Flame-retardant polycarbonate composition

Abstract

The present application relates to a flame-retardant polycarbonate composition and shaped articles made therefrom. The polycarbonate composition comprises the following components: a polycarbonate, a bisphenol-A-bis(diphenyl phosphate), a hydride-functional polysiloxane, a vinyl-terminated siloxane, a catalyst, and optional impact modifiers. The shaped article made from the polycarbonate composition according to the present invention has a good flame retardancy.

Description

[0001] 2025PF30037-FC

[0002] -1-

[0003] FLAME-RETARDANT POLYCARBONATE COMPOSITION

[0004] The present invention relates to a polycarbonate composition. In particular, the present invention relates to a flame-retardant polycarbonate composition and a shaped article made therefrom.

[0005] In the flame-retardant (FR) polymeric materials, Polytetrafluoroethylene (PTFE) is usually used as antidripping agent, along with other flame-retardant agents, to ensure passing standard FR testing such as UL94 VO and / or 5VA / 5VB. The content of PTFE in polycarbonate (PC) compositions is typically from 0.2 wt.% to 0.5 wt.%, which is especially critical to pass UL94 VO in which the failure is often due to dripping.

[0006] In spite of the advantage of PTFE for FR performance, certain restrictions have been given by some regional regulations due to the fact that PTFE contains fluorine. This is mainly based on the concern of the negative effect of fluorine and fluorine-containing compounds on environment and eco-system. The VIN / VDE (Deutsche Institut fur Normung / Verband Der Elektrotechnik) standard restricts the fluorine content in a material to be less than 0.1 wt.%, which corresponds to a PTFE content of 0.13 wt.%. In 2020, five European countries proposed a restriction on the use of PFAS (per- & polyfluoroalkyl substances), which also include PTFE. Therefore, it is highly possible that PTFE can be put in the SVHC (Substances of Very High Concern) listing of REACH in near future. In that case, the PTFE content in compositions will be restricted or even eliminated.

[0007] Efforts have been made to develop non-halogen anti-dripping agents to replace PTFE.

[0008] US 10,100,192 B2 discloses a combination of vinyl-terminated polydimethylsiloxane, hydride-functional polysiloxane and potassium 3-(phenylsulfonyl)benzenesulfonate as non-halogen flame retardant package in polycarbonate compositions, which can achieve a FR level of UL94 V0 at a thickness of 3.2 mm. However, such flame-retardant performance of non-halogenated FR polycarbonate compositions is still not enough robust for electrical & electronic applications.

[0009] Therefore, it is necessary to develop polycarbonate compositions without intentionally added fluorine compounds, which can achieve good FR performance to meet electrical & electronic applications.

[0010] One object of the present application is thus to provide a polycarbonate composition without intentionally added fluorine compounds, which has a good flame retardancy.

[0011] Another object of the present application is to provide a molded article which has a good flame retardancy.2025PF30037-FC

[0012] -2-

[0013] Thus, in a first aspect, the present invention provides a polycarbonate composition comprising the following components, relative to the total weight of the composition:

[0014] A) from 68 to 90 wt.% of a polycarbonate,

[0015] B) from 6 wt.% to 20 wt.% of a bisphenol-A bis(diphenyl phosphate),

[0016] C) from 0.2 wt.% to 8 wt.% of a hydride-functional polysiloxane,

[0017] D) from 3 wt.% to 10 wt.% of a vinyl-terminated siloxane having a viscosity of 100K -lOOOK cst (0.100000 m2 / s to 1.000000 m2 / s), as determined according to the standard testing method DIN-53019 at 23 °C, and E) a catalyst for the addition reaction between component C and component D.

[0018] The inventors have discovered that molded parts made from the composition according to the present invention have a flame retardancy level of V0 at a thickness of 1.5 mm as measured according to UL94:2023.

[0019] According to a second aspect, the present invention provides a shaped article made from the composition according to the first aspect of the present invention.

[0020] According to a third aspect, the present invention provides a method for preparing the shaped article mentioned above, comprising injection moulding, extrusion moulding, blow moulding process or thermoforming the composition according to the present invention.

[0021] Other subjects and characteristics, aspects and advantages of the present invention will emerge even more clearly on reading the description and the examples that follow.

[0022] In that which follows and unless otherwise indicated, the limits of a range of values are included within this range, in particular in the expressions "between ... and ..." and "from ... to ...".

[0023] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention pertains. When the definition of a term in the present description conflicts with the meaning as commonly understood by those skilled in the art the present invention belongs to, the definition described herein shall apply.

[0024] Throughout the instant application, the term “comprising” is to be interpreted as encompassing all specifically mentioned features as well optional, additional, unspecified ones. As used herein, the use of the term “comprising” also discloses the embodiment wherein no features other than the specifically mentioned features are present (i.e. “consisting of’).2025PF30037-FC

[0025] -3-

[0026] Unless otherwise specified, all numerical values expressing amount of ingredients and the like which are used in the description and claims are to be understood as being modified by the term “about”.

[0027] Component A

[0028] The polycarbonate composition according to the present invention comprises a polycarbonate as component A.

[0029] According to the invention, “aromatic polycarbonates” or else just “polycarbonates” is to be understood as meaning both homopolycarbonates and copolycarbonates, in particular aromatic ones. These polycarbonates may be linear or branched in known fashion. According to the invention, mixtures of polycarbonates may also be used.

[0030] Aromatic polycarbonates selected in accordance with the invention preferably have weight-average molecular weights Mwof 15 000 to 40 000 g / mol, more preferably of 16 000 to 34 000 g / mol, even more preferably of 17000 to 33 000 g / mol, most preferably of 19000 to 32000 g / mol. The values for Mwhere are determined by a gel permeation chromatography, calibrated against bisphenol A polycarbonate standards using dichloromethane as eluent, calibration with linear polycarbonates (made of bisphenol A and phosgene) of known molar mass distribution from PSS Polymer Standards Service GmbH, Germany; calibration according to method 2301-0257502-09D (2009 Edition in German) from Currenta GmbH & Co. OHG, Leverkusen. The eluent is dichloromethane. Column combination of crosslinked styrene-divinylbenzene resins. Diameter of analytical columns: 7.5 mm; length: 300 mm. Particle sizes of column material: 3 pm to 20 pm. Concentration of solutions: 0.2% by weight. Flow rate: 1.0 ml / min, temperature of solutions: 30°C. Detection using a refractive index (RI) detector.

[0031] The polycarbonates are preferably produced by the interfacial process or the melt transesterification process, which have been described many times in the literature.

[0032] With regard to the interfacial process reference is made for example to H. Schnell, “Chemistry and Physics of Polycarbonates”, Polymer Reviews, Vol. 9, Interscience Publishers, New York 1964 p. 33 et seq., to Polymer Reviews, Vol. 10, “Condensation Polymers by Interfacial and Solution Methods”, Paul W. Morgan, Interscience Publishers, New York 1965, Chapt. VIII, p. 325, to Dres. U. Grigo, K. Kircher andP. R- Muller “Polycarbonate” in Becker / Braun, Kunststoff-Handbuch, Volume 3 / 1, Polycarbonate, Polyacetale, Polyester, Celluloseester, Carl Hanser Verlag Munich, Vienna 1992, pp. 118-145 and also to EP 0517044 Al.2025PF30037-FC

[0033] -4-

[0034] The melt transesterification process is described, for example, in the “Encyclopedia of Polymer Science”, Vol. 10 (1969), Chemistry and Physics of Polycarbonates, Polymer Reviews, H. Schnell, Vol. 9, John Wiley and Sons, Inc. (1964), and in patent specifications DE 1031 512 A and US 6,228,973 Bl.

[0035] Particulars pertaining to the production of polycarbonates are disclosed in many patent documents spanning approximately the last 40 years. Reference may be made here by way of example to Schnell, “Chemistry and Physics of Polycarbonates”, Polymer Reviews, Volume 9, Interscience Publishers, New York, London, Sydney 1964, to D. Freitag, U. Grigo, P.R. Muller, H. Nouvertne, BAYER AG, “Polycarbonates” in Encyclopedia of Polymer Science and Engineering, Volume 11, Second Edition, 1988, pages 648-718, and finally to U. Grigo, K. Kirchner and P.R. Muller “Polycarbonate” in Becker / Braun, Kunststoff-Handbuch, Volume 3 / 1, Polycarbonate, Polyacetale, Polyester, Celluloseester, Carl Hanser Verlag Munich, Vienna 1992, pages 117-299.

[0036] The production of aromatic polycarbonates is effected for example by reaction of dihydroxyaryl compounds with carbonic halides, preferably phosgene, and / or with aromatic dicarboxyl dihalides, preferably benzenedicarboxyl dihalides, by the interfacial process, optionally using chain terminators and optionally using trifunctional or more than trifunctional branching agents, production of the polyester carbonates being achieved by replacing a portion of the carbonic acid derivatives with aromatic dicarboxylic acids or derivatives of the dicarboxylic acids, specifically with aromatic dicarboxylic ester structural units according to the carbonate structural units to be replaced in the aromatic polycarbonates. Preparation via a melt polymerization process by reaction of dihydroxyaryl compounds with, for example, diphenyl carbonate is likewise possible.

[0037] Dihydroxyaryl compounds suitable for the production of polycarbonates are for example hydroquinone, resorcinol, dihydroxydiphenyls, bis(hydroxyphenyl)alkanes, bis(hydroxyphenyl)cycloalkanes, bis(hydroxyphenyl) sulfides, bis(hydroxyphenyl) ethers, bis(hydroxyphenyl) ketones, bis(hydroxyphenyl) sulfones, bis(hydroxyphenyl) sulfoxides, a,a’-bis(hydroxyphenyl)diisopropylbenzenes, phthalimidines derived from derivatives of isatin or phenolphthalein and the ring-alkylated, ring-arylated and ring-halogenated compounds thereof.

[0038] Preferred dihydroxyaryl compounds are 4,4’-dihydroxydiphenyl, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 2, 4-bis(4-hydroxyphenyl)-2 -methylbutane, 1 , 1 -bis(4-hydroxyphenyl)-p-diisopropylbenzene, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, dimethylbisphenol A, bis(3,5-dimethyl-4-hydroxyphenyl)methane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, bis(3,5-dimethyl-4-2025PF30037-FC

[0039] hydroxyphenyl)sulfone, 2,4-bis(3 ,5 -dimethyl-4-hydroxyphenyl)-2-methylbutane, 1 , 1 -bi s(3 , 5 -dimethyl -4-hydroxyphenyl)-p-diisopropylbenzene and l,l-bis(4-hydroxyphenyl)-3, 3, 5 -trimethylcyclohexane and also the bisphenols (I) to (III)

[0040]

[0041] in which R’ in each case stands for Ci- to C4-alkyl, aralkyl or aryl, preferably for methyl or phenyl, very particularly preferably for methyl.

[0042] Particularly preferred dihydroxyaryl compounds are 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 2,2-bis(3 ,5-dimethyl-4-hydroxyphenyl)propane, 1 , 1 -bis(4-hydroxyphenyl)cyclohexane, 1 , 1 -bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4’-dihydroxybiphenyl, and dimethylbisphenol A and also the diphenols of formulae (I), (II) and (III).

[0043] These and other suitable dihydroxyaryl compounds are described for example in US 3 028635 A, US 2999 825 A, US 3 148 172 A, US 2991 273 A, US 3271 367 A, US 4982014 A und US 2999 846 A, in DE 1 570703 A, DE 2063 050 A, DE 2036052 A, DE 2211 956 A and US 2999 846 A, in DE 1 570703 A, DE 2063050 A, DE 2036052 A, DE 2211 956 A and DE 3 832396 A, in FR 1 561 518, in the monograph “H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York 1964” and also in JP 62039 / 1986 A, JP 62040 / 1986 A and JP 105550 / 1986 A.

[0044] In the case of homopolycarbonates only one dihydroxyaryl compound is used; in the case of copolycarbonates two or more dihydroxyaryl compounds are used. The dihydroxyaryl compounds employed, similarly to all other chemicals and assistants added to the synthesis, may be contaminated with the contaminants from their own synthesis, handling and storage. However, it is desirable to use raw materials of the highest possible purity.

[0045] Suitable carbonic acid derivatives are for example phosgene and diphenyl carbonate.2025PF30037-FC

[0046] -6-

[0047] Suitable chain terminators that may be used in the production of polycarbonates are monophenols. Suitable monophenols are for example phenol itself, alkylphenols such as cresols, p-tert-butylphenol, cumylphenol and mixtures thereof.

[0048] Preferred chain terminators are the phenols mono- or polysubstituted by linear or branched Ci- to Cso-alkyl radicals, preferably unsubstituted or substituted by tert-butyl. Particularly preferred chain terminators are phenol, cumylphenol and / or p-tert-butylphenol.

[0049] The amount of chain terminator to be employed is preferably 0.1 to 5 mol% based on the moles of diphenols employed in each case. The addition of the chain terminators may be effected before, during or after the reaction with a carbonic acid derivative.

[0050] Suitable branching agents are the trifunctional or more than trifunctional compounds familiar in polycarbonate chemistry, in particular those having three or more than three phenolic OH groups. Suitable branching agents are for example l,3,5-tri(4-hydroxyphenyl)benzene, 1,1,1 -tri (4-hydroxyphenyl)ethane, tri(4-hydroxyphenyl)phenylmethane, 2,4-bis(4-hydroxyphenylisopropyl)phenol, 2, 6-bis(2 -hydroxy-5 ’ -methylbenzyl)-4-methylphenol, 2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl)propane, tetra(4-hydroxyphenyl)methane, tetra(4-(4-hydroxyphenylisopropyl)phenoxy)methane and l,4-bis((4‘,4“-dihydroxytriphenyl) methyl)benzene and 3,3-bis(3-methyl-4-hydroxyphenyl)-2-oxo-2,3-dihydroindole.The amount of the branching agents for optional employment is preferably 0.05 mol% to 2.00 mol%, based on moles of dihydroxyaryl compounds used in each case. The branching agents may be either initially charged together with the dihydroxyaryl compounds and the chain terminators in the aqueous alkaline phase or added dissolved in an organic solvent before the phosgenation. In the case of the transesterification process the branching agents are employed together with the dihydroxyaryl compounds.

[0051] Particularly preferred polycarbonates are the homopolycarbonate based on bisphenol A, the homopolycarbonate based on l,l-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4’-dihydroxybiphenyl, and the copolycarbonates based on the two monomers bisphenol A and l,l-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane and also homo- or copolycarbonates derived from the diphenols of formulae (I), (II) and (III)2025PF30037-FC

[0052] -7-

[0053]

[0054] in which R’ in each case stands for Ci- to C4-alkyl, aralkyl or aryl, preferably for methyl or phenyl, very particularly preferably for methyl.

[0055] Preferred are also polycarbonates for the production of which dihydroxyaryl compounds of the following formula (IV) have been used:

[0056]

[0057] wherein

[0058] R5stands for hydrogen or Ci- to C4-alkyl, Ci- to C4-alkoxy, preferably for hydrogen or methyl or methoxy particularly preferably for hydrogen,

[0059] R6, R7, R8and R9mutually independently stand for Ce- to Cn-aryl or Ci- to C4-alkyl, preferably phenyl or methyl, in particular for methyl,

[0060] Y stands for a single bond, SO2-, -S-, -CO-, -O-, Ci- to Ce-alkylene, C2- to Ce-alkylidene, Ce- to Cn-arylene, which can optionally be condensed with further aromatic rings containing hetero atoms, or for a C5- to Ce-cycloalkylidene residue, which can be singly or multiply substituted with Ci- to C4-alkyl, preferably for a single bond, -O-, isopropylidene or for a Ce-to Ce-cycloalkylidene residue, which can be singly or multiply substituted with Ci- to C4-alkyl,

[0061] V stands for oxygen, C2- to Ce-alkylene or C3- to Ce-alkylidene, preferably for oxygen or C3- alkylene, p, q and r mutually independently each stand 0 or 1,

[0062] if q = 0, W is a single bond, if q = 1 and r = 0 is, W stands for -O-, C2- to Ce-alkylene or C3- to Ce-alkylidene, preferably for -O- or G-alkylcnc.

[0063] if q = 1 and r = 1, W and V mutually independently stand for C2- to Ce-alkylene or C3- to Ce-alkylidene, preferably for C3 alkylene,

[0064] Z stands for Ci- to Ce-alkylene, preferably C2-alkylene,2025PF30037-FC

[0065] -8-

[0066] o stands for an average number of repeating units from 10 to 500, preferably 10 to 100 and

[0067] m stands for an average number of repeating units from 1 to 10, preferably 1 to 6, particularly preferably 1.5 to 5.

[0068] It is also possible to use dihydroxyaryl compounds, in which two or more siloxane blocks of general formula (la) are linked via terephthalic acid and / or isophthalic acid under formation of ester groups.

[0069] Especially preferable are (poly)siloxanes of the formulae (V) and (VI)

[0070]

[0071] wherein R1stands for hydrogen, Ci - to C4-alkyl, preferably for hydrogen or methyl and especially preferably for hydrogen,

[0072] R2mutually independently stand for aryl or alkyl, preferably for methyl,

[0073] X stands for a single bond, -SO2-, -CO-, -O-, -S-, Ci- to Ce-alkylene, C2- to Cs-alkylidene or for Ce- to C12-arylene, which can optionally be condensed with further aromatic rings containing hetero atoms,

[0074] X stands for a single bond, -SO2-, -CO-, -O-, -S-, Ci- to Ce-alkylene, C2- to Cs-alkylidene, C5- to C12-cycloalkylidene or for Ce- to Cn-arylene, which can optionally be condensed with further aromatic rings containing hetero atoms,

[0075] X preferably stands for a single bond, isopropylidene, C5- to Cn-cycloalkylidene or oxygen, and especially preferably stands for isopropylidene,

[0076] n means an average number from 10 to 400, preferably 10 and 100, especially preferably 15 to 50 and m stands for an average number from 1 to 10, preferably 1 to 6 and especially preferably from 1.5 to 5. Also preferably the siloxane block can be derived from one of the following structures (VII-IX) :

[0077]

[0078] 3 (VII)2025PF30037-FC

[0079] (VIII), preferably (IXa)

[0080] (IXa), or

[0081] CH3CH3CH3Si“O4SrO)Si

[0082] HO CH3CH3CH3

[0083] a

[0084]

[0085] (IXb),

[0086] wherein a in formulae (VII), (VIII) und (IX) means an average number from 10 to 400, preferably from 10 to 100 and especially preferably from 15 to 50.

[0087] It is equally preferable, that at least two of the same or different siloxane blocks of the general formulae (VII), (VIII) und (IX) are linked via terephthalic acid and / isophthalic acid under formation of ester groups. It is also preferable, if p = 0 in formula (IV), V stands for C3-alkylene,

[0088] if r = 1, Z stands for C2-alkylene, R8and R9stand for methyl,

[0089] if q = I, W stands for C3-alkylene,

[0090] if m = I, R5stands for hydrogen or Ci- to C4-alkyl, preferably for hydrogen or methyl, R6and R7mutually independently stand for Ci- to C4-alkyl, preferably methyl, and o stands for 10 to 500.

[0091] Copolycarbonates with monomer units of the general formula (la), in particular with bisphenol A, and in particular the production of those copolycarbonates are described in WO 2015 / 052106 A2.

[0092] As examples of polycarbonate suitable for the present invention, mention can be made of those produced from bisphenol A and phosgene, and sold under the trade name Makrolon® 2400, Makrolon® 2600, Makrolon® 2800, Makrolon® 3100 by Covestro Co., Ltd. Copolycarbonates suitable for the present invention can be polycarbonate-polysiloxane copolymers, sold under the trade name WH S2060 by Wanhua Chemical Co. Ltd.

[0093] Advantageously, the polycarbonate is present in the polycarbonate composition according to the present invention in an amount ranging from 68 wt. % to 90 wt. %, relative to the total weight of the polycarbonate composition.2025PF30037-FC

[0094] Component B

[0095] The polycarbonate composition according to the present invention comprises bisphenol-A-bis(diphenyl phosphate) (BDP) according to formula (X) as component B:

[0096]

[0097] wherein N = 1.0 to 3.0, preferably 1.05 to 2.0, more preferably 1.05 to 1.6, even more preferably 1.0 to 1.2, in particular N = 1.1.

[0098] Advantageously, the flame retardant BDP is present in the polycarbonate composition according to the present invention in an amount ranging from 6 wt.% to 20 wt.%, relative to the total weight of the polycarbonate composition.

[0099] Component C

[0100] The polycarbonate composition according to the present invention comprises a hydride-functional polysiloxane as component C.

[0101] Among hydride-functional polysiloxanes, a hydride-functional MQ resin will be preferred for use in this invention. As used herein, M means silicon with one oxygen group, two alkyl groups and one hydrogen group and / or silicon surrounded by one oxygen group, three alkyl groups; Q means silicon surrounded by four oxygen groups. The above-mentioned alkyls can be methyl, ethyl etc. When the alkyls are methyl groups, the hydride-functional MQ resin has the structure (XI) shown below.2025PF30037-FC

[0102] B a 1

[0103] [<W88-57-S] / VT,

[0104]

[0105] 1 1(XI)

[0106] The composition according to the invention preferably comprises this resin as hydride-functional polysiloxane; more preferably the hydride-functional polysiloxane is this resin. In the above structure, the percentage of M units in the MQ resin can range from about 1 to 99 wt.% and preferably from about 5 to about 99 wt.%. This hydride-functional MQ resin is a network of tefrafiinctional silicon atoms (silicon surrounded by four oxygen groups) end capped with mono functional silicon atom (e.g. silicon surrounded by one oxygen group, two methyl groups, and one hydrogen group and / or silicon surrounded by one oxygen group, three methyl groups).

[0107] As examples of commercially available hydride-functional polysiloxanes, mention can be made of a hydride-functional MQ resin sold under the trade name Powder-B, XJY8207S by Jiangxi New Jiayi new materials Co. Ltd.

[0108] Advantageously, the hydride-functional polysiloxane is present in the polycarbonate composition according to the present invention in an amount ranging from 0.2 wt. % to 8 wt. %, relative to the total weight of the polycarbonate composition.

[0109] Component D

[0110] The polycarbonate composition according to the present invention comprises a vinyl-terminated siloxane used as component D.

[0111] Preferably, the vinyl-terminated siloxane is selected from monovinyl-terminated siloxanes, bivinyl-terminated siloxanes, and frivinyl-terminated siloxanes.

[0112] More preferably, the vinyl-terminated siloxane is selected from bivinyl -terminated siloxanes containing two vinyl-terminated groups.2025PF30037-FC

[0113] -12-

[0114] A typical example for bivinyl-terminated siloxane is bivinyl-terminated polydimethylsiloxane (PDMS). The bivinyl-terminated PDMS is commercially available and has the following structure (XII).

[0115]

[0116] Other bivinyl-terminated siloxanes including divinyl-terminated polydimethyl siloxane-co-polydiethyl siloxanes (XIII), divinyl-terminated polymethylphenyl siloxanes (XIV), divinyl-terminated polydimethyl siloxane-co-poly diphenyl siloxanes (XV), and their structures are shown as follows:

[0117]

[0118] 2025PF30037-FC

[0119] -13-

[0120] The viscosity of the bivinyl-terminated siloxanes is in a range of 100K to 1500K cst (0.100000 m2 / s to 1.500000 m2 / s), as determined according to the standard testing method DIN-53019 at 23 °C.

[0121] Advantageously, the bivinyl-terminated siloxane is present in the polycarbonate composition according to the present invention in an amount ranging from 3 wt. % to 10 wt. %, relative to the total weight of the polycarbonate composition.

[0122] An adduct is formed by an in-situ hydrosilylation reaction and is believed to react between the vinyl-terminated siloxane and silicone-hydrogen (Si-H) groups on the surface of MQ resins. Because the unsaturated vinyl-terminated siloxanes are capable of multiple reactions, silicone-hydrogen groups on the surface of MQ resins become crosslinking agent for adjacent vinyl-terminated siloxanes. Without being limited to a particular theory, drip suppression is achieved in compounds of the invention because the resulting structure of PDMS-MQ adducts upon exposure to sufficient temperature inside the extruder barrel to begin the addition reaction under the presence of a catalyst.

[0123] Specially, the invention is based on the chemical bonding between bivinyl-terminated PDMS and the hydride-functional MQ resin to achieve anti -dripping effect in FR PC compositions without using fluorine-containing anti-dripping agents such as PTFE.

[0124] Component E

[0125] The polycarbonate composition according to the present invention comprises a catalyst for the reaction between components C and D as component E.

[0126] The reaction of the vinyl-terminated siloxane and the hydride functional MQ resins should be catalyzed. For that purpose, a catalyst such as an organo-metallic complex can be used, preferably a Pt complex, a Mn complex, a Fe complex, a Zn complex, a Cu complex, or a Ti complex. The platinum complex (platinum divinylteframethyldisiloxane) has the following structure (XVI):

[0127] H3C CH3

[0128] Si-=CH2

[0129] q pt

[0130] Si — — CH2

[0131] H3C CH3 (XVI)

[0132] The above Pt complex catalyst is often used in a form of solution in vinyl terminated PDMS oil. Other organometallics can be used as hydrosilylation catalysts such as Mn, Fe, V, Zr, Zn, Cu, Ti, and others which have been disclosed in PCT Patent Publications WO 2013043912 A2, WO 2013043874 A2, etc.2025PF30037-FC

[0133] -14-

[0134] Advantageously, the catalyst is present in the polycarbonate composition according to the present invention in an amount range from 0.05 ppm-1 ppm, relative to the total weight of the polycarbonate composition.

[0135] Advantageously, components A to E are present in the polycarbonate composition according to the present invention in an amount of at least 90 wt.%, preferably at least 95 wt.%, more preferably at least 98 wt.%, relative to the total weight of the polycarbonate composition.

[0136] Additional components

[0137] In addition to components A-E mentioned above, the polycarbonate composition according to the present invention can optionally comprise one or more additional components conventionally used in polycarbonate compositions. Such additional components are, for example, impact modifiers, heat stabilizers, antistatic agents, pigments (such as carbon black), colorants, lubricants (such as waxes), demoulding agents (such as pentaerythrityl tetrastearate), antioxidants, flow improvers agents, etc.

[0138] The composition does not comprise intentionally added fluorine-containing compounds. The fluorine content in the composition is less than 0.1 wt.%, preferably, the fluorine content in the composition is less than 0.05 wt.%, more preferably, the fluorine content in the composition is less than 0.01 wt.%.

[0139] The person skilled in the art can select the type of the additional components so as not to adversely affect the desired flame retardancy properties of the polycarbonate composition according to the present invention.

[0140] Preferably, the composition according to the present invention comprises up to 10 wt.%, more preferably up to 5 wt. -%, based on the total weight of composition, of one or more additional components selected from the group consisting of impact modifiers, antioxidants, heat stabilizers, UV stabilizers, IR stabilizers, flame retardants, optical brighteners, hydrolysis stabilizers, transesterification stabilizers, additives for laser marking, demoulding agents, antistatic agents, pigments, colorants, flow improvers, and lubricants.

[0141] In some embodiments, the composition according to the present invention further comprises, up to 5 wt.%, based on the total weight of composition, an additional component selected from the group consisting of impact modifiers, antioxidants, heat stabilizers, demoulding agents, antistatic agents, pigments, and lubricants.

[0142] Preferably, the composition according to the present invention comprises

[0143] A) from 68 to 90 wt.% of a polycarbonate,2025PF30037-FC

[0144] -15-

[0145] B) from 6 wt.% to 20 wt.% of a bisphenol-A bis(diphenyl phosphate),

[0146] C) from 0.2 wt.% to 8 wt.% of a a hydride-functional polysiloxane, comprising the resin with CAS number 68083-19-2, more preferably, the resin with CAS number 68083-19-2 is the only hydride-functional polysiloxane contained,

[0147] D) from 3 wt.% to 10 wt.% of a vinyl-terminated PDMS, the viscosity of the vinyl-terminated PDMS is 100K - WOOK cst (0.100000 m2 / s to 1.000000 m2 / s), and

[0148] E) a catalyst for the addition reaction between components C and D.

[0149] In some embodiments, the polycarbonate composition according to the present invention comprises, relative to the total weight of the composition,

[0150] A) from 68 to 90 wt.% of a polycarbonate,

[0151] B) from 6 wt.% to 20 wt.% of a bisphenol-A bis(diphenyl phosphate),

[0152] C) from 0.2 wt.% to 8 wt.% of a hydride-functional MQ resin,

[0153] D) from 3 wt.% to 10 wt.% of a vinyl-terminated PDMS, the viscosity of the vinyl-terminated PDMS is 100K - WOOK cst (0.100000 m2 / s to 1.000000 m2 / s), and

[0154] E) a catalyst for the addition reaction between components C and D.

[0155] Those compositions exemplified may also contain one or more additives as mentioned before.

[0156] Most preferably, the composition according to the invention does not contain any additional components, except from optionally contained additives according to the lists mentioned before, which means, they consist of the before-mentioned components.

[0157] Preparation of the polycarbonate composition

[0158] The polycarbonate composition according to the present invention can be in the form of, for example, pellets.

[0159] The polycarbonate composition according to the present invention demonstrates a good processing behaviour and can be prepared by a variety of methods. For example, the materials contained in the composition of the present invention are fed into the throat of a twin-screw extruder via a hopper. Alternatively, at least one of the components can be incorporated into the composition by feeding it directly into the extruder at the throat and / or downstream through a side stuffer. Additives can also be compounded into a masterbatch with a desired polymeric resin and fed into the extruder. The extruder is generally operated at a temperature higher than that necessary to cause the composition to flow. The extrudate is immediately quenched in a water bath and pelletized. The pellets can be one-fourth inch (0.635 cm, i.e.

[0160] 0.00635 m) long or less as desired. Such pellets can be used for subsequent molding, shaping or forming.2025PF30037-FC

[0161] -16-

[0162] Melt blending methods are preferred due to the availability of melt blending equipment in commercial polymer processing facilities.

[0163] Illustrative examples of equipment used in such melt processing methods include co-rotating and counterrotating extruders, single screw extruders, co-kneaders, and various other types of extrusion equipment.

[0164] The temperature of the melt in the processing is preferably minimized in order to avoid excessive degradation of the polymers. It is often desirable to maintain the melt temperature between 230 °C and 300 °C in the molten resin composition, although higher temperatures can be used provided that the residence time of the resin in the processing equipment is kept short.

[0165] In some cases, the melting composition exits from a processing equipment such as an extruder through small exit holes in a die. The resulting strands of the molten resin are cooled by passing the strands through a water bath. The cooled strands can be chopped into small pellets or other suitable shapes for packaging and further handling.

[0166] Shaped articles

[0167] The polycarbonate composition according to the present invention can be used, for example for the production of various types of shaped articles.

[0168] In the second aspect, the present invention also provides a shaped article made from a polycarbonate composition according to the first aspect of the present invention.

[0169] The polycarbonate composition according to the present invention can be molded into shaped articles such as, housings for electronic device, etc.

[0170] The shaped articles made from the polycarbonate composition according to the present invention have a good flame retardancy.

[0171] Preparation of shaped articles

[0172] The polycarbonate composition according to the present invention can be processed into shaped articles by a variety of means such as injection moulding, extrusion moulding, blow moulding or thermoforming to form shaped articles.2025PF30037-FC

[0173] -17-

[0174] In the third aspect, the present invention provides a process for preparing the shaped article made from the composition according to the first aspect of the present invention, comprising injection moulding, extrusion moulding, blow moulding or thermoforming the polycarbonate composition according to the present invention.

[0175] During preparing shaped articles with the thermoplastic resin composition according to this invention, the melting temperature for the molding process preferably is in the range of 250-300°C, more preferably 255-290°C, even more preferably 260-280°C. The mold temperature could be in the range of 40-110 °C, preferably 50-90 °C, and the injection pressure can be in the range of 300-2500 bar, and preferably 500-2000 bar.

[0176] Examples

[0177] The present invention will be illustrated in detail below with reference to the examples below. The examples are only for the purpose of illustration, rather than limiting the scope of the present invention.

[0178] Materials used

[0179] Component A

[0180] Al : aromatic polycarbonate, which is a linear polycarbonate based on bisphenol A having a weight average molecular weight (Mw) of 31000 g / mol, as determined by means of Gel Permeation Chromatography (GPC) in methylene chloride at 25 °C using a polycarbonate standard, available under the trade name Makrolon M3106 from Covestro Polymer (China) Co., Ltd.

[0181] A2: polycarbonate-polysiloxane copolymer having a polysiloxane content of 20 wt.%, available under the trade name Clamate S2060 from Wanhua Chemical Co. Ltd.

[0182] Component B

[0183] Bl: BDP: bisphenol-A bis(diphenyl phosphate), available from the company Zhejiang Wansheng Science China.

[0184] B2: KSS, a potassium salt of diphenyl sulfone sulfonate, available under the trade name of Arichem KSS-FR from Arichem Co., Ltd.

[0185] Component C

[0186] A hydride-functional MQ resin, available under the trade name Powder-B, XJY8207S from Jiangxi New Jiayi new materials Co. Ltd.2025PF30037-FC

[0187] -18-

[0188] Component D

[0189] DI: a bivinyl-terminated PDMS having a viscosity of 100,000 cst (0.100000 m2 / s) at 23 °C as determined according to the testing method DIN-53019, available under the trade name GYV-100000 from Hangzhou Top Win Technology Development Co. Ltd.

[0190] D2: a bivinyl -terminated PDMS having a viscosity of 50,000 cst (0.050000 m2 / cst) at 23 °C as determined according to the testing method DIN-53019, available under the trade name GYV-50000 from Hangzhou Top Win Technology Development Co. Ltd.

[0191] D3: a bivinyl-terminated PDMS having a viscosity of 200,000 cst (0.200000 m2 / s) at 23 °C as determined according to the testing method DIN-53019, available under the trade name GYV-200000 from Hangzhou Top Win Technology Development Co. Ltd.

[0192] D4: a bivinyl-terminated PDMS having a viscosity of 200,000 cst (0.200000 m2 / s) at 23 °C as determined according to the testing method DIN-53019, available under the trade name MSK SF3000E 200000 from MSK Co. Ltd.

[0193] D5: a bivinyl-terminated PDMS having a viscosity of 1000,000 cst (1.000000 m2 / s) at 23 °C as determined according to the testing method DIN-53019, available under the trade name Momentive PDMS-Vi 1000000 from Momentive Co. Ltd.

[0194] Component E

[0195] A Pt complex catalyst, in the form of a solution of 100 ppm catalyst in vinyl silicone oil, available under the trade name PT-100GC from Su zhou create win-win New material Co., Ltd.

[0196] Additional Components

[0197] AC1820: ethylene-methyl acrylate copolymer: comprising 20 % methyl acrylate content, available as Elvaloy AC 1820 from the company Dupont China.

[0198] ABS: produced by emulsion polymerisation of 42-45 wt. %, based on the ABS polymer, of a mixture of 1 wt. % acrylonitrile and 73 wt. % styrene in the presence of 55-58 wt. %, based on the ABS polymer, of a crosslinked polybutadiene rubber, available as ABS HRG powder P60 from Styrolution.

[0199] MBS: Methyl methacrylate-butadiene-styrene, available as Kane Ace M732 from Japan Kaneka Chemical Co., Ltd.

[0200] S-2130: silicone-acrylic rubber based impact modifier, available under the trade name Metablen S-2130 from Mitsubishi Chemical Corporation.

[0201] XJY-8011: polymethylsilsesquioxane, available under the trade name XJY-8011 from Jiangxi New Jiayi new materials Co. ltd.2025PF30037-FC

[0202] -19-

[0203] Test methods

[0204] Flame retardancy

[0205] The flame retardancy level UL94 VX was measured on specimens with a thickness of 1.5 mm at 23 °C according to UL94:2023.

[0206] Inventive Examples (IE1-23) and Comparative Examples (CE1-CE4)

[0207] The materials listed in Table 1 to Table 4 (the contents are expressed in % by weight relative to the total weight of each composition, unless otherwise indicated) were compounded on a twin-screw extruder (ZSK-26) (from Coperion, Werner and Pfleiderer) at a speed of rotation of 480 rpm, a throughput of 30 kg / h, and a machine barrel temperature of 240°C-260 °C and granulated.

[0208] The granules were processed into corresponding testing specimens on an injection moulding machine (from Arburg) with a melting temperature of 270-300 °C and a mold temperature of 60-80 °C.

[0209] The flame retardancy property of the polycarbonate compositions obtained were tested and the results were summarized in Table 1 to Table 4.

[0210] Table 1: Inventive Examples (IE1-IE10) and their flame retardancy properties

[0211] Components IE1 IE2 IE3 IE4 IE5 IE6 IE7 IE8 IE9 IE10 Al 79.7 82.7 84.7 86.7 88.7 79.95 79.9 79.85 80.5 80.1 Bl 15 12 10 8 6 15 15 15 15 15 C 1 1 1 1 1 1 1 1 0.2 0.6 DI 4 4 4 4 4 4 4 4 4 4 E(ppm) 0.3 0.3 0.3 0.3 0.3 0.05 0.1 0.15 0.3 0.3 UL94 VX VO VO VO VO VO VO VO VO VO VO

[0212]

[0213] 2025PF30037-FC

[0214] -20-

[0215] Table 2: Inventive Examples (IE11-IE19) and their flame retardancy properties

[0216] Components

[0217] IE11 IE 12 IE13 IE 14 IE15 IE16 IE17 IE18 IE19

[0218] Al 80.7 79.7 77.75 73.75 74.2 78.1 75.5 72.95 73.5

[0219] A2 10

[0220] Bl 15 15 14 14 20 14 14 14 12

[0221] C 1 1 4 8 1.6 1.5 2 2.5 1.5

[0222] DI 3 4 4 4 4 6 8 10 3

[0223] E (ppm) 0.3 0.3 0.25 0.25 0.25 0.4 0.4 0.5 0.2

[0224] UL94 VX VO VO VO VO VO VO VO VO VO

[0225]

[0226] It can be seen from Tables 1-2 that the molded parts based on polycarbonate compositions of inventive examples 1-19 (IE 1 -IE 19) according to the present invention can achieve a FR level of UL94 VO at the thickness of 1.5 mm.

[0227] Table 3: comparative examples (CE1-CE4), inventive examples (IE20-IE24) and their FR properties Components CE1 CE2 CE3 CE4 IE20 IE21 IE22 IE23 IE24 Al 82.7 84 83.8 95.5 83.6 83.8 83.8 83.8 83.8 Bl 15 12 12 12 12 12 12 12 B2 0.3

[0228] C 1 1 1 1 1 1 1 1 1 DI 1 3 3 3

[0229] D2 3

[0230] D3 3

[0231] D4 3 3

[0232] D5 3

[0233] E (ppm) 0.3 0 0.2 0.2 0.2 0.2 0.5 0.2 0.2 UL94 VX V2 V2 V2 V2 VO VO VO VO VO

[0234]

[0235] It can be seen from Table 3, when the content of the divinyl-terminated PDMS (DI) is low (1 wt.%) in CE1, a FR level of UL94 VO at the thickness of 1.5 mm cannot be reached for the molded part based on CEE Without the catalyst in CE2, the molded part based on CE2 only achieve a FR level of UL94 V2 at the thickness of 1.5 mm. When the viscosity of the divinyl-terminated PDMS is 50000 cst (0.050000 m2 / s) (D2) in the2025PF30037-FC

[0236] -21-

[0237] polycarbonate composition (CE3), the molded part based on CE3 also can not achieve a FR level of UL94 VO at the thickness of 1.5 mm. When KSS is used as the flame retardant in the polycarbonate composition (CE4), the molded part based on CE4 still only achieve the FR level of UL94 V2 at the thickness of 1.5 mm.

[0238] When the viscosity of the divinyl-terminated PDMS is from 100K to lOOOK cst (0.100000 m2 / s to 1.000000 m2 / s) (components DI, D3-D5) in the polycarbonate compositions (IE20-IE24), the molded parts based on IE20-IE24 can achieve the FR level of UL94 V0 at the thickness of 1.5 mm.

[0239] It can be seen from CE.3 and IE20-IE24, the viscosity of the divinyl -terminated PDMS is also very important in order to achieve a good flame retardancy performance in polycarbonate compositions in this invention.

[0240] Table 4: Inventive examples (IE25-IE29) and their FR properties

[0241] Components IE25 IE26 IE27 IE28 IE29

[0242] Al 74.67 74.67 74.67 74.67 74.67

[0243] Bl 15 15 15 15 15

[0244] C 1.33 1.33 1.33 1.33 1.33

[0245] D3 4 4 4 4 4

[0246] E (ppm) 0.3 0.3 0.3 0.3 0.3

[0247] AC 1820 5

[0248] ABS 5

[0249] MBS 5

[0250] S-2130 5

[0251] XJY-8011 5

[0252] UL94 VX VO VO VO VO VO

[0253]

[0254] It can be seen from Table 4, when an impact modifier, such as ABS, or MBS, or Elvaloy 1820 AC, or Metablen S2130, is used in the polycarbonate compositions (IE25-IE28), a FR level of UL94 VO at the thickness of 1.5 mm can also be reached for the molded parts based on IE25-IE28.

[0255] When 5 wt.% of polymethylsilsesquioxane used in the polycarbonate composition (IE29), a FR level of UL94 VO at the thickness of 1.5 mm can also be achieved for the molded part based on IE29.

Claims

2025PF30037-FC-22-Claims1. A polycarbonate composition comprising the following components, relative to the total weight of the composition:A) from 68 to 90 wt.% of a polycarbonate,B) from 6 wt.% to 20 wt.% of a bisphenol-A bis(diphenyl phosphate),C) from 0.2 wt.% to 8 wt.% of a hydride-functional polysiloxane,D) from 3 wt.% to 10 wt.% of a vinyl-terminated siloxane having a viscosity of 100K -lOOOK cst (0.100000 m2 / s to 1.000000 m2 / s), as determined according to DIN-53019 at 23 °C, andE) a catalyst for the addition reaction between component C and component D.

2. The composition according to claim 1, wherein the polycarbonate has a weight average molecular weight in a range of 24000 to 32000 g / mol, as determined by means of Gel Permeation Chromatography (GPC) in methylene chloride at 25 °C using a polycarbonate standard.

3. The composition according to claim 1 or 2, wherein the vinyl -terminated siloxane contains two vinyl-terminated groups.

4. The composition according to any of claims 1-3, wherein the vinyl -terminated siloxane is selected from the group consisting of divinyl-terminated polydimethyl siloxanes, divinyl-terminated polydimethyl siloxane-co-polydiethyl siloxanes, divinyl-terminated polymethylphenyl siloxanes, and divinyl-terminated polydimethyl siloxane-co-polydiphenyl siloxanes.

5. The composition according to any of claims 1-4, wherein the hydride-functional polysiloxane comprises the resin with CAS number 68083-19-2.

6. The composition according to claim 5, wherein the hydride-functional polysiloxane is the resin with CAS number 68083-19-2.

7. The composition according to any of claims 1-6, wherein the catalyst is selected from the group consisting of organo-metallic complex, preferably Pt complex, Mn complex, Fe complex, Zn complex, Cu complex, or Ti complex.2025PF30037-FC-23-8. The composition according to claim 7, wherein the catalyst is platinum divinyltetramethyldisiloxane.

9. The composition according to any of claims 1-8, wherein the content of the catalyst is between 0.1 and 1 ppm, relative to the total weight of the composition.

10. The composition according to any of claims 1-9, further comprising one or more additional components selected from the group consisting of impact modifiers, heat stabilizers, antioxidants; and mold release agents.

11. The composition according to claim 10, wherein the total amount of the additional components is up to 5 wt. % relative to the total weight of the composition.

12. The composition according to claim 1, comprising the following components, relative to the total weight of the composition:A) from 68 to 90 wt.% of a polycarbonate,B) from 6 wt.% to 20 wt.% of a bisphenol-A bis(diphenyl phosphate),C) from 0.2 wt.% to 8 wt.% of a hydride-functional polysiloxane, wherein the hydride-functional polysiloxane comprises the resin with CAS number 68083-19-2,D) from 3 wt.% to 10 wt.% of a vinyl-terminated PDMS, the viscosity of the vinyl-terminated PDMS is 100K - WOOK cst (0.100000 m2 / s to 1.000000 m2 / s), andE) a catalyst for the addition reaction between components C and D.

13. A shaped article made from the composition according to any of claims 1-12.

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