Flame retardant and Anti-drip thermoplastic compositions
Patent Information
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- SABIC GLOBAL TECHNOLOGIES BV
- Filing Date
- 2025-11-25
- Publication Date
- 2026-06-04
Smart Images
Figure EP2025084152_04062026_PF_FP_ABST
Abstract
Description
24T&I0029-WO-ORD 1FLAME RETARDANT AND ANTI-DRIP THERMOPLASTIC COMPOSITIONSCROSS REFERENCE TO RELATED APPLICATIONS
[0001] Not applicable.FIELD
[0002] The present disclosure is generally directed to a flame retardant composition including a polymeric resin, in particular a polycarbonate, a sulfonated phosphazene and a fluoropolymer.BACKGROUND
[0003] Polycarbonates (PC) are widely used in construction, automotive, electronic, electrical laminate, wire and cable, textile, and other applications due to their excellent mechanical properties and transparency. However, polycarbonates are inherently flammable and can drip hot molten material causing nearby materials to catch fire as well. To address these issues, flame retardant (FR) and anti-drip additives are commonly incorporated into PC formulations to improve fire and drip resistance. Generally, increasing the amounts of flame retardant and anti-drip additives in the composition improves the flame retardancy and drip resistance properties of the polycarbonates. However, it impacts the optical and mechanical properties of the polycarbonates.
[0004] Rimar salt (potassium perfluorobutane sulfonate, PFBS) is used widely in polycarbonate compositions to enhance flame retardancy as it exhibits good thermal stability and has minimal impact on the mechanical and optical properties. However, Rimar salt is a perfluoroalkyl sub stance (PFAS) and it is taken as a substance of very high concern (SVHC) under Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH) regulations.
[0005] Alternatively, phosphazenes have been tried as FR additives in specific polymer systems. For example, U. S. published application no. 2005-0245670 describes certain substituted cyclic phosphazenes as FR additives in polycarbonate resin compositions. Although phosphazene compounds can provide flame retardancy (as indicated by certain standardized tests), they often do not have other attributes that are necessary in a good FR additive. In some cases, the24T&I0029-WO-ORD 2 phosphazene compounds are simply too expensive to be practical. Many of the phosphazene FR additives have been found to be inefficient and require somewhat large loadings in order to be effective.
[0006] Thus, for the foregoing reasons, there remains a need for developing alternative polycarbonate composition capable of providing excellent flame retardancy properties at lower loadings of FR additives.
[0007] Accordingly, there is a need to develop new thermoplastic polycarbonate compositions that contain PFAS-free flame retardant and have improved drip resistance performance with no or minimal impact on mechanical performances.SUMMARY
[0008] The present disclosure generally describes a flame retardant thermoplastic composition including a polycarbonate resin, a sulfonated phosphazene and a fluoropolymer. In one embodiment, the flame retardant thermoplastic composition includes: at least 5 wt.% of an aromatic polycarbonate; at least 0.01 wt.% of a sulfonated phosphazene of formulawhere each of Ai-Ae are selected fromwherein, Ro is an alkyl group having from 1 to 10 carbon atoms, wherein, each of R1-R5 are selected from H, an alkyl group, an alkoxyl group having 1-10 carbon atoms, -NO2, -CN, -SO2R, -CO2R, -N(R)2, and -SO3M,R is an alkyl group,24T&I0029-WO-ORD 3M is selected from Li, Na, K, Cs, Zn, Mg, Ca, Ce and Al; and wherein at least one of Ai-Ae iswith at least one of Ri, R2, R3, R4 or R5 being -SO3M; and at least 0.01 wt.% of a fluoropolymer and where the wt.% is based on the total weight of the flame retardant thermoplastic composition.
[0009] In another embodiment, the sulfonated phosphazene has the formulawhere each of Ai-Ae are selected fromwherein, Ro is an alkyl group having from 1 to 10 carbon atoms, wherein, each of R1-R5 independently selected from H, an alkyl group, an alkoxyl group having 1-10 carbon atoms, -NO2, -CN, -SO2R, -CO2R, -N(R)2, and -SO3M,R is an alkyl group,M is selected from Li, Na, K, Cs, Zn, Mg, Ca, Ce and Al; and wherein at least one of Ai-Ae isand at least one of Ri, R2, R3, R4 or R5 being -SO3M.24T&I0029-WO-ORD 4
[0010] In yet another embodiment, there is provided a method of making the flame retardant thermoplastic composition. The method generally includes combining the polycarbonate with the sulfonated phosphazene and fluoropolymer to form a mixture and mixing the mixture to form the flame retardant thermoplastic composition.BRIEF DESCRIPTION OF THE DRAWINGS
[0011] Not applicableDETAILED DESCRIPTION
[0012] If appearing herein, the term "comprising" and derivatives thereof are not intended to exclude the presence of any additional component, step or procedure, whether or not the same is disclosed herein. In order, to avoid any doubt, all compositions claimed herein through use of the term "comprising" may include any additional additive, adjuvant, or compound, unless stated to the contrary. In contrast, the term, "consisting essentially of' if appearing herein, excludes from the scope of any succeeding recitation any other component, step or procedure, except those that are not essential to operability and the term "consisting of, if used, excludes any component, step or procedure not specifically delineated or listed. The terms "or" and “and / or”, unless stated otherwise, refer to the listed members individually as well as in any combination. For example, the expression A and / or B refers to A alone, B alone, or to both A and B.
[0013] The articles "a" and "an" are used herein to refer to one or to more than one (i.e. to at least one) of the grammatical objects of the article. By way of example, "a polymer" means one polymer or more than one polymer. The phrases "in one embodiment", "according to one embodiment" and the like generally mean the particular feature, structure, or characteristic following the phrase is included in at least one embodiment of the present disclosure and may be included in more than one embodiment of the present disclosure. Importantly, such phrases do not necessarily refer to the same embodiment. If the specification states a component or feature "may", "can", "could", or "might" be included or have a characteristic, that particular component or feature is not required to be included or have the characteristic.24T&I0029-WO-ORD 5
[0014] The terms “preferred” and “preferably” refer to embodiments that may afford certain benefits, under certain circumstances. However, other embodiments may also be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful and is not intended to exclude other embodiments from the scope of the present disclosure.
[0015] The term “about” as used herein can allow for a degree of variability in a value or range, for example, it may be within 10%, within 5%, or within 1% of a stated value or of a stated limit of a range.
[0016] Values expressed in a range format should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but to also include all of the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a range such as from 1 to 6, should be considered to have specifically disclosed sub-ranges, such as, from 1 to 3, from 2 to 4, from 3 to 6, etc., as well as individual numbers within that range, for example, 1, 2, 3, 4, 5, and 6. This applies regardless of the breadth of the range.
[0017] The term “optional” or “optionally” means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.
[0018] The term “PFAS-free flame retardant composition” refers to a composition in which a PF AS-containing flame retardant is present in an amount that has no material effect on the overall composition. In some embodiments, “PFAS-free flame retardant composition” may refer to a composition in which the PFAS-containing flame retardant is present in the composition in an amount of less than about 5 wt.%, or less than about 4 wt.%, or less than about 3 wt.% or less than about 2 wt.% or less than about 1 wt.%, or less than about 0.5 wt.%, or less than about 0.1 wt.%, or less than about 0.05 wt.%, or even less than about 0.01 wt.% based on the total weight of the composition, or that no amount of PFAS-containing flame retardant is present in the respective composition.24T&IOD29-WO-ORD 6
[0019] The term “synergistic amount” of the sulfonated phosphazene and a fluoropolymer is used herein to indicate that the combined addition of the sulfonated phosphazene and a fluoropolymer to the thermoplastic composition has a “synergistic effect” on certain properties of the resulting flame-retardant thermoplastic composition or article prepared therefrom, i.e., the effect of the addition of the synergistic amount of the different components is greater than the effect of each component individually, and moreover, is greater than the sum of the individual component effects.
[0020] The present disclosure generally provides a flame retardant thermoplastic composition including a polycarbonate resin, a sulfonated phosphazene and a fluoropolymer.
[0021] According to one embodiment, the halogen flame retardant composition includes:(A) at least 65 wt.% of an aromatic polycarbonate;(B) at least 0.07 wt.% of a sulfonated phosphazene having the formulawhere each of Ai-Ae are selected fromwherein Ro is an alkyl group having from 1 to 10 carbon atoms, each of R1-R5 are selected from H, an alkyl group, an alkoxyl group having 1-10 carbon atoms, -NO2, -CN, -SO2R, -CO2R, -N(R)2, and -SO3M,R is an alkyl group,M is selected from Li, Na, K, Cs, Zn, Mg, Ca, Ce and Al;24T&IOD29-WO-ORD 7 and wherein at least one of Ai-Ae isand at least one of Ri, R2, R3, R4 or R5 is -SO3M, and(C) least 0.01 wt.% of a fluoropolymer, where the wt.% is based on the total weight of the flame retardant thermoplastic composition.
[0022] According to another embodiment, the aromatic polycarbonate useful in the present disclosure can be prepared from the reaction of diphenols with carbonoic acid halides, preferably phosgene, and / or with aromatic dicarboxylic acid dihalides, preferably benzenedicarboxylic acid dihalides, by an interfacial process, optionally using chain terminators, for example monophenols. Preparation by a melt polymerization process by reaction of diphenols with, for example, diphenyl carbonate is also possible. Such processes are further described below.
[0023] The diphenols which may be used in preparing the aromatic polycarbonates may have the general formulawhere A represents a single bond, Ci-Cs-alkylene, C2-Cs-alkylidene, Cs-Ce-cycloalkylidene, -O- , -SO-, -CO-, -S-, -SO2-, Ce-Ci2-arylene, to which there can be fused further aromatic rings, or a radical of formulae24T&I0029-WO-ORD 8where B in each case represents Ci- to Cn-alkyl, preferably methyl, x in each case independently of the other represents 0, 1 or 2, p is 1 or 0, andR5and R6can be chosen individually for each X1and represent, independently of one another, hydrogen or Ci-Ce-alkyl, preferably hydrogen, methyl or ethyl,X1represents carbon and m represents an integer from 4 to 7, preferably 4 or 5, with the proviso that on at least one atom X1, R5and R6are simultaneously alkyl.
[0024] Examples of diphenols include, but are not limited to, hydroquinone, resorcinol, dihydroxy diphenols, bis-(hydroxyphenyl)-Ci-Cs-alkanes, bis-(hydroxyphenyl)-Cs-C6- cycloalkanes, bis-(hydroxyphenyl) ethers, bis-(hydroxyphenyl) sulfoxides, bis-(hydroxyphenyl) ketones, bis-(hydroxyphenyl)-sulfones and a,a-bis-(hydroxy-phenyl)-diisopropylbenzenes.Particularly preferred diphenols include 4,4'-dihydroxydiphenyl, bisphenol A, 2,4-bis(4- hydroxyphenyl)-2-methylbutane, 1 , 1 -bis-(4-hydroxyphenyl)-cyclohexane, 1 , 1 -bis-(4- hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4'-dihydroxydiphenyl sulfide and 4,4 '-dihydroxy- diphenyl sulfone. In one preferred embodiment, the diphenol is bisphenol A.
[0025] Examples of chain terminators are, for example, phenol, p-chlorophenol, p-tert- butylphenol or 2,4,6-tribromophenol, and also long-chained alkylphenols, such as 4-[2-(2,4,4- trimethylpentyl)]-phenol, 4-(l,3-tetramethylbutyl)-phenol, monoalkylphenols or dialkylphenols having a total of from 8 to 20 carbon atoms in the alkyl substituents, such as 3,5-di-tert-24T&I0029-WO-ORD 9 butylphenol, p-isooctylphenol, p-tert-octylphenol, p-dodecylphenol and 2-(3,5-dimethylheptyl)- phenol and 4-(3,5-dimethylheptyl)-phenol. The amount of chain terminators that may be used is generally from 0.5 mol % to 10 mol %, based on the molar sum of the diphenols used in a particular case.
[0026] Aromatic polycarbonates are generally manufactured using two different technologies. In a first technology, known as the interfacial technology or interfacial process, phosgene is reacted with a diphenol, typically bisphenol A (BPA) in a liquid phase. Another well- known technology is the so-called melt technology, sometimes also referred to as melt transesterification or melt polycondensation technology. In the melt technology, or melt process, a diphenol, typically BPA, is reacted with a carbonate, typically diphenyl carbonate (DPC), in the melt phase. The aromatic polycarbonate obtained by the melt transesterification process is known to be structurally different from aromatic polycarbonate obtained by the interfacial process. In that respect, it is noted that, the so called “melt polycarbonate” typically has a minimum amount of Fries branching, which is generally absent in “interfacial polycarbonate”. Apart from that, melt polycarbonate typically has a higher number of phenolic hydroxy end groups while polycarbonate obtained by the interfacial process is typically end-capped and has at most 150 ppm, preferably at most 50 ppm, more preferably at most 10 ppm of phenol hydroxyl end-groups.
[0027] According to an embodiment, it is preferred that the aromatic polycarbonate includes bisphenol A polycarbonate or a mixture of bisphenol A polycarbonates. Preferably, the aromatic polycarbonate of the disclosure herein includes at least 75 wt. %, preferably at least 95 wt. % of bisphenol A polycarbonate based on the total weight of aromatic polycarbonate. In an embodiment, the aromatic polycarbonate in the composition essentially consists or consists of bisphenol A polycarbonate.
[0028] In an embodiment, the aromatic polycarbonate has a weight average molecular weight (Mw) of 15,000 g / mol to 100,000 g / mol, preferably 15,000 g / mol to 80,000 g / mol, more preferably 15,000 g / mol to 50,000 g / mol, determined using gel permeation chromatography with polycarbonate standards.24T&I0029-WO-ORD 10
[0029] In an embodiment, the aromatic polycarbonate is an interfacial polycarbonate. In another embodiment, the aromatic polycarbonate is a melt polycarbonate. In yet another embodiment, the polycarbonate is a mixture of from 20 wt.% to 80 wt. % or 40 wt.% to 60 wt.% of interfacial polycarbonate and from 80 wt.% to 20 wt.% or 60 wt.% to 40 wt.% of melt aromatic polycarbonate, based on the weight of the aromatic polycarbonate.
[0030] In another embodiment, the aromatic polycarbonate may be a mixture of two or more aromatic polycarbonates differing in melt flow rates. For example, the aromatic polycarbonate may be a mixture of two or more bisphenol A polycarbonate homopolymers with mutually different weight average molecular weights. The polycarbonate can have a melt flow rate, determined in accordance with ASTM D1238 (300 °C, 1.2 kg) of 1 to 50 g / 10 min, preferably 2 to 40 g / 10 min, more preferably 2 to 20 g / 10 min. In an embodiment, the polycarbonate includes a polycarbonate copolymer comprising structural units of bisphenol A and structural units from another bisphenol.
[0031] In an embodiment, the flame retardant thermoplastic composition includes at least 65 wt.%, or at least 70 wt.%, or at least 75 wt.%, or at least 80 wt.%, or at least 85 wt.%, or at least 90 wt.%, or at least 95 wt.%, or at least 99 wt.% of combined amount of aromatic polycarbonate, based on the total weight of the flame retardant thermoplastic composition. In another embodiment, the flame retardant thermoplastic composition includes from 65 wt.% to 99.99 wt.%, or from 70 wt.% to 98 wt.%, or from 70 wt.% to 95 wt.%, or from 70 wt.% to 94 wt.% of the combined amount of aromatic polycarbonate, based on the total weight of the flame retardant thermoplastic composition.
[0032] In another embodiment, the flame retardant thermoplastic composition includes at least 1 wt.%, or at least 2 wt.%, or at least 3 wt.%, or at least 4 wt.%, or at least 5 wt.%, or at least 6 wt.%, or at least 7 wt.%, or at least 8 wt.%, or at least 9 wt.%, or at least 10 wt.%, or 15 wt.%, or at least 20 wt.%, or at least 25 wt.%, or at least 30 wt.%, or at least 35 wt.%, or at least 40 wt.%, or at least 45 wt.%, or 50 wt.%, or at least 55 wt.%, or at least 60 wt.%, or at least 65 wt.%, or at least 70 wt.%, or at least 75 wt.%, or at least 80 wt.%, or at least 85 wt.%, or at least 90 wt.%, of the aromatic polycarbonate, based on the total weight of the flame retardant thermoplastic24T&I0029-WO-ORD 11 composition. In a preferred embodiment, the flame retardant thermoplastic composition includes 5.0 wt.% to 99.97 wt.%, preferably 5.0 wt.% to 99.95 wt.%, more preferably 5.0 wt.% to 99.90 wt.%, more preferably 5.0 wt.% to 99.75 wt.% of the aromatic polycarbonate, based on the total weight of the flame retardant thermoplastic composition.
[0033] According to an embodiment, M in the sulfonated phosphazene, is a metal. In some embodiments, a single metal or combination of metals is used. In one particular embodiment, M is selected from Li, Na, K, Zn, Mg, Ca, Ce and Al. In another particular embodiment, M is selected from Li, Na, and K. Preferably M is selected from Na and K.
[0034] According to one embodiment, the flame retardant thermoplastic composition includes at least 0.01 wt.%, or at least 0.02 wt.%, or at least 0.03 wt.%, or at least 0.04 wt.%, or at least 0.05 wt.%, or at least 0.06 wt.%, or at least 0.07 wt.%, or at least 0.08 wt.%, or at least 0.09 wt.%, or 0.1 wt.%, or at least 0.1 wt.%, or at least 0.2 wt.%, or at least 0.3 wt.%, or at least 0.4 wt.%, or at least 0.5 wt.%, or at least 0.6 wt.%, or at least 0.7 wt.%, or at least 0.8 wt.%, or at least 0.9 wt.%, or at least 1.0 wt.%, of the sulfonated phosphazene, based on the total weight of the flame retardant thermoplastic composition. In another embodiment, the amount of sulfonated phosphazene may be an amount from 0.01 wt.% to 5.0 wt.%, or from 0.01 wt.% to 4.0 wt.%, or from 0.01 wt.% to 3.0 wt.%, or from 0.01 wt.% to 2.0 wt.% or from 0.01 wt.% to 1.0 wt.% of the sulfonated phosphazene, based on the total weight of the flame retardant thermoplastic composition.
[0035] According to an embodiment, the Ai-Ae or A groups of the sulfonated phosphazenes described above are selected from compounds having formulas Ila - Ilh and a mixture thereof:24T&I0029-WO-ORD 12The sulfonated phosphazenes above include at least one or a combination of Ai-Ae or A groups selected from compounds having the formulas Ila - Ilh. In a particular embodiment, the Ai-Ae or A groups are selected from compounds having formulas Ila - lie. Preferably Ai-Ae or A is a compound having formula lib.
[0036] It has been surprisingly found when the combination of the sulfonated phosphazene and fluoropolymer is added to the aromatic polycarbonate in a synergistic amount, the flame retardancy and anti-drip properties of the flame retardant thermoplastic composition are enhanced as compared to the addition of a sulfonated phosphazene of formula I. In an embodiment, the flame retardant composition of the present disclosure includes:(A) at least 5 wt.% of an aromatic polycarbonate;(B) at least 0.01 wt.% of a sulfonated phosphazene of the formulawhere each of Ai-Ae are selected fromwherein Ro is an alkyl group having from 1 to 10 carbon atoms,24T&I0029-WO-ORD 13 each of R1-R5 are selected from H, an alkyl group, an alkoxyl group having 1-10 carbon atoms, -NO2, -CN, -SO2R, -CO2R, -N(R)2, and -SO3M,R is an alkyl group,M is selected from Li, Na, K, Cs, Zn, Mg, Ca, Ce and Al; and wherein at least one of Ai-Ae isand at least one of Ri, R2, R3, R4 or R5 is -SO3M; and(C) at least 0.01 wt.% of a fluoropolymer, where the wt.% is based on the total weight of the thermoplastic composition.In another embodiment, the sulfonated phosphazene has the formulawhere each of Ai-Ae are selected fromwherein Ro is an alkyl group having from 1 to 10 carbon atoms, each of R1-R5 are selected from H, an alkyl group, an alkoxyl group having 1-10 carbon atoms, -NO2, -CN, -SO2R, -CO2R, -N(R)2, and -SO3M,R is an alkyl group,24T&I0029-WO-ORD 14M is selected from Li, Na, K, Cs, Zn, Mg, Ca, Ce and Al; and wherein at least one of Ai-Ae isand at least one of Ri, R2, R3, R4 or R5 is -SO3M.
[0037] According to an embodiment, the flame retardant thermoplastic composition includes a fluoropolymer. The fluoropolymer is a polytetrafluoroethylene (PTFE) or PTFE- containing composition or masterbatch of PTFE with styrene or methyl methacrylate-containing polymers. In a particular embodiment, the fluoropolymer is an encapsulated fluoropolymer. Yet, in another particular embodiment, the fluoropolymer is a copolymer of styrene-acrylonitrile (SAN) encapsulated PTFE. PTFE encapsulated in SAN is known as TSAN. The TSAN having different amounts of PTFE and SAN may be used, for example, 20 wt.% to 80 wt.% PTFE or 20 wt.% to 80 wt.% wt.% SAN. In a particular embodiment, TSAN may include about 50 wt.% PTFE and about 50 wt.% SAN, based on the total weight of the encapsulated fluoropolymer. The SAN may include, for example, 20 wt.% to 80 wt.% styrene, based on the total weight of the copolymer of styrene-acrylonitrile (SAN) encapsulated PTFE. In a particular embodiment, SAN includes 75 wt.% styrene and 25 wt.% acrylonitrile, based on the total weight of the copolymer of styrene- acrylonitrile (SAN) encapsulated PTFE.
[0038] According to one embodiment, the flame retardant thermoplastic composition includes at least 0.01 wt.%, or at least 0.02 wt.%, or at least 0.03 wt.%, or at least 0.04 wt.%, or at least 0.05 wt.%, or at least 0.06 wt.%, or at least 0.07 wt.%, or at least 0.08 wt.%, or at least 0.09 wt.%, or at least 0.1 wt.%, or at least 0.2 wt.%, or at least 0.3 wt.%, or at least 0.4 wt.%, or at least 0.5 wt.%, or at least 0.6 wt.%, or at least 0.7 wt.%, or at least 0.8 wt.%, or at least 0.9 wt.%, or at least 1.0 wt.% of the fluoropolymer, based on the total weight of the flame retardant thermoplastic composition. In other embodiments, the amount of fluoropolymer may be an amount from 0.01 wt.% to 5.0 wt.%, or from 0.01 wt.% to 4.0 wt.%, or from 0.01 wt.% to 3.0 wt.%, or from 0.01 wt.% to 2.0 wt.%, or from 0.01 wt.% to 1.0 wt.%, or from 0.01 wt.% to 0.5 wt.%, or from 0.0124T&I0029-WO-ORD 15 wt.% to 0.4 wt.%, or from 0.01 wt.% to 0.3 wt.%, or from 0.01 wt.% to 0.2 wt.%, or from 0.01 wt.% to 0.1 wt.% of the fluoropolymer, based on the total weight of the flame retardant thermoplastic composition.
[0039] According to an embodiment, the flame retardant thermoplastic composition also includes at least one of a siloxane and a branched polycarbonate. In an embodiment, the siloxane is selected from the group consisting of a cyclotrisiloxane, a cyclotetrasiloxane, a linear polysiloxane, a branched polysiloxane, a polyoctahedral silsesquioxanes, and a mixture thereof. According to another embodiment, the branched aromatic polycarbonate may be selected from branched polycarbonates disclosed in US20130136883A1, US20140179843A,US20130317146A1 and US5104964A, the contents of which are incorporated herein by reference. In one embodiment, the branched aromatic polycarbonate includes branched bisphenol A polycarbonate or a mixture of branched bisphenol A polycarbonates. Preferably, the branched aromatic polycarbonate of the disclosure herein includes at least 75 wt. %, preferably at least 95 wt. % of branched bisphenol A polycarbonate based on the total weight of branched aromatic polycarbonate. More preferably, the branched aromatic polycarbonate in the composition essentially consists or consists of branched bisphenol A polycarbonate.
[0040] In one embodiment, the flame retardant thermoplastic composition includes the siloxane in an amount of from 0.01 wt.% to 30 wt.%, based on the total weight of the flame retardant thermoplastic composition. In a particular embodiment, the amount of siloxane is from 0.01 wt.% to 20 wt.%, from 0.01 wt.% to 15 wt.%, from 0.01 wt.% to 10 wt.%, based on the total weight of the flame retardant thermoplastic composition. Preferably, the amount of siloxane from 0.01 wt.% to 5.0 wt.%, from 0.01 wt.% to 4.0 wt.%, from 0.01 wt.% to 3.0 wt.%, from 0.01 wt.% to 2.0 wt.% and from 0.01 wt.% to 1.0 wt.%, based on the total weight of the flame retardant thermoplastic composition.
[0041] In one embodiment, the flame retardant thermoplastic composition includes at least 1 wt.% or at least 2 wt.% or at least 3 wt.% or at least 4 wt.% or at least 5 wt.% or at least 6 wt.% or at least 7 wt.% or at least 8 wt.% or at least 9 wt.% or at least 10 wt.% or 15 wt.% or at least 20 wt.% or at least 25 wt.% or at least 30 wt.% or at least 35 wt.% or at least 40 wt.% or at least 45 wt.% or 50 wt.% or at least 55 wt.% or at least 60 wt.% or at least 65 wt.% or at least 70 wt.% or at least 75 wt.% or at least 80 wt.% or at least 85 wt.% or at least 90 wt.% or at least 95 wt.% of24T&I0029-WO-ORD 16 the branched aromatic polycarbonate, based on the total weight of the flame retardant thermoplastic composition. In a preferred embodiment, the flame retardant thermoplastic composition includes 5.0 wt.% to 90.0 wt.%, preferably 5.0 wt.% to 80.0 wt.%, preferably 5.0 wt.% to 70.0 wt.%, preferably 5.0 wt.% to 65.0 wt.%, more preferably 5.0 wt.% to 60.0 wt.%, more preferably 5.0 wt.% to 50.0 wt.% more preferably 5.0 wt.% to 40.0 wt.% of the branched aromatic polycarbonate, based on the total weight of the flame retardant thermoplastic composition.
[0042] In a preferred embodiment, the flame retardant thermoplastic composition of the present disclosure is opaque. The term “opaque” means absorbing maximum amount of incident light in the visible spectrum (400-700 nm wavelength) and may be reflecting a small amount of incident light.
[0043] In another embodiment, the flame retardant thermoplastic composition of the present disclosure contains 0 to 5 wt. % of other additives, based on the total weight of the flame retardant thermoplastic composition. Theses additives include, but are not limited to one or more of flame retardant synergists, anti-drip agents, lubricants and mold release agents (for example pentaerythritol tetrastearate), nucleating agents, stabilizers, antistatics (for example conductive carbon blacks, chopped carbon fibers, carbon nanotubes and organic antistatics, such as polyalkylene ethers, alkylsulfonates or polyamide-containing polymers), acids, fillers and reinforcing substances and dyestuffs and pigments. In a particular embodiment, the additives include an antioxidant, a mold release agent, or a UV stabilizer.
[0044] In an embodiment, the flame retardant composition of the present disclosure, after curing, has a UL94 rating of V0 at a thickness of <3.2 mm, preferably<2.5 mm, preferably <2.3 mm, more preferably <1.0 mm.
[0045] In an embodiment, the present disclosure provides a method of making the flame retardant composition including: a) combining at least 5.0 wt.% of an aromatic polycarbonate and at least 0.01 wt.% of a fluoropolymer, with at least 0.01 wt.% of the sulfonated phosphazene described aboveto form a mixture; and b) mixing the mixture to form the composition, where the wt.% is based on the total weight of the composition.24T&IOD29-WO-ORD 17
[0046] In an embodiment, the flame retardant thermoplastic compositions of the present disclosure can be manufactured by various methods known in the art. For example, aromatic polycarbonate, phosphazene, sulfonated phosphazene, fluoropolymer and other additives, if any, are first blended, in a high-speed mixer (dry blender) or by hand mixing to form a blend. The blend is then fed into the throat of a twin-screw extruder via a hopper. Alternatively, at least one of the additives or components of the flame retardant thermoplastic composition can be incorporated into the composition by feeding it directly into the extruder at the throat and / or downstream through a side feeder, or by being compounded into a masterbatch with a desired aromatic polycarbonate and fed into the extruder. For example, flame retardant thermoplastic compositions can be prepared using a Toshiba TEM-37BS intermeshing 10-barrel twin screw extruder of diameter 25 mm and L / D ratio 41. The temperature in the extruder may be from 180 °C to 340 °C along the screw length. The extrudate can be immediately cooled in a water bath and pelletized. The pellets so prepared can be 0.6 cm in length or less as desired. Such pellets can be used for subsequent molding, shaping, or forming.
[0047] Shaped, formed, or molded articles comprising the compositions are also provided. The flame retardant compositions can be molded into articles by a variety of methods, such as injection molding, extrusion, and thermoforming. Some examples of articles include articles used in interior or exterior automotive applications and also in electrical & electronic applications such as software products (mobiles, notebooks, monitors, tablets, data storage etc.) computer and (tele) communication applications and across other different segments and applications such as consumer products & appliances, automotive lighting, automotive under the hood, electric vehicle applications, electrical parts, electronic displays, energy storage, lighting applications, as building materials like roofing, lighting fixtures, and as in mass transportation like in train or in bus.
[0048] Accordingly, the present disclosure relates to an article including the flame retardant composition disclosed herein. In a particular embodiment, the present disclosure relates to manufacture of an article, preferably an automotive part or electrical or electronic part that includes the flame retardant composition disclosed herein. Likewise, the present disclosure relates to a vehicle or an electrical or electronic equipment including the automotive part or the electrical or electronic part.24T&IOD29-WO-ORD 18
[0049] The present disclosure will now be further elucidated based on the following nonlimiting examples.Test Methods24T&I0029-WO-ORD 19
[0050] Sodium salt of sulfonated hexaphenoxycyclotriphosphazene (CPS-6Na)Synthesis of CPS-6Na: A solution of Sodium 4-hydroxybenzenesulfonate dihydrate (SBS, 23.4 g, 100 mmol), and 4 g of sodium hydroxide (100 mmol) was added dropwise into a solution of hexachlorophosphazene (HCCP) (5 g, 14.4 mmol) and then refluxed 2 days under N2 atmosphere. The reaction solution was neutralized by diluted HC1 to pH=7. A white solid was obtained after recrystallization. 1H NMR (DMSO, 5, ppm): 5=7.62 (12H, Ar-H), 6.73 (12H, Ar-H); 13C-NMR (DMSO, 5, ppm): 5= 150.23, 145.31, 128.02, 120.40; 31P-NMR (DMSO, 5, ppm): 5=8.87 (s, cyclotriphosphazene). FT-IR (KBr, cm-1): v 3456, 3072, 1595, 1495, 1220 1192, 1126, 1041, 1012, 966, 844.The same method was used for synthesizing CPS-6K and other salts.
[0051] FR PC formulations:A Toshiba TEM-37BS twin screw extruder was used to prepare FR PC formulations for UL94 testing. In a typical experiment, 2.0 kg of total of ingredients were pre-mixed in a vessel and subsequently added into the hopper. Processing conditions included barrel temperature up to 280 °C and screw speed of 300 RPM. The extrudate was immediately cooled under water and run through pelletizer. Next day, dried pellets were transferred to an Demag 100T injection molding machine of L&T make with a mold temperature of 70 °C, injection pressure up to 200 bar and hold time of 20 seconds to create standard UL 94 bars. UL 94 vertical burning tests were conducted in a standard UL cabinet manufactured by ATLAS. The flame was calibrated based on the UL 94 standard before testing. In a typical analysis, a plastic UL bar at a fixed height was positioned above cotton and exposed tolO-second applications of burning twice. After each 10 second flame24T&I0029-WO-ORD 20 application, observations of the flame out time and dripping behavior were recorded to determine UL classification. The components of the compositions and their source are listed in Table 1.Table 1 : Components of the compositions and their sourceTable 2: FR PC Formulations24T&I0029-WO-ORD 21Table 3: FR PC Formulations PropertiesTable 3 clearly shows that combination of the sulfonated phosphazene and TSAN of the present i. 5 invention, when added to the polycarbonates in a synergistic amount, enhanced the flame retardancy and anti-drip properties of thermoplastic composition. For example, the results show a synergism of TSAN (anti-drip agent) with a sulfonated phenoxyphosphazene (CPS-6Na) which can render VO UL 94 rating (see for e.g., examples IE-1 & IE-2). Without TSAN (CE-1, CE-2, & CE-3), the composition experiences significant dripping with such low concentrations of CPS-6Na. 10 (i.e. 0.05% and 0.2%) to render only V2 performance. There is a clear trend of reduced total flame out time (TFOT) with increasing CPS-6Na (CE-2 and CE-3; IE-1 and IE-2).Table 4: FR PC Formulations24T&I0029-WO-ORD 22Table 5: FR PC Formulations Properties
Claims
24T&I0029-WO-ORDC LA I M S1. A flame retardant thermoplastic composition comprising:(A) at least 5 wt.% of an aromatic polycarbonate;(B) at least 0.01 wt.% of a sulfonated phosphazene of formulawhere each of Ai-Ae are selected fromwherein, Ro is an alkyl group having from 1 to 10 carbon atoms, wherein each of R1-R5 are selected from H, an alkyl group, an alkoxyl group having 1-10 carbon atoms, -NO2, -CN, -SO2R, -CO2R, -N(R)2, and -SO3M,R is an alkyl group,M is selected from Li, Na, K, Cs, Zn, Mg, Ca, Ce and Al; and wherein at least one of Ai-Ae iswith at least one of Ri, R2, R3, R4 or R5 being -SO3M; and(C) at least 0.01 wt.% of a fluoropolymer, wherein, the wt.% is based on the total weight of the thermoplastic composition.
2. The flame retardant thermoplastic composition of claim 1, wherein each Ai-Ae is selected from compounds having formulas Ila - Ilh:24T&I0029-WO-ORD 243. The flame retardant thermoplastic composition of any one or more of claims 1-2, wherein each Ai-Ae is selected from formulas Ila - lie, preferably formula lib.
4. The flame retardant thermoplastic composition of any one or more of claims 1-3, wherein M is selected from Li, Na, and K, preferably Na and K.
5. The flame retardant thermoplastic composition of any one or more of claims 1-4, wherein the aromatic polycarbonate comprises bisphenol A polycarbonate.
6. The flame retardant thermoplastic composition of any one or more of claims 1-5, wherein the aromatic polycarbonate has a weight average molecular weight of 15,000 g / mol to 100,000 g / mol, preferably 15,000 g / mol to 80,000 g / mol, more preferably 15,000 g / mol to 50,000 g / mol, determined using gel permeation chromatography with polycarbonate standards.
7. The flame retardant thermoplastic composition of any one or more of claims 1-6, wherein the fluoropolymer is a polytetrafluoroethylene (PTFE), a PTFE-containing composition, masterbatch of PTFE with styrene or methyl methacrylate-containing polymers, or a copolymer of styrene-acrylonitrile (SAN) encapsulated PTFE.
8. The flame retardant thermoplastic composition of any one or more of claims 1-7, wherein the fluoropolymer is a copolymer of styrene-acrylonitrile (SAN) encapsulated PTFE.24T&IOD29-WO-ORD 259. The flame retardant thermoplastic composition of any one or more of claims 1-7, wherein the thermoplastic composition comprises:A) 5.0 wt.% to 99.98 wt.% of the aromatic polycarbonate, preferably 5.0 wt.% to 99.90 wt.%, preferably 5.0 wt.% to 99.5 wt.%, preferably 5.0 wt.% to 99.0 wt.%, preferably 5.0 wt.% to 98.5 wt.%, preferably 5.0 wt.% to 98.0 wt.%, preferably 5.0 wt.% to 97.0 wt.%;B) 0.01 wt.% to 5 wt.% of the sulfonated phosphazene of formula I, preferably 0.01 wt.% to 3.0 wt.%, more preferably 0.01 wt.% to 2.0 wt.%, more preferably 0.01 wt.% to 1.0 wt.%; andC) 0.01 wt.% to 5 wt.% of a fluoropolymer, preferably 0.05 wt.% to 4.0 wt.%, preferably 0.1 wt.% to 3.0 wt.%, more preferably 0.1 wt.% to 2.0 wt.%, more preferably 0.15 wt.% to 2.0 wt.%.
10. The flame retardant thermoplastic composition of any one or more of claims 1-9, wherein the composition further comprises one or more of an antioxidant, a mold release agent or an UV stabilizer.
11. The flame retardant thermoplastic composition of any one or more of claims 1-10, wherein the composition, after curing, has a UL94 rating of V-0 at a thickness of <3.2 mm, preferably <2.5 mm, preferably <2.3 mm, more preferably <1.0 mm.
12. A method of making a flame retardant thermoplastic composition of claim 1 comprising: a) combining at least 5.0 wt.% of a aromatic polycarbonate and at least 0.01 wt.% of a fluoropolymer, with at least 0.01 wt.% of the sulfonated phosphazene to form a mixture; and b) mixing the mixture to form the composition, wherein, the wt.% is based on the total weight of the composition.
13. The flame retardant thermoplastic composition of any one or more of claims 1-12, wherein the composition selected to have a notched Izod impact strength determined in accordance with ISO 180-1A at a temperature of 23°C of at least 12 kJ / m2.24T&I0029-WO-ORD 2614. An article comprising the flame retardant thermoplastic composition of any one or more of claims 1-13.
15. Use of a flame retardant thermoplastic composition of any one or more of claims 1-12 for the manufacture of an article, preferably an automotive part, an electrical part or an electronic part.