (6) comprises 10-20 mol% of bisphenol A carbonate units, 20-98 mol% of isophthalic acid-terephthalic acid-resorcinol ester units, and optionally 1-60 mol% of resorcinol carbonate units, isophthalic acid-terephthalic acid-bisphenol A phthalate units, or combinations thereof.

[0061] Certain polycarbonates in the polycarbonate composition may include poly(ester-carbonate-siloxane) containing bisphenol A carbonate units, bisphenol A isophthalate-bisphenol A terephthalate units and siloxane units (e.g., blocks containing 5 to 200 dimethylsiloxane units).

[0062] The high-heat poly(ester-carbonate) can have a molecular weight (Mw) of 2,000-100,000 g / mol, preferably 3,000-75,000 g / mol, more preferably 4,000-50,000 g / mol, more preferably 5,000-35,000 g / mol, and even more preferably 17,000-30,000 g / mol. Molecular weight was determined using GPC with a cross-linked styrene-divinylbenzene column at a sample concentration of 1 mg / mL, calibrated with bisphenol A homopolymer polycarbonate standards. The sample was eluted with dichloromethane at a flow rate of 1.0 mL / min.

[0063] The polycarbonate in the polycarbonate composition may include polycarbonate derived from linear C6-20 Aliphatic dicarboxylic acids (including their reactive derivatives), specifically, linear C 6-12 Poly(aliphatic ester-carbonates) of aliphatic dicarboxylic acids (including their reactive derivatives). Specific dicarboxylic acids include adipic acid, sebacic acid, and α,ω-C... 12 Dicarboxylic acids, such as dodecanoic acid (DDDA). Specific poly(aliphatic ester)-polycarbonates have formula (8):

[0064]

[0065] Among them, each R 1 The units may be the same or different, and as described in formula (1), m is 4 to 18, preferably 4 to 10, and the average molar ratio x:y of the ester units to the carbonate units is 99:1 to 1:99, including 13:87 to 2:98, or 9:91 to 2:98, or 8:92 to 2:98. In one specific aspect, the poly(aliphatic ester)-polycarbonate copolymer comprises bisphenol A sebacic acid ester units and bisphenol A carbonate units, having an average molar ratio x:y of, for example, 2:98 to 8:92, or, for example, 6:94.

[0066] Poly(aliphatic ester-carbonate) can have a weight-average molecular weight of 15,000 g / mol to 40,000 g / mol, including 20,000 g / mol to 38,000 g / mol (based on polystyrene standards measured by GPC and calculated for polycarbonate).

[0067] Polycarbonates can be manufactured by methods such as interfacial polymerization and melt polymerization, which are known and described, for example, in WO 2013 / 175448 A1 and WO 2014 / 072923 A1. End-capping agents (also known as chain terminators or chain capping agents) may be included during polymerization to provide end groups, such as monocyclic phenols like phenol, p-cyanophenol, and C64. 1-22Alkyl-substituted phenols such as p-cumylphenol, resorcinol monobenzoate, and p-tert-butylphenol; monoethers of diphenols such as p-methoxyphenol; monoesters of diphenols such as resorcinol monobenzoate; functionalized chlorides of aliphatic monocarboxylic acids such as acryloyl chloride and methacryloyl chloride; and monochloroformates such as phenyl chloroformate, alkyl-substituted phenyl chloroformate, p-cumylphenyl chloroformate, and toluene chloroformate. Combinations of different end groups can be used. Branched polycarbonate blocks can be prepared by adding branching agents during polymerization, such as trimellitic acid, trimellitic anhydride, trimellityl chloride, tri-p-hydroxyphenyl ethane, indigo-bisphenol, pyroxene TC (1,3,5-tris((p-hydroxyphenyl)isopropyl)benzene), pyroxene PA (4(4(1,1-bis(p-hydroxyphenyl)-ethyl)α,α-dimethylbenzyl)phenol), 4-chloroformylphthalic anhydride, benzopyridine, and benzophenone tetracarboxylic acid. The branching agent can be added at a level of 0.05 to 4.0 wt%, preferably 0.25 to 2.0 wt%. Combinations including linear polycarbonate and branched polycarbonate can be used.

[0068] End-capping agents (also known as chain terminators or chain capping agents) may be included during polymerization to provide end groups. The end-capping agent (and therefore the end groups) is selected based on the desired properties of the polycarbonate. Exemplary end-capping agents are illustrated below by example: monocyclic phenols such as phenol and C... 1-22 Alkyl-substituted phenols such as p-cumylphenol, resorcinol monobenzoate, and p-tert-butylphenol; monoethers of diphenols such as p-methoxyphenol; and alkyl-substituted phenols having branched alkyl substituents (having 8 to 9 carbon atoms); 4-substituted 2-hydroxybenzophenones and their derivatives; aryl salicylate esters; monoesters of diphenols such as resorcinol monobenzoate; 2-(2-hydroxyaryl)-benzotriazoles and their derivatives; 2-(2-hydroxyaryl)-1,3,5-triazines and their derivatives; monocarboxylic acid chlorides such as benzoyl chloride; C 1-22 Alkyl-substituted benzoyl chloride, tolueneyl chloride, bromobenzoyl chloride, cinnamoyl chloride, and 4-bridged methylenetetrahydrophthalimide benzoyl chloride, polycyclic monocarboxylic acid chlorides (such as trimellitic anhydride chloride), and naphthyl chloride, functionalized chlorides of aliphatic monocarboxylic acids such as acryloyl chloride and methacryloyl chloride, and monochloroformates such as phenyl chloroformate, alkyl-substituted phenyl chloroformate, p-cumylphenyl chloroformate, and toluene chloroformate. Combinations of different end groups can be used.

[0069] The polycarbonate composition comprises poly(carbonate-siloxane), also known in the art as a polycarbonate-polysiloxane copolymer. The polysiloxane block comprises repeating diorganosiloxane units as shown in formula (10).

[0070]

[0071] Where each R is independently C 1-13 Monovalent organic groups. For example, R can be C. 1-13 Alkyl, C 1-13 Alkoxy, C 2-13 alkenyl, C 2-13 alkenyloxy group, C 3-6 cycloalkyl, C 3-6 Cycloalkoxy, C 6-14 Aryl, C 6-10 aryloxy group, C 7-13 Arylalkylene, C 7-13 Arylalkyleneoxy, C 7-13 alkylarylene, or C 7-13 Alkylaryloxy groups. These groups can be completely or partially halogenated by fluorine, chlorine, bromine, or iodine, or combinations thereof. In one aspect, when a transparent poly(carbonate-siloxane) is desired, R is not halogenated. Combinations of the aforementioned R groups can be used in the same copolymer.

[0072] The E value in formula (10) can vary widely depending on the type and relative amount of each component in the polycarbonate composition, the desired properties of the composition, etc. Typically, E has an average value of 2 to 1,000, preferably 2 to 500, 2 to 200, or 2 to 125, 5 to 80, or 10 to 70. In one aspect, E has an average value of 10 to 80 or 10 to 40, and in another aspect, E has an average value of 40 to 80 or 40 to 70. When E has a lower value, for example less than 40, a relatively large amount of poly(carbonate-siloxane) copolymer can be expected to be used. Conversely, when E is a higher value, for example greater than 40, a relatively low amount of poly(carbonate-siloxane) copolymer can be used. A combination of first and second (or more) poly(carbonate-siloxane) copolymers can be used, wherein the average value of E of the first copolymer is less than the average value of E of the second copolymer.

[0073] In one respect, the polysiloxane block has formula (11):

[0074]

[0075] Where E and R are defined as in equation (10); each R can be the same or different, and as defined above; and Ar can be the same or different, and is substituted or unsubstituted C. 6-30 The aryl group is a group in which the bond is directly attached to the aromatic moiety. The Ar group in formula (11) can be derived from C. 6-30Dihydroxyaryl compounds, such as those of formula (3) or (6). These dihydroxyaryl compounds are 1,1-bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, 1,1-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)n-butane, 2,2-bis(4-hydroxy-1-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl sulfide), and 1,1-bis(4-hydroxy-tert-butylphenyl)propane.

[0076] In another aspect, the polysiloxane block has formula (13):

[0077]

[0078] Where R and E are as described above, and each R 5 Independently is divalent C 1-30 Organic groups, wherein the polymerized polysiloxane unit is a reactive residue of its corresponding dihydroxy compound. In one specific aspect, the polysiloxane block has the formula (14):

[0079]

[0080] Where R and E are as defined above. R in equation (14) 6 It is divalent C 2-8 Aliphatic groups. Each M in formula (14) may be the same or different, and may be halogen, cyano, nitro, C 1-8 Alkylthio, C 1-8 Alkyl, C 1-8 Alkoxy, C 2-8 alkenyl, C 2-8 alkenyloxy group, C 3-8 cycloalkyl, C 3-8 Cycloalkoxy, C 6-10 Aryl, C 6-10 aryloxy group, C 7-12 Aryl alkyl, C 7-12 Arylalkoxy, C 7-12 alkylaryl, or C 7-12 Alkyl aryloxy groups, wherein each n is independently 0, 1, 2, 3 or 4.

[0081] In one respect, M is bromine or chlorine, alkyl such as methyl, ethyl, or propyl, alkoxy such as methoxy, ethoxy, or propoxy, or aryl such as phenyl, chlorophenyl, or tolyl; R 6 It is dimethylene, trimethylene, or tetramethylene; and R is C. 1-8Alkyl, haloalkyl such as trifluoropropyl, cyanoalkyl, or aryl such as phenyl, chlorophenyl, or tolyl. In another aspect, R is methyl, or a combination of methyl and trifluoropropyl, or a combination of methyl and phenyl. In yet another aspect, R is methyl, M is methoxy, n is 1, and R... 6 It is divalent C 1-3 Aliphatic groups. Specific polysiloxane blocks have the following formula:

[0082]

[0083] Or combinations thereof, where E has an average value of 2 to 200, 2 to 125, 5 to 125, 5 to 100, 5 to 50, 20 to 80, or 5 to 20.

[0084] The blocks of formula (14) can be derived from the corresponding dihydroxy polysiloxanes, which can then be prepared to achieve platinum-catalyzed addition between siloxane hydrides and aliphatic unsaturated monohydric phenols (such as eugenol, 2-alkylphenol, 4-allyl-2-methylphenol, 4-allyl-2-phenylphenol, 4-allyl-2-bromophenol, 4-allyl-2-tert-butoxyphenol, 4-phenyl-2-phenylphenol, 2-methyl-4-propylphenol, 2-allyl-4,6-dimethylphenol, 2-allyl-4-bromo-6-methylphenol, 2-allyl-6-methoxy-4-methylphenol, and 2-allyl-4,6-dimethylphenol). Poly(carbonate-siloxane) copolymers can then be prepared, for example, via the synthetic procedure for preparation 2 by Hoover's European Patent Application Publication No. 0 524 731A1, page 5.

[0085] The poly(carbonate-siloxane) copolymer may comprise 50 to 99 weight percent of carbonate units and 1 to 50 weight percent of siloxane units. Within this range, the poly(carbonate-siloxane) copolymer may comprise 70 to 98 weight percent, more preferably 75 to 97 weight percent of carbonate units and 2 to 45 weight percent, more preferably 5 to 10 or 30 to 45 weight percent of siloxane units.

[0086] In one aspect, blends were used, particularly blends of bisphenol A homopolymer carbonates and poly(carbonate-siloxane) block copolymers of bisphenol A blocks and eugenol-terminated polydimethylsiloxane blocks:

[0087]

[0088] Wherein, x is 1 to 200, preferably 5 to 85, more preferably 10 to 70, more preferably 15 to 65, and even more preferably 40 to 60; x is 1 to 500, or 10 to 200, and z is 1 to 1000, or 10 to 800. In one aspect, x is 1 to 200, y is 1 to 90, and z is 1 to 600; and in another aspect, x is 30 to 50, y is 10 to 30, and z is 45 to 600. The polysiloxane blocks may be randomly or controlledly distributed in the polycarbonate blocks.

[0089] In one aspect, based on the total weight of the poly(carbonate-siloxane) copolymer, the poly(carbonate-siloxane) copolymer contains 10 wt% or less, preferably 8 wt% or less, of polysiloxane. In another aspect, based on the total weight of the poly(carbonate-siloxane) copolymer, the poly(carbonate-siloxane) copolymer contains 10 wt% or more, preferably 14 wt% or more, and more preferably 18 wt% or more of polysiloxane copolymer.

[0090] In one respect, based on the total weight of the poly(carbonate-siloxane) copolymer, the poly(carbonate-siloxane) copolymer contains 30-70 wt%, preferably 35-65 wt%, more preferably 35-55 wt%, and even more preferably 35-45 wt% of polysiloxane.

[0091] Poly(carbonate-siloxane) copolymers may include a single poly(carbonate-siloxane). In some aspects, the polycarbonate composition comprises a poly(carbonate-siloxane) copolymer containing 10 wt% or less of a siloxane content, a poly(carbonate-siloxane) copolymer containing 30-70 wt% of a siloxane content, or a poly(carbonate-siloxane) copolymer containing more than 10 wt% but less than 30 wt% of a siloxane content. Poly(carbonate-siloxane) copolymers may include combinations of poly(carbonate-siloxane) copolymers, such as combinations of two or more of the above. The polycarbonate composition may contain a poly(carbonate-siloxane) copolymer containing 10 wt% or less of a siloxane content, a poly(carbonate-siloxane) copolymer containing more than 10 wt% but less than 30 wt% of a siloxane content, a poly(carbonate-siloxane) copolymer containing 30-70 wt% of a siloxane content, or combinations thereof, each based on the total weight of each poly(carbonate-siloxane) copolymer. In some respects, the polycarbonate composition comprises a poly(carbonate-siloxane) copolymer containing 10 wt% or less of a siloxane content and a poly(carbonate-siloxane) copolymer containing 30-70 wt% of a siloxane content, each based on the total weight of each poly(carbonate-siloxane) copolymer.

[0092] Poly(carbonate-siloxane) can have a weight-average molecular weight of 2,000 g / mol to 100,000 g / mol, preferably 5,000 g / mol to 50,000 g / mol, as measured by gel permeation chromatography using a cross-linked styrene-divinylbenzene column at a sample concentration of 1 mg / mL with polystyrene standards and calculated for polycarbonate.

[0093] Poly(carbonate-siloxane) can have a melt volumetric flow rate of 1 to 50 cc / 10min, preferably 2 to 30 cc / 10min, measured at 300°C / 1.2 kg. The overall desired flow properties can be achieved using combinations of poly(carbonate-siloxane) with different flow properties.

[0094] The polycarbonate composition may contain 1 to 10 wt% or 2-5 wt% siloxane, each based on the total composition.

[0095] Polycarbonate compositions may be substantially free of polyetherimides, substantially free of elastomeric-modified graft copolymers, or combinations thereof. In some aspects, a polycarbonate composition is “substantially free of polyetherimides.” As used herein, “substantially free of polyetherimides” means 5 wt% or less, 1 wt% or less, 0.5 wt% or less, 0.1 wt% or less, 0.05 wt% or less, 0.01 wt% or less, or less than 0.01 wt%, each based on the total weight of the polycarbonate composition. In some aspects, a polycarbonate composition is “substantially free of elastomeric-modified graft copolymers.” As used herein, “substantially free of elastomeric-modified graft copolymers” means 5 wt% or less, 1 wt% or less, 0.5 wt% or less, 0.1 wt% or less, 0.05 wt% or less, 0.01 wt% or less, or less than 0.01 wt%, each based on the total weight of the polycarbonate composition.

[0096] The reinforcing composition of the polycarbonate composition comprises mineral fillers including talc, kaolin, calcium carbonate, wollastonite, or combinations thereof, such as calcium carbonate such as chalk, limestone, marble, synthetic precipitated calcium carbonate, etc.; talc such as fibrous, modular, acicular, layered talc, etc.; wollastonite; surface-treated wollastonite; and kaolin, such as hard kaolin, soft kaolin, calcined kaolin, and kaolin with various coatings known in the art to promote compatibility with the polymer matrix. Additional mineral fillers or reinforcing agents may also be present. Other possible fillers or reinforcing agents include, for example, silicate and silica powders such as aluminum silicate (mullite), synthetic calcium silicate, zirconium silicate, fused silica, crystalline silica graphite, natural silica sand, etc.; boron powders such as boron nitride powder, boron silicate powder, etc.; oxides such as TiO2, aluminum oxide, magnesium oxide, etc.; calcium sulfate (as its anhydride, dihydrate, or trihydrate); glass spheres such as hollow and solid glass spheres, silicate spheres, coal spores, aluminosilicates, etc. Armored spheres, etc.; monocrystalline fibers or whiskers, such as silicon carbide, alumina, boron carbide, iron, nickel, copper, etc.; fibers (including continuous and chopped fibers) such as asbestos, carbon fibers, sulfides such as molybdenum sulfide, zinc sulfide, etc.; barium compounds, such as barium titanate, barium ferrite, barium sulfate, barite, etc.; metals and metal oxides such as granular or fibrous aluminum, bronze, zinc, copper, and nickel, etc.; sheet-like fillers, such as glass flakes, sheet-like silicon carbide, diboron, etc. Aluminum oxide, aluminum flakes, steel flakes, etc.; fibrous fillers, such as short inorganic fibers derived from blends containing at least one of aluminum silicate, alumina, magnesium oxide, and calcium sulfate hemihydrate; natural fillers and reinforcing materials, such as wood flour obtained by crushing wood, fiber products such as cellulose, cotton, sisal, jute, starch, cork flour, lignin, peanut shells, corn, rice husks, etc.; organic fillers, such as polytetrafluoroethylene; reinforcing organic fiber fillers formed from organic polymers capable of forming fibers, such as poly(ether ketone), polyimide, polybenzoxazole, poly(phenylene sulfide), polyester, polyethylene, aromatic polyamide, aromatic polyimide, polyetherimide, polytetrafluoroethylene, acrylic polymers, poly(vinyl alcohol), etc.; and other fillers and reinforcing agents such as mica, clay, feldspar, flue dust, magnesium aluminosilicate, quartz, quartzite, perlite, diatomite, diatomaceous earth, carbon black, etc., or combinations thereof.

[0097] Fillers and reinforcing agents can be coated with a metallic layer to promote conductivity, or surface-treated with silanes to improve adhesion and dispersion with the polymer matrix. Furthermore, reinforcing fillers can be provided in the form of monofilaments or multifilaments, and can be used alone or in combination with other types of fibers, for example, through co-weaving or core / sheath, side-by-side, orange-type, or matrix and fibril structures, or by other methods known to those skilled in the art of fiber manufacturing. Co-weaving structures include glass fiber-carbon fiber, carbon fiber-aromatic polyimide (aromatic polyamide) fibers, and aromatic polyimide glass fiber, etc. Fiber fillers can be provided in the following forms: for example, rovings, braided fiber reinforcements such as 0-90 degree fabrics, etc.; nonwoven fiber reinforcements such as continuous filament mats, chopped strand mats, weaves, paper, and felts, etc.; or three-dimensional reinforcements such as braids.

[0098] The reinforcing composition of the polycarbonate composition includes glass fibers. The term "glass" refers to a natural or synthetic material containing silica (SiO2) or silicon dioxide as its primary material. Glass fibers can be textile glass fibers such as E, A, C, ECR, R, S, D, and / or NE glass fibers, and ideally E-type glass fibers. Glass fibers can be provided in the form of monofilaments or multifilaments and can be used alone or in combination with other types of fibers, for example, co-woven or core / sheath, side-by-side, sheath-core, or matrix and fibril structures. Glass fibers can be provided in the following forms: rovings, woven fiber reinforcements such as 0-90 degree fabrics, etc.; nonwoven fiber reinforcements such as continuous filament mats, chopped strand mats, weaves, paper, and felts, etc.; or three-dimensional reinforcements such as braids. Preferred filaments for plastic reinforcement are produced by mechanical drawing.

[0099] Glass fibers can be chopped glass fibers, long glass fibers, glass filaments, braided glass fibers, or combinations thereof. In one aspect, glass fibers can be further combined with carbon fibers, braided carbon fibers, ceramic fibers, or combinations thereof.

[0100] Glass fibers can be continuous or chopped, preferably chopped. Chopped filament glass fibers can have lengths from 0.3 mm to 10 cm, preferably 0.5 mm to 5 cm, or 3 mm to 13 mm. Glass fibers can have lengths of 0.2-20 mm, preferably 0.2-10 mm, more preferably 0.7-7 mm. Glass fibers can have any cross-section, such as circular (or round), flat, bilobed, or irregular cross-sections. The average diameter of the glass fibers can be 1-25 micrometers (μm), preferably 3-20 μm, more preferably 4-18 μm, and even more preferably 5-17 μm. Glass fibers can be short glass fibers with a diameter of 10 μm or 14 μm. In one aspect, the glass fibers have a circular cross-section. Flat glass or bilobed fibers can be used to provide articles with, for example, low warpage, high strength, and high elongation.

[0101] Glass fibers can have a circular (or round), flat, or irregular cross-section. Therefore, non-circular fiber cross-sections can be used. However, in some instances, glass fibers can have a circular cross-section. The width or diameter of the glass fiber can be from about 1 to about 20 μm, or from about 5 to about 20 μm. In another instance, the width or diameter of the glass fiber can be from about 5 μm to about 15 μm. In some compositions, the glass fiber can have a width or diameter of about 14 μm.

[0102] Glass fibers can be bonded or unbonded. As used herein, "unbonded glass fiber" refers to glass fiber coated with a sizing composition that results in poor adhesion between the coated glass fiber and the polycarbonate matrix. In other words, unbonded glass fiber is coated with a sizing composition that is incompatible with the polycarbonate matrix, as opposed to unbonded glass fiber (referred to herein as "bonded glass fiber" because they are bonded relative to polycarbonate) coated with a sizing composition that has improved adhesion to the polycarbonate matrix.

[0103] The reinforcing composition of the polycarbonate composition covering the combination of glass fiber and mineral filler may be present in amounts of 11-25 wt%, 11-20 wt%, or 11-15 wt%, each based on the total weight of the composition. The reinforcing composition comprises glass fiber and mineral filler. Glass fiber may be present in amounts of 10-24 wt%, 10-20 wt%, or 10-15 wt%. Mineral filler may be present in amounts of 1-10 wt%, 1-7 wt%, or 1-5 wt%, each based on the total weight of the composition.

[0104] The ratio of glass fiber to mineral filler can be greater than 1:2 or greater than 1:1. In some aspects, the wt% of glass fiber is equal to the wt% of mineral filler. In some aspects, the wt% of glass fiber is greater than the wt% of mineral filler. In some aspects, the weight ratio of glass fiber to mineral filler can be in the range of greater than 1:2 to 9:1 or greater than 1:2 to 5:1. In some aspects, the ratio of glass fiber to mineral filler can be in the range of greater than 1:1 to 9:1, 2:1 or greater, or 2:1 to 9:1.

[0105] Polycarbonate compositions may contain organophosphorus flame retardants. In aromatic organophosphorus compounds having at least one organic aromatic group, the aromatic group may be a substituted or unsubstituted C-terminal containing one or more monocyclic or polycyclic aromatic moieties (which may optionally contain up to three heteroatoms (N, O, P, S, or Si)) and optionally also containing one or more non-aromatic moieties (e.g., alkyl, alkenyl, ynyl, or cycloalkyl). 3-30 Aromatic groups. The aromatic portion of an aromatic group may be directly bonded to a phosphorus-containing group or bonded via another portion (e.g., an alkylene group). In one aspect, the aromatic group is the same as the aromatic group of the polycarbonate backbone, such as a bisphenol group (e.g., bisphenol A), a monoarylene (e.g., 1,3-phenylene or 1,4-phenylene), or a combination comprising at least one of the foregoing.

[0106] The phosphorus-containing group can be a phosphate ester (P(=O)(OR)3), a phosphite (P(OR)3), a phosphonate (RP(=O)(OR)2), a hypophosphonate (R2P(=O)(OR)), a phosphonium oxide (R3P(=O)), or a phosphonium (R3P), wherein each R in the above phosphorus-containing group can be the same or different, provided that at least one R is an aromatic group. Combinations of different phosphorus-containing groups can be used. The aromatic group can be directly or indirectly bonded to phosphorus, or bonded to the oxygen of the phosphorus-containing group (i.e., the ester).

[0107] In one aspect, aromatic organophosphorus compounds are monomeric phosphates. Representative monomeric aromatic phosphates have the formula (GO)3P=O, where each G is independently an alkyl, cycloalkyl, aryl, alkylarylene, or arylalkylene group having up to 30 carbon atoms, provided that at least one G is an aromatic group. Two G groups can be linked together to provide a cyclic group. In some aspects, G corresponds to a monomer used to form polycarbonate, such as resorcinol. Exemplary phosphate esters include phenyl bis(dodecyl) phosphate, phenyl bis(neopentyl) phosphate, phenyl bis(3,5,5'-trimethylhexyl) phosphate, ethyl diphenyl phosphate, 2-ethylhexyl di(p-tolyl) phosphate, bis(2-ethylhexyl)p-tolyl phosphate, tricresyl phosphate, bis(2-ethylhexyl)phenyl phosphate, tri(nonylphenyl) phosphate, bis(dodecyl)p-tolyl phosphate, dibutylphenyl phosphate, 2-chloroethyl diphenyl phosphate, p-tolyl bis(2,5,5'-trimethylhexyl) phosphate, 2-ethylhexyl diphenyl phosphate, etc. Specific aromatic phosphate esters are phosphate esters in which each G is aromatic, such as triphenyl phosphate, tricresyl phosphate, isopropylated triphenyl phosphate, etc.

[0108] Bifunctional or polyfunctional aromatic organophosphorus compounds are also useful, for example, compounds of the following formula:

[0109]

[0110] Among them, each G 1 C is independent 1-30 Hydrocarbon group; each G 2 Independently for C 1-30 hydrocarbon group or hydroxyl group; X a It is as defined in equation (3) or equation (4); each X is independently bromine or chlorine; m is 0 to 4, and n is 1 to 30. In one specific aspect, X a It is a single bond, methylene, isopropylidene, or 3,3,5-trimethylcyclohexylidene.

[0111] Specific aromatic organophosphorus compounds include esters of formula (9):

[0112]

[0113] Among them, each R 16 C is independent 1-8 Alkyl, C 5-6 cycloalkyl, C 6-20 Aryl, or C 7-12 Arylalkylene groups, each optionally C 1-12 Alkyl groups, specifically C 1-4Alkyl substitution, and X is a mononuclear or polynuclear aromatic C. 6-30 Partially or linearly or branched C 2-30 Aliphatic groups, which may be OH-substituted and may contain up to eight ether bonds, provided that at least one R 16 Or X is an aromatic group; each n is independently 0 or 1; and q is from 0.5 to 30. In some respects, each R 16 C is independent 1-4 Alkyl, naphthyl, phenyl (C 1-4 ) alkylene, aryl, optionally C 1-4 Alkyl substitution; each X is a mononuclear or polynuclear aromatic C 6-30 In some respects, each n is 1; and q ranges from 0.5 to 30. In some aspects, each R... 16 It is aromatic, such as phenyl; each X is a mononuclear or polynuclear aromatic C. 6-30 The part includes the part derived from equation (2); n is 1; and q is from 0.8 to 15. In other respects, each R 16 X is phenyl; X is tolyl, xylyl, propylphenyl, or butylphenyl, one of the following divalent groups.

[0114]

[0115] Or a combination of one or more of the foregoing; n is 1; and q is 1 to 5, or 1 to 2. In some respects, at least one R 16 Or X corresponds to the monomer used to form polycarbonate, such as bisphenol A, resorcinol, etc. This type of aromatic organophosphorus compound includes hydroquinone bis(diphenyl) phosphate, resorcinol bis(diphenyl) phosphate (RDP), and bisphenol A bis(diphenyl) phosphate (BPADP), as well as their oligomeric and polymeric counterparts.

[0116] Organophosphorus flame retardants containing phosphorus-nitrogen bonds can be phosphazenes, chlorophosphazenes, phosphatidyl amides, phosphoramides, phosphonamides, phosphinic acid amides, or tri(aziridinyl)phosphine oxide. These flame retardant additives are commercially available. In one aspect, organophosphorus flame retardants containing phosphorus-nitrogen bonds are phosphazenes or cyclic phosphazenes of the following formula:

[0117]

[0118] Where w1 is 3 to 10,000; w2 is 3 to 25, or 3 to 7; and each R w C is independent 1-12 Alkyl, alkenyl, alkoxy, aryl, aryloxy, or polyoxyalkylene groups. In these groups, at least one hydrogen atom may be substituted by a group having an N, S, O, or F atom or by an amino group. For example, each R... wIt can be substituted or unsubstituted phenoxy, amino, or polyoxyalkylene compounds. Any given R w Further, crosslinking to another phosphazene group may be possible. Exemplary crosslinking includes a bisphenol group, such as a bisphenol A group. Examples include phenoxycyclotriphosphazene, octaphenoxycyclotetraphosphazene, decaphenoxycyclopentaphosphazene, etc. In one aspect, the phosphazene has a structure represented by the following formula:

[0119]

[0120] Commercially available phenoxyphosphazenes having the above structure are LY202 manufactured and sold by Lanyin Chemical Co., Ltd., FP-110 manufactured and sold by Fushimi Pharmaceutical Co., Ltd., and SPB-100 manufactured and sold by Otsuka Chemical Co., Ltd.

[0121] The organophosphorus flame retardant may be present in up to 1.5 wt%, up to 1.2 wt%, up to 1.0 wt%, up to 0.8 wt%, up to 0.6 wt%, or up to 0.4 wt%, each based on the total weight of the composition.

[0122] In addition to organophosphorus flame retardants, polycarbonate compositions may contain flame retardants. Inorganic flame retardants, such as C, may also be used. 2-16Salts of alkyl sulfonates such as potassium perfluorobutane sulfonate (Rimar salt), potassium perfluorooctane sulfonate, and tetraethylammonium perfluorohexane sulfonate; salts of aromatic sulfonates such as sodium benzenesulfonate and sodium toluenesulfonate (NATS); and salts of aromatic sulfonates such as potassium diphenyl sulfone sulfonate (KSS); and salts formed by reactions of alkali metals or alkaline earth metals (e.g., lithium, sodium, potassium, magnesium, calcium, and barium salts) and inorganic acids, such as oxygen-anions (e.g., alkali metal and alkaline earth metal salts of carbonic acid, such as Na₂CO₃, K₂CO₃, MgCO₃, CaCO₃, and BaCO₃), or fluorine-anion complexes such as Li₃AlF₆, BaSiF₆, KBF₄, K₃AlF₆, KAlF₄, K₂SiF₆, or Na₃AlF₆. Rimar salts and KSS and NATS, alone or in combination with other flame retardants, are particularly useful. Rimar salts and KSS and NATS, alone or in combination with other flame retardants, are particularly useful. Based on the total weight of the composition, perfluoroalkyl sulfonates may be present in an amount of 0.30 to 1.00 wt%, preferably 0.40 to 0.80 wt%, more preferably 0.45 to 0.70 wt%. Aromatic sulfonates may be present in the final polycarbonate composition in an amount of 0.01 to 0.1 wt%, preferably 0.02 to 0.06 wt%, and more preferably 0.03 to 0.05 wt%. Based on the total weight of the polycarbonate composition, exemplary amounts of aromatic sulfone sulfonates may be 0.01 to 0.6 wt%, preferably 0.1 to 0.4 wt%, and more preferably 0.25 to 0.35 wt%.

[0123] Besides organophosphorus flame retardants, halogenated materials can also be used as flame retardants, such as the following representative bisphenols: 2,2-bis-(3,5-dichlorophenyl)-propane; bis-(2-chlorophenyl)-methane; bis(2,6-dibromophenyl)-methane; 1,1-bis-(4-iodophenyl)-ethane; 1,2-bis-(2,6-dichlorophenyl)-ethane; 1,1-bis-(2-chloro-4-iodophenyl)-ethane; 1,1-bis-(2-chloro-4-methylphenyl)-ethane; 1,1-bis-(3,5-dichlorophenyl)-ethane; 2,2-bis-(3-phenyl-4-bromophenyl)-ethane; 2,6-bis-(4,6-dichloronaphthyl)-propane; and 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane; 2,2-bis-(3-bromo-4-hydroxyphenyl)-propane. Other halogenated materials include 1,3-dichlorobenzene, 1,4-dibromobenzene, 1,3-dichloro-4-hydroxybenzene, and biphenyls such as 2,2'-dichlorobiphenyl, polybrominated 1,4-diphenoxybenzene, 2,4'-dibromobiphenyl, and 2,4'-dichlorobiphenyl, as well as decabromodiphenyl ether, and oligomerized and polymerized halogenated aromatic compounds such as bisphenol A and tetrabromobisphenol A copolycarbonates with carbonate precursors (e.g., phosgene). Metal synergists, such as antimony oxide, may also be used with the flame retardant. When present, the amount of the halogenated flame retardant is 1 to 25 parts by weight, more preferably 2 to 20 parts by weight, based on 100 parts by weight of the total composition excluding any fillers.

[0124] Anti-dripping agents, such as fluoropolymers that form fibrils or nonfibrils, like polytetrafluoroethylene (PTFE), may also be used in the composition. The anti-dripping agent can be encapsulated by a rigid copolymer, such as styrene-acrylonitrile copolymer (SAN). PTFE encapsulated in SAN is referred to as TSAN. Based on the total weight of the encapsulated fluoropolymer, TSAN contains 50 wt% PTFE and 50 wt% SAN. Based on the total weight of the copolymer, SAN may contain, for example, 75 wt% styrene and 25 wt% acrylonitrile. Based on 100 parts by weight of the total composition excluding any fillers, the anti-dripping agent can be used in amounts from 0.1 to 10 parts by weight.

[0125] The polycarbonate composition may comprise a polycarbonate comprising linear bisphenol A homopolymer; a poly(carbonate-siloxane) present in an amount of 1-10 wt% of total siloxane based on the total weight of the composition; and 11-25 wt% of a reinforcing composition comprising 10-24 wt% glass fiber and 1-10 wt% mineral filler. Each poly(carbonate-siloxane) copolymer may comprise, based on the total weight of each copolymer, a poly(carbonate-siloxane) copolymer containing 10 wt% or less of siloxane, a poly(carbonate-siloxane) copolymer containing more than 10 wt% to less than 30 wt% of siloxane, a poly(carbonate-siloxane) copolymer containing 30-70 wt% of siloxane, or a combination thereof.

[0126] The polycarbonate composition may comprise polycarbonate, including linear bisphenol A homopolymer and brominated polycarbonate; poly(carbonate-siloxane) present in an amount of 1-10 wt% total siloxane based on the total weight of the composition; and 11-25 wt% of a reinforcing composition comprising 10-24 wt% glass fiber and 1-10 wt% mineral filler. Each poly(carbonate-siloxane) copolymer may comprise, based on the total weight of each copolymer, a poly(carbonate-siloxane) copolymer with a siloxane content of 10 wt% or less, a poly(carbonate-siloxane) copolymer with a siloxane content of greater than 10 wt% but less than 30 wt%, a poly(carbonate-siloxane) copolymer with a siloxane content of 30-70 wt%, or a combination thereof.

[0127] The polycarbonate composition may comprise a polycarbonate comprising linear bisphenol A homopolymer polycarbonate and poly(ester-carbonate-siloxane); a poly(carbonate-siloxane) present in an amount of 1-10 wt% of total siloxane based on the total weight of the composition; and 11-25 wt% of a reinforcing composition comprising 10-24 wt% glass fiber and 1-10 wt% mineral filler. In some aspects, the poly(ester-carbonate-siloxane) comprises bisphenol A carbonate units, bisphenol A isophthalate-bisphenol A terephthalate units, and siloxane units, such as blocks comprising 5 to 200 dimethylsiloxane units. Based on the total weight of each poly(carbonate-siloxane) copolymer, the polycarbonate composition may contain a poly(carbonate-siloxane) copolymer containing 10 wt% or less of siloxane, a poly(carbonate-siloxane) copolymer containing more than 10 wt% to less than 30 wt% of siloxane, a poly(carbonate-siloxane) copolymer containing 30-70 wt% of siloxane, or a combination thereof.

[0128] The polycarbonate composition may comprise: a polycarbonate including poly(aliphatic ester-carbonate) and poly(ester-carbonate-siloxane); a poly(carbonate-siloxane) present in an amount of 1-10 wt% of total siloxane based on the total weight of the composition; and 11-25 wt% of a reinforcing composition comprising 10-24 wt% glass fiber and 1-10 wt% mineral filler. In some aspects, the poly(aliphatic ester-carbonate) comprises bisphenol A carbonate units and sebacic acid-bisphenol A ester units. In some aspects, the poly(ester-carbonate-siloxane) comprises bisphenol A carbonate units, bisphenol A isophthalate-bisphenol A terephthalate units, and siloxane units, such as blocks comprising 5 to 200 dimethylsiloxane units. Based on the total weight of each poly(carbonate-siloxane) copolymer, the polycarbonate composition may contain a poly(carbonate-siloxane) copolymer containing 10 wt% or less of siloxane, a poly(carbonate-siloxane) copolymer containing more than 10 wt% to less than 30 wt% of siloxane, a poly(carbonate-siloxane) copolymer containing 30-70 wt% of siloxane, or a combination thereof.

[0129] The polycarbonate composition may comprise polycarbonate, including poly(phthalate-carbonate); poly(carbonate-siloxane) present in an amount of 1-10 wt% of total siloxane based on the total weight of the composition; and 5-25 wt% of a reinforcing composition comprising 11-24 wt% glass fiber and 1-10 wt% mineral filler. In some aspects, the poly(phthalate-carbonate) comprises bisphenol A carbonate units and bisphenol A isophthalate-bisphenol A terephthalate units. Based on the total weight of each poly(carbonate-siloxane) copolymer, the polycarbonate composition may comprise a poly(carbonate-siloxane) copolymer containing 10 wt% or less of siloxane, a poly(carbonate-siloxane) copolymer containing more than 10 wt% to less than 30 wt% of siloxane, a poly(carbonate-siloxane) copolymer containing 30-70 wt% of siloxane, or combinations thereof.

[0130] The polycarbonate composition may comprise polycarbonate, including poly(ester-carbonate); poly(carbonate-siloxane) present in an amount of 1-10 wt% of total siloxane based on the total weight of the composition; and 11-25 wt% of a reinforcing composition comprising 10-24 wt% glass fiber and 1-10 wt% mineral filler. In some aspects, the poly(ester-carbonate) comprises resorcinol resorcinate and terephthalate units and bisphenol A carbonate units. Based on the total weight of each poly(carbonate-siloxane) copolymer, the polycarbonate composition may comprise a poly(carbonate-siloxane) copolymer containing 10 wt% or less of siloxane, a poly(carbonate-siloxane) copolymer containing more than 10 wt% to less than 30 wt% of siloxane, a poly(carbonate-siloxane) copolymer containing 30-70 wt% of siloxane, or a combination thereof.

[0131] Polycarbonate compositions can be prepared by various methods. For example, in a HENSCHEL high-speed mixer, powdered polycarbonate and optional components are first blended with fillers. Other low-shear processes, including but not limited to hand mixing, can also achieve this blending. The blend is then fed through a hopper into the throat of a twin-screw extruder. Alternatively, at least one component can be incorporated into the composition by direct feeding into the extruder via a side filler at the throat or downstream. Additives can also be mixed with the desired polymer to form a masterbatch and fed into the extruder. The extruder is typically operated at a temperature above that necessary to cause flow in the composition. The extrudate is immediately quenched in a water bath and granulated. The granules thus prepared can be quarter-inch long or smaller, depending on the requirements. Such granules can be used for subsequent molding, shaping, or forming.

[0132] Also provided are shaped, molded, or molded articles comprising polycarbonate compositions. Polycarbonate compositions can be molded into useful shaped articles by a variety of methods, such as injection molding, extrusion, rotational molding, blow molding, and thermoforming. In one aspect, the articles are extruded articles, molded articles, pultruded articles, thermoformed articles, foamed articles, layers of multilayer articles, substrates for coated articles, or substrates for metallized articles.

[0133] Transportation components are also provided, particularly interior train components molded or extruded from polycarbonate compositions. Molding can be performed in various ways, such as injection molding, rotational molding, blow molding, etc. In one aspect, molding is performed by injection molding. Exemplary cladding includes, for example, interior vertical surfaces such as sidewalls, front walls, end walls, partitions, compartment dividers, fins, boxes, engine hoods, and louvers; interior doors and linings for interior and exterior doors; window insulation, galley interior surfaces, interior horizontal surfaces such as ceiling panels, flaps, boxes, engine hoods, and louvers; baggage storage areas such as overhead and vertical baggage racks, baggage containers, and compartments; driver's desktop applications such as paneling and driver's desktop surfaces; inner surfaces of gangways such as gangway membranes (corrugated pipes) and the inside of interior linings; window frames (including sealants and gaskets); (folded) tables with downward-facing surfaces; air duct interior and exterior surfaces; passenger information equipment (such as information displays), etc.

[0134] The data in the examples show that the compositions used here can meet the requirements of HL2 for R1 and R6 applications.

[0135] While the compositions described herein are designed preferably for use in railway interiors, it should be understood that they are also useful for R1 and R6 applications in other interior components that require compliance with the testing standards for HL2. Internal bus assemblies are particularly mentioned. Current discussions concerning improved bus safety include proposals to apply the HL2 standard to internal bus assemblies. The invention therefore includes internal bus assemblies comprising the seat assembly and cladding as described above, and containing the preferred compositions described herein, and particularly those described below, that meet the tests specified in the aforementioned HL2 standard.

[0136] Among its particularly advantageous features, the compositions described herein meet other stringent standards for rail applications. For example, for internal applications used in the U.S. rail market, materials need to meet NFPA 130 (2010 edition). This standard sets requirements for smoke generation rate and surface flammability. Smoke generation is measured by the ASTM E662-12 smoke density test, requiring a preferred smoke density (Ds1.5) of 100 or lower after 1.5 minutes, and a preferred smoke density (Ds4) of 200 or lower after 4 minutes in either combustion or non-combustion mode. Surface flammability is measured by the ASTM E162-12a flame spread test, requiring a maximum flame spread index (Is) of 35 or lower, and prohibiting burning, running, or dripping. It is calculated by multiplying the flame spread factor (Fs) and the heat factor (Q) determined during the test. Certain preferred compositions described herein, and particularly below, also meet these standards.

[0137] This disclosure is further illustrated by the following examples, which are not limiting.

[0138] Example

[0139] The following components are used in the examples. Unless otherwise specified, the amount of each component is in wt% based on the total weight of the composition.

[0140] Use the materials shown in Table 2.

[0141] Table 2

[0142]

[0143]

[0144] The test sample is prepared as described below and the following test method is used.

[0145] A typical compounding procedure is described below: All raw materials are compounded on a 25mm Werner Pfleiderer ZSK co-rotating twin-screw extruder with a vacuum-depleted standard mixing screw operating at a screw speed of 300 rpm. Glass fiber is added via a side feeder located downstream. The temperature profile is given in Table 1. The stock is cooled in a water bath before granulation. The granules are dried in a forced-air circulating oven at 90–110°C for 3–4 hours before injection molding. Typical extrusion profiles are listed in Table 3.

[0146] Table 3

[0147]

[0148]

[0149] Engel 45, 75, and 90 molding machines are used to mold test parts for standard physical performance testing. (See Table 4 for parameters).

[0150] Table 4

[0151] parameter unit Pre-drying time h 34 Pre-drying temperature ℃ 90-110 Hopper temperature ℃ 40 Zone 1 temperature ℃ 260-290 Zone 2 temperature ℃ 270-300 Zone 3 temperature ℃ 280-310 Nozzle temperature ℃ 275-305 mold temperature ℃ 75-100 Screw speed rpm 25 back pressure -bar 5 Injection time s 1.9 Approximate cycle time s 45

[0152] The sample preparation and testing methods are described in Table 5.

[0153] Table 5

[0154]

[0155] Examples 1-12

[0156] Table 6 shows the composition and performance of Examples 1-8 and Comparative Examples 9-12.

[0157] Table 6

[0158]

[0159]

[0160] *Comparative Examples

[0161] The compositions of Examples 1-8, including homopolymer carbonate and poly(carbonate-siloxane) (PC-Si-1) and (PC-Si-2), provide the desired combination of properties: a DS4 of less than or equal to 300 and a MAHRE value of 90 or less. Examples 1-3 show that the combination of glass fiber (NBGF) and talc provides the desired properties. In Examples 1-3, the ratio of glass fiber to talc ranges from 2:1 to 4:1. As shown in Example 5, reducing the talc loading does not adversely affect the performance (comparing Examples 5 and Examples 1-3). Examples 4 and 6-8 show that when an organophosphorus flame retardant (P-FR) is incorporated, the DS4 and MAHRE values ​​are within the desired range. Comparative Examples 9-10, which include glass fiber and exclude talc, provide DS4 values ​​within the desired range, but MAHRE values ​​are outside the desired range. Comparative Example 11, which included glass fiber (20 wt%), excluded talc but included an organophosphorus flame retardant (4 wt%, 0.43 wt% phosphorus), resulting in both DS4 and MAHRE values ​​being outside the expected range. Comparative Example 12, with a reduced glass fiber loading (15 wt%), resulted in a DS4 value outside the expected range and a MAHRE value within the expected range.

[0162] In summary, using only 10-20% glass fiber as the sole filler in compositions comprising polycarbonate, polycarbonate-siloxane copolymers, and optionally organophosphorus flame retardants can result in smoke density and / or heat release performance limits that are at or above the thresholds required to meet the R6-HL2 requirements of the EN45545 European rail standard (i.e., DS4 less than 300 and MAHRE less than 90 kW / m). 2 (As shown for Comparative Examples 9-12). The use of a combination of glass fiber and mineral filler (such as talc) results in a reduction in smoke density (DS4 value below 250 and MAHRE value below 90 kW / m³) at similar total loadings of 10-25 wt% of the reinforcing composition. 2 Synergistic effect.

[0163] Examples 13-24

[0164] Table 7 shows the composition and performance of Examples 13-24.

[0165] Table 7

[0166]

[0167]

[0168] The compositions in Table 7 include poly(carbonate-siloxane), polycarbonate other than poly(carbonate-siloxane), and reinforcing compositions comprising a combination of glass fiber and talc. Examples 13-24 demonstrate that in compositions comprising a combination of glass fiber and talc as a reinforcing composition (13.5 wt% of total load), a desired combination of DS4 values ​​less than or equal to 300 and MAHRE values ​​of 90 or less can be achieved. In such compositions, polycarbonates other than poly(carbonate-siloxane) include: linear BPA homopolymers (e.g., Examples 13, 17-29, and 24); combinations of linear BPA homopolymers and poly(ester-carbonate-siloxane) (i.e., Example 15); combinations of poly(ester-carbonate-siloxane) and poly(aliphatic ester-carbonate) (i.e., Example 16); combinations of poly(phthalate-carbonate) and linear BPA homopolymers (i.e., Examples 20-22); or poly(ester-carbonate) (i.e., Example 23).

[0169] This disclosure further covers the following aspects.

[0170] Aspect 1. A polycarbonate composition comprising: a polycarbonate including homopolymer, poly(ester-carbonate-siloxane), poly(aliphatic ester-carbonate), poly(ester-carbonate-siloxane), brominated polycarbonate, poly(ester-carbonate), or combinations thereof, and optionally, poly(phthalate-carbonate); poly(carbonate-siloxane) present in an amount effectively providing 1-10 wt% of total siloxane based on the total weight of the composition; 11-25 wt% of a reinforcing composition comprising 10-24 wt% glass fiber and 1-10 wt% mineral filler comprising talc, kaolin, calcium carbonate, wollastonite, or combinations thereof; optionally, an organophosphorus flame retardant effectively providing up to 1.5 wt% of phosphorus; and optionally, up to 10 wt% of an additive composition, wherein the amounts are based on the total weight of the polycarbonate composition and the sum of the amounts is 100 wt%.

[0171] Aspect 1a. The polycarbonate composition according to aspect 1, wherein the polycarbonate comprises homopolymer or a combination of homopolymer and brominated polycarbonate, and the poly(carbonate-siloxane) has a siloxane content in the range of 30-70 wt% based on the total weight of the poly(carbonate-siloxane).

[0172] Aspect 1b. The polycarbonate composition according to aspect 1, wherein the polycarbonate comprises poly(ester-carbonate-siloxane), poly(aliphatic ester-carbonate), poly(ester-carbonate-siloxane), brominated polycarbonate, poly(ester-carbonate), poly(phthalate-carbonate), and optionally homopolymer polycarbonate.

[0173] Aspect 2. The polycarbonate composition according to aspect 1, wherein the ratio of glass fiber to mineral filler is 1:1 or greater, preferably 2:1 or greater.

[0174] Aspect 3. A polycarbonate composition according to Aspect 1 or Aspect 2, wherein a molded sample of the composition has a smoke density (DS4) of 300 or less after 4 minutes, measured according to ISO 5659-2 on a 3 mm thick plate; and has a smoke density of 90 kW / m², measured according to ISO 5660-1 on a 3 mm thick plate. 2 Or even lower heat release (MAHRE); optionally, molded samples of the composition have a heat release of 20 kW / m² measured on a 3 mm thick plate according to ISO 5658-2. 2 Or even smaller critical heat flux (CFE) at extinction.

[0175] Aspect 4a. The polycarbonate composition according to aspect 1 or 3, wherein the poly(carbonate-siloxane) further comprises a poly(carbonate-siloxane) copolymer containing 10 wt% or less of a siloxane content, a poly(carbonate-siloxane) copolymer containing more than 10 wt% to less than 30 wt% of a siloxane content, or a combination thereof, each based on the total weight of each respective poly(carbonate-siloxane) copolymer.

[0176] Aspect 4b. The polycarbonate composition according to aspect 2 or 3, wherein the poly(carbonate-siloxane) comprises a poly(carbonate-siloxane) copolymer containing 10 wt% or less of a siloxane content, a poly(carbonate-siloxane) copolymer containing more than 10 wt% to less than 30 wt% of a siloxane content, a poly(carbonate-siloxane) copolymer containing 30-70 wt% of a siloxane content, or a combination thereof, each based on the total weight of each respective poly(carbonate-siloxane) copolymer.

[0177] Aspect 5. A polycarbonate composition according to any of the preceding aspects, wherein the organophosphorus flame retardant comprises a monomer or oligophosphate (P(=O)(OR)3), phosphite (P(OR)3), phosphonate (RP(=O)(OR)2), hypophosphonate (R2P(=O)(OR)), phosphine oxide (R3P(=O)), or phosphine (R3P), wherein each R may be the same or different, provided that at least one R is an aromatic group; a monomer or oligomer having at least one phosphorus-nitrogen bond; or a combination thereof.

[0178] Aspect 6. The polycarbonate composition according to any one of the preceding aspects, wherein the organophosphorus flame retardant comprises:

[0179]

[0180] Or combinations thereof, where G appears each time 1 C is independent 1-30 Hydrocarbon group; G appears each time 2 C is independent 1-30 Hydrocarbon or hydroxyl group; each X is independently bromine or chlorine; m is 0 to 4 and n is 1 to 30;

[0181]

[0182] Among them, R 16 R 17 R 18 and R 19 Each is C independently 1-8 Alkyl, C 5-6 cycloalkyl, C 6-20 Aryl, or C 7-12Arylalkylene groups, each optionally C 1-12 Alkyl, preferably C 1-4 Alkyl substitution, and X is a mononuclear or polynuclear aromatic C. 6-30 Partially or linearly or branched C 2-30 Aliphatic groups, each optionally substituted with OH and optionally containing up to eight ether bonds, provided that R 16 R 17 R 18 R 19 At least one of X and X is an aromatic group; or a combination thereof.

[0183] Aspect 7. A polycarbonate composition according to any one of the preceding aspects, wherein the organophosphorus flame retardant comprises phosphazene, chlorinated phosphazene, phosphatidyl amide, phosphoramide, phosphonamide, phosphinic acid amide, or tri(aziridinyl)phosphine oxide; or phosphazene or cyclic phosphazene of the following formula:

[0184]

[0185] Where w1 is 3 to 10,000; w2 is 3 to 25, or 3 to 7; and each R w C is independent 1-12 Alkyl, alkenyl, alkoxy, aryl, aryloxy, or polyoxyalkylene, optionally with at least one hydrogen atom substituted with an N, S, O, or F atom or with an amino group.

[0186] Aspect 8. The polycarbonate composition according to any one of the preceding aspects, wherein the mineral filler further comprises mica, clay, feldspar, quartz, quartzite, perlite, diatomite, diatomaceous earth, aluminum silicate, synthetic calcium silicate, fused silica, fumed silica, sand, boron nitride powder, boron silicate powder, calcium sulfate, calcium carbonate, talc, wollastonite, or combinations thereof.

[0187] Aspect 9. The polycarbonate composition according to any one of the preceding aspects, wherein the additive composition comprises a filler different from a mineral filler, a reinforcing agent different from a mineral filler, an antioxidant, a heat stabilizer, a light stabilizer, an ultraviolet light stabilizer, a plasticizer, a lubricant, a mold release agent, an antistatic agent, a colorant, a surface effect additive, a radiation stabilizer, a flame retardant different from an organophosphorus flame retardant, an anti-dripping agent, or a combination thereof.

[0188] Aspect 10a. A polycarbonate composition according to any one of Aspects 1 and 3 to 9, comprising: homopolymer polycarbonate or a combination of homopolymer polycarbonate and brominated polycarbonate, wherein the poly(carbonate-siloxane) comprises: poly(carbonate-siloxane) having a siloxane content of 30-70 wt% based on the total weight of the poly(carbonate-siloxane), 11-25 wt% of a reinforcing composition comprising 10-24 wt% glass fiber and 1-10 wt% mineral filler (including talc); an organophosphorus flame retardant effectively providing up to 1.5 wt% phosphorus; optionally, up to 10 wt% of an additive composition, wherein the amounts are based on the total weight of the polycarbonate composition and the sum of the amounts is 100 wt%.

[0189] Aspect 10b. A polycarbonate composition according to any one of Aspects 2 to 9, comprising: polycarbonate, including poly(ester-carbonate-siloxane), poly(aliphatic ester-carbonate), poly(ester-carbonate-siloxane), brominated polycarbonate, poly(ester-carbonate), poly(phthalate-carbonate), or combinations thereof, and optionally, all polycarbonate; a poly(carbonate-siloxane) copolymer containing more than 10 wt% to less than 30 wt% of siloxane, or a poly(carbonate-siloxane) copolymer containing 30-70 wt% of siloxane. The composition, or combinations thereof, is based on the total weight of each respective poly(carbonate-siloxane) copolymer, wherein the poly(carbonate-siloxane) comprises: poly(carbonate-siloxane); 11-25 wt% of a reinforcing composition comprising 10-24 wt% glass fiber and 1-10 wt% of a mineral filler comprising talc; an organophosphorus flame retardant effectively providing up to 1.5 wt% of phosphorus; and optionally, up to 10 wt% of an additive composition, wherein each amount is based on the total weight of the polycarbonate composition and the sum of the amounts is 100 wt%.

[0190] Aspect 10b-1. A polycarbonate composition according to aspect 10b, wherein the polycarbonate comprises poly(aliphatic ester-carbonate), or a combination of poly(ester-carbonate-siloxane) and poly(aliphatic ester-carbonate), wherein brominated polycarbonate is optionally present.

[0191] Aspect 10b-2. A polycarbonate composition according to aspect 10b, wherein the polycarbonate comprises a combination of poly(ester-carbonate-siloxane) and homopolymer polycarbonate, wherein brominated polycarbonate is optionally present.

[0192] Aspect 10b-3. A polycarbonate composition according to aspect 10b, wherein the polycarbonate comprises poly(ester-carbonate), wherein brominated polycarbonate is optionally present.

[0193] Aspect 10b-4. A polycarbonate composition according to aspect 10b, wherein the polycarbonate comprises a combination of poly(phthalate-carbonate) and homopolymer, wherein brominated polycarbonate is optionally present.

[0194] Aspect 11. An article comprising a polycarbonate composition of any of the foregoing aspects, preferably wherein the article is a track assembly, preferably an internal track assembly.

[0195] Aspect 12. Articles of manufacture according to Aspect 11, wherein the articles of manufacture include seat assemblies, extruded interior train cladding, molded interior train cladding, table trays, headrests, privacy dividers, center consoles, armrests, leg rests, food trays, end bays, covers, kickboards, footwells, document pockets, monitors, sunshades, wiring replacement units, foot pedals, luggage racks, luggage containers, luggage compartments, floor composites, wall composites, air ducts, strips, passenger information equipment, window frames, interior linings, interior vertical surfaces, interior doors, linings for internal doors, linings for external doors, interior horizontal surfaces, electrical components, or lighting components.

[0196] Aspect 13. A method for forming an article according to aspect 12, comprising molding, casting or extruding a composition to provide the article.

[0197] Alternatively, compositions, methods, and articles may comprise, consist of, or consist substantially of any suitable materials, steps, or components disclosed herein. Compositions, methods, and articles may be formulated additionally or alternatively to be free of, or substantially free of, any materials (or species), steps, or components that are not essential to achieving the function or purpose of the composition, method, and article.

[0198] All scopes disclosed herein include endpoints, and endpoints may be combined independently of each other (e.g., the scope of “up to 25 wt%, or more specifically, 5 wt% to 20 wt%” includes the endpoints and all intermediate values ​​of the “5 wt% to 25 wt%” scope, etc.). “Combination” includes blends, mixtures, alloys, reaction products, etc. The terms “first,” “second,” etc., do not indicate any order, quantity, or importance, but are used to distinguish one element from another. Unless otherwise indicated herein or obviously contradicted by the context, the terms “an,” “a,” and “the” do not indicate a limitation of quantity, but are interpreted to cover both singular and plural. Unless otherwise expressly stated, “or” means “and / or.” Throughout the specification, references to “some aspects,” “an aspect,” etc., mean that the specific element described in connection with that aspect is included in at least one aspect described herein and may or may not be present in other aspects. Furthermore, it should be understood that the described elements may be combined in any suitable manner in each aspect. “Combination of them” is open and includes any combination that comprises at least one of the listed components or properties, optionally together with similar or equivalent components or properties not listed.

[0199] Unless otherwise specified herein, all test standards are the most recent standards effective from 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.

[0200] Unless otherwise defined, the technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains. All cited patents, patent applications, and other references are incorporated herein by reference in their entirety. However, if any terminology in this application contradicts or conflicts with terminology in the incorporated references, the terminology from this application shall take precedence over the conflicting terminology from the incorporated references.

[0201] Compounds should be described using standard nomenclature. For example, any position not substituted by any indicator group should be understood as having its valence filled by a bond or hydrogen atom as indicated. A dash ("-") not between two letters or symbols is used to indicate the connection point of a substituent. For example, -CHO is connected through the carbonyl group.

[0202] The term "alkyl" refers to a branched or straight-chain, unsaturated aliphatic hydrocarbon group, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, sec-pentyl, and n-hexyl and sec-hexyl. "Alkenyl" refers to a straight-chain or branched monovalent hydrocarbon group having at least one carbon-carbon double bond (e.g., vinyl(-HC=CH2)). "Alkoxy" refers to an alkyl group linked via oxygen (i.e., alkyl-O-), such as methoxy, ethoxy, and sec-butoxy. "Alkylene" refers to a straight-chain or branched, saturated, divalent aliphatic hydrocarbon group (e.g., methylene(-CH2-) or propylene(-(CH2)3-)). "Cycloalkylene" refers to a divalent cyclic alkylene group, -C n H 2n-x Where x is the number of hydrogen atoms cyclized and substituted. "Cycloalkenyl" refers to a monovalent group having one or more rings and one or more carbon-carbon double bonds within those rings, wherein all ring members are carbon (e.g., cyclopentyl and cyclohexyl). "Aryl" refers to an aromatic hydrocarbon group containing a specified number of carbon atoms, such as phenyl, cycloheptatrienone, indenyl, or naphthyl. "Arylidene" refers to a divalent aryl group. "Alkylarylidene" refers to an arylidene substituted with an alkyl group. "Arylalkylene" refers to an alkylene substituted with an aryl group (e.g., benzyl). The prefix "halogenated" refers to a group or compound comprising one or more of fluorine, chlorine, bromine, or iodine substituents. Combinations of different halogen groups (e.g., bromine and fluorine) or only chlorine groups may be present. The prefix "heterogeneous" refers to a compound or group comprising at least one ring member that is a heteroatom (e.g., 1, 2, or 3 heteroatoms), wherein each heteroatom is independently N, O, S, Si, or P. "Substituted" means that a compound or group is replaced by at least one (e.g., 1, 2, 3, or 4) substituents instead of hydrogen, and each substituent can be an independent C14 group. 1-9 Alkoxy, C 1-9 Halogenated alkoxy, nitro (-NO2), cyano (-CN), C 1-6 alkylsulfonyl (-S(=O)2-alkyl), C 6-12 Arylsulfonyl (-S(=O)2-aryl), mercapto (-SH), cyanothio (-SCN), toluenesulfonyl (CH3C6H4SO2-), C 3-12 cycloalkyl, C 2-12 alkenyl, C 5-12 Cycloalkenyl, C 6-12 Aryl, C 7-13 Arylalkylene, C 4-12 Heterocyclic alkyl groups and C 3-12 Heteroaryl groups are defined as those whose valence does not exceed the normal valence of the substituted atoms. The number of carbon atoms indicated in the group does not include any substituents. For example, -CH2CH2CN is a C2 alkyl group substituted with a nitrile.

[0203] While specific aspects have been described, alternatives, modifications, variations, improvements, and substantial equivalents may be conceived by the applicant or others skilled in the art that are currently unforeseeable or likely to be unforeseeable. Therefore, the appended claims, as filed and as they may be modified, are intended to cover all such alternatives, modifications, variations, improvements, and substantial equivalents.

Claims

1. A polycarbonate composition comprising: Homopolymer carbonate, or a combination of homopolymer carbonate and brominated polycarbonate; A poly(carbonate-siloxane) containing 30-70 wt% siloxane content, wherein the poly(carbonate-siloxane) is present in an amount that effectively provides 1-10 wt% total siloxane based on the total weight of the composition; 11-25 wt% of a reinforcing composition, said reinforcing composition comprising: 10-24 wt% glass fiber, and 1-10 wt% mineral filler, wherein the mineral filler includes talc; Optionally, an organophosphorus flame retardant can be provided in an amount of up to 1.5 wt% phosphorus; Optionally, up to 10 wt% of the additive composition, in, Each amount is based on the total weight of the polycarbonate composition, and the sum of the amounts is 100 wt%.

2. A polycarbonate composition comprising: Polycarbonate, the polycarbonate comprising poly(ester-carbonate-siloxane), poly(aliphatic ester-carbonate), brominated polycarbonate, poly(ester-carbonate), poly(phthalate-carbonate), or combinations thereof, and optionally, all polycarbonate; Poly(carbonate-siloxane), based on the total weight of the composition, the poly(carbonate-siloxane) is present in an amount that effectively provides 1-10 wt% of total siloxane; 11-25 wt% of a reinforcing composition, said reinforcing composition comprising: 10-24 wt% glass fiber, and 1-10 wt% mineral filler, wherein the mineral filler includes talc; Optionally, an organophosphorus flame retardant can be provided in an amount of up to 1.5 wt% phosphorus; Optionally, up to 10 wt% of the additive composition, in, Each amount is based on the total weight of the polycarbonate composition, and the sum of each amount is 100 wt%.

3. The polycarbonate composition according to claim 1 or 2, wherein, The weight ratio of glass fiber to mineral filler is 1:1 or greater.

4. The polycarbonate composition according to claim 1 or 2, wherein, The molded sample of the composition has the following characteristics: Smoke density of 300 or less after 4 minutes, measured on a 3 mm thick plate according to ISO 5659-2; and 90 kW / m measured on a 3 mm thick plate according to ISO 5660-1 2 Or even smaller maximum average heat release; Optionally, the molded sample of the composition has a power output of 20 kW / m² measured on a 3 mm thick plate according to ISO 5658-2. 2 Or even smaller critical heat flux during extinction.

5. The polycarbonate composition according to claim 1 or 2, wherein, The poly(carbonate-siloxane) comprises: Poly(carbonate-siloxane) copolymers containing 10 wt% or less of siloxane content, Poly(carbonate-siloxane) copolymers containing more than 10 wt% to less than 30 wt% siloxane content. Poly(carbonate-siloxane) copolymers, or combinations thereof, containing 30-70 wt% siloxane content. Each is based on the total weight of each poly(carbonate-siloxane) copolymer.

6. The polycarbonate composition according to claim 1 or 2, wherein, The organophosphorus flame retardant includes: Monomers or oligophosphates P(=O)(OR)3, phosphites P(OR)3, phosphonates RP(=O)(OR)2, hypophosphonates R2P(=O)(OR), phosphine oxides R3P(=O), or phosphine R3P, wherein each R is the same or different, provided that at least one R is an aromatic group. Monomers or oligomers having at least one phosphorus-nitrogen bond; Or a combination thereof.

7. The polycarbonate composition according to claim 1 or 2, wherein, The organophosphorus flame retardant includes: Or a combination of them, Among them, each occurrence of G 1 C is independent 1-30 Hydrocarbon group, each time G appears 2 C is independent 1-30 hydrocarbon group or hydroxyl group, X a It is a single bond, -O-, -S-, -S(O)-, -S(O)2-, -C(O)-, or C. 1-60 Organic groups, each X being bromine or chlorine independently, m being 0 to 4, and n being 1 to 30; Among them, R 16 R 17 R 18 and R 19 Each is C independently 1-8 Alkyl, C 5-6 cycloalkyl, C 6-20 Aryl, or C 7-12 Arylalkylene groups, each optionally C 1-12 Alkyl substitution, and X' is a mononuclear or polynuclear aromatic C 6-30 Partially or linearly or branched C 2-30 Aliphatic groups, each optionally OH-substituted and optionally containing up to eight ether bonds, provided that: R 16 R 17 R 18 R 19 At least one of X' and X' is an aromatic group; Or a combination thereof.

8. The polycarbonate composition according to claim 1 or 2, wherein, The organophosphorus flame retardant includes: Phosphazene, chlorinated phosphazene, phosphoamide, phosphoramide, phosphonamide, hypophosphonamide, or tri(aziridinyl)phosphine oxide.

9. The polycarbonate composition according to claim 1 or 2, wherein, The mineral filler further includes mica, clay, feldspar, quartz, quartzite, perlite, diatomite, diatomaceous earth, aluminum silicate, synthetic calcium silicate, fused silica, fumed silica, sand, boron nitride powder, boron silicate powder, calcium sulfate, calcium carbonate, wollastonite, or combinations thereof.

10. The polycarbonate composition according to claim 1 or 2, wherein, The additive composition comprises antioxidants, heat stabilizers, light stabilizers, ultraviolet stabilizers, plasticizers, lubricants, release agents, antistatic agents, colorants, surface effect additives, radiation stabilizers, flame retardants other than the organophosphorus flame retardants, anti-dripping agents, or combinations thereof.

11. The polycarbonate composition according to claim 1, comprising: Homopolymer carbonate or a combination of homopolymer carbonate and brominated polycarbonate; Poly(carbonate-siloxane), based on the total weight of the poly(carbonate-siloxane), the poly(carbonate-siloxane) has a siloxane content of 30-70 wt%; 11-25 wt% of a reinforcing composition, said reinforcing composition comprising: 10-24 wt% glass fiber; 1-10 wt% talc; Effectively provides organophosphorus flame retardants with up to 1.5 wt% phosphorus; Optionally, up to 10 wt% of the additive composition, in, Each amount is based on the total weight of the polycarbonate composition, and the sum of each amount is 100 wt%.

12. The polycarbonate composition according to claim 2, comprising: Polycarbonate, the polycarbonate comprising poly(ester-carbonate-siloxane), poly(aliphatic ester-carbonate), brominated polycarbonate, poly(ester-carbonate), poly(phthalate-carbonate), or combinations thereof, and optionally, all polycarbonate; Poly(carbonate-siloxane), wherein, The poly(carbonate-siloxane) comprises: Based on the total weight of the poly(carbonate-siloxane), the poly(carbonate-siloxane) having a siloxane content of 30-70 wt%, Poly(carbonate-siloxane) having a siloxane content of up to 10 wt% and poly(carbonate-siloxane) having a siloxane content of 30-70 wt%, respectively based on the total weight of each corresponding poly(carbonate-siloxane), or The poly(carbonate-siloxane) having a siloxane content of greater than 10 wt% to less than 30 wt% based on the total weight of the poly(carbonate-siloxane); 11-25 wt% of a reinforcing composition, said reinforcing composition comprising: 10-24 wt% glass fiber; 1-10 wt% mineral filler, said mineral filler including talc, kaolin, calcium carbonate, wollastonite, or combinations thereof; Effectively provides organophosphorus flame retardants with up to 1.5 wt% phosphorus; Optionally, up to 10 wt% of the additive composition, The amounts are based on the total weight of the polycarbonate composition, and the sum of the amounts is 100 wt%.

13. The polycarbonate composition according to claim 1 or 2, wherein, The weight ratio of glass fiber to mineral filler is 2:1 or greater.

14. The polycarbonate composition according to claim 7, wherein, R 16 R 17 R 18 and R 19 Each is C independently 1-8 Alkyl, C 5-6 cycloalkyl, C 6-20 Aryl, or C 7-12 Arylalkylene groups, each optionally C 1-4 Alkyl substitution.

15. The polycarbonate composition according to claim 1 or 2, wherein, The organophosphorus flame retardant includes: Phosphazenes or cyclic phosphazenes of the following formula: or Where w1 is 3 to 10,000; w2 is 3 to 25; and each R w C is independent 1-12 Alkyl, alkenyl, alkoxy, aryl, aryloxy, or polyoxyalkylene, optionally wherein at least one hydrogen atom is substituted with an N, S, O, or F atom or with an amino group.

16. The polycarbonate composition according to claim 15, wherein, w2 is 3 to 7.

17. An article comprising the polycarbonate composition according to any one of claims 1 to 16.

18. The article of claim 17, wherein, The product in question is a track assembly.

19. The article of claim 17, wherein, The product in question is an internal track assembly.

20. The article of manufacture according to claim 17, wherein, The articles include seat assemblies, extruded interior train cladding, molded interior train cladding, table trays, headrests, privacy dividers, center consoles, armrests, leg rests, food trays, end compartments, covers, kickboards, footwells, document pockets, monitors, sunshades, wiring replacement units, foot pedals, luggage racks, luggage containers, luggage compartments, floor composites, wall composites, air ducts, strips, passenger information equipment, window frames, interior linings, interior vertical surfaces, interior doors, linings for interior doors, linings for exterior doors, interior horizontal surfaces, electrical components, or lighting components.

21. A method for forming an article of claim 20, comprising molding, casting, or extruding the composition to provide the article.

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