Flame-retardant polycarbonate composition

Abstract

This invention relates to a flame-retardant polycarbonate composition comprising the following components, relative to the total weight of the composition: A) 30-70 wt% of at least one aromatic polycarbonate, B) 20-60 wt% of at least one polysiloxane-polycarbonate block condensate, C) 0.5-5 wt% of at least one cyclophosphonitrile, D) 1-5 wt% of at least one silicone-acrylate rubber-based impact modifier, E) 0.3-3 wt% of kaolin, F) 0.1-1 wt% of at least one anti-dripping agent, and G) 0.1-1 wt% of at least one ultraviolet absorber. The invention also relates to molded articles made from said composition. The polycarbonate composition according to the invention has a good combination of low-temperature impact resistance, flame retardancy, hydrolytic stability, UV resistance, and heat resistance.

Description

Technical Field

[0001] This invention belongs to the field of polycarbonate. In particular, this invention relates to a flame-retardant polycarbonate composition and molded articles made therefrom. Background Art

[0002] In outdoor applications facing harsh environmental conditions, such as extreme high or low temperatures, high humidity, and fire risks, high requirements are placed on plastic casing materials. In most cases, these materials need good low-temperature impact resistance, good hydrolytic stability, good UV resistance, high flame retardancy, and high heat resistance.

[0003] Polycarbonate (PC) resin exhibits high heat resistance and good impact resistance at room temperature. However, at low temperatures, such as below 0°C or even lower, PC resin is sensitive to small defects and residual internal stress, thus unable to withstand large external impacts. To improve low-temperature impact strength, impact modifiers (mostly with a core-shell structure of a rubber core and grafted chains) are often compounded with polycarbonate raw materials. However, some residual acids, emulsifiers, and metal ions are detrimental to the hydrolytic stability of polycarbonate compounds. Furthermore, large amounts of impact modifiers also lead to reduced flame retardancy. The addition of flame retardants, such as traditional phosphorus flame retardants (bisphenol A bis(diphenyl phosphate) (BDP), tetraphenylresorcinol diphosphate (RDP), etc.), tends to improve flame retardancy but sacrifices impact resistance, heat resistance, and hydrolytic stability.

[0004] Polysiloxane-polycarbonate copolymers (Si-co-PC) have been promising candidates to replace traditional core-shell impact modifiers for providing good low-temperature impact performance without negatively impacting flame retardancy. However, most commercially available Si-co-PC resins have low siloxane content (<10%) and cannot provide good low-temperature impact strength on their own.

[0005] Therefore, for polycarbonate compounds used in outdoor applications, a major challenge is to achieve a balance between low-temperature impact resistance, flame retardancy, hydrolytic stability, UV resistance, and heat resistance.

[0006] WO2015022676A discloses blended thermoplastic compositions comprising at least one polycarbonate component, at least one impact modifier, at least one mineral filler, and at least one flame retardant. The resulting compositions can be used to prepare articles requiring high modulus, ultra-high ductility, good flowability, thin-wall flame retardancy, and good heat resistance. All examples in this document contain 15% mineral filler. Materials with this composition are expected to have poor low-temperature impact properties and low heat resistance.

[0007] WO2003 / 042305A1 discloses a flame-retardant resin composition comprising (i) at least one aromatic polycarbonate, (ii) at least one silicone source, (iii) at least one boron source, and (iv) at least one member optionally selected from anti-dripping agents, a second thermoplastic resin that is not a polycarbonate resin, and a rubber-modified graft copolymer. The boron compound used therein may negatively affect the thermal and hydrolytic stability of the composition.

[0008] WO2007 / 037952A1 discloses a flame-retardant thermoplastic composition comprising a polycarbonate component; an impact modifier; a filler with a surface treatment comprising pretreating the filler with or mixing it with a vinyl-functionalized silane coupling agent; a polycarbonate-polysiloxane copolymer; and a flame retardant. All examples in this document contain 10% filler and use BDP as the flame retardant. Materials with this composition are expected to have poor low-temperature impact properties and low heat resistance.

[0009] Therefore, there remains a need for polycarbonate compositions that offer a good combination of low-temperature impact resistance, flame retardancy, hydrolytic stability, UV resistance, and heat resistance. SUMMARY OF THE INVENTION

[0011] One object of this application is to provide a polycarbonate composition having a good combination of low-temperature impact resistance, flame retardancy, hydrolytic stability, UV resistance and heat resistance.

[0012] Therefore, according to a first aspect, the present invention provides a flame-retardant polycarbonate composition comprising the following components, relative to the total weight of the composition:

[0013] A) 30-70% by weight of at least one aromatic polycarbonate,

[0014] B) 20-60% by weight of at least one polysiloxane-polycarbonate copolymer,

[0015] C) 0.5-5% by weight of at least one cyclophosphinitrogen,

[0016] D) 1-5% by weight of at least one silicone-acrylate rubber-based impact modifier,

[0017] E) 0.3-3% by weight of kaolin,

[0018] F) 0.1-1% by weight of at least one anti-dripping agent, and

[0019] G) 0.1-1% by weight of at least one ultraviolet absorber.

[0020] According to a second aspect, the present invention provides a molded article made of a polycarbonate composition according to a first aspect of the present invention.

[0021] According to a third aspect, the present invention provides a method for preparing a molded article according to a second aspect of the present invention, comprising injection molding, extrusion molding, blow molding or thermoforming a polycarbonate composition according to a first aspect of the present invention.

[0022] The polycarbonate composition and molded articles according to the present invention have good flame retardancy, excellent low-temperature impact resistance, good heat resistance and good hydrolytic stability.

[0023] The polycarbonate compositions and molded articles according to the present invention are suitable for outdoor applications requiring relatively high flame retardancy (such as UL945VB), good hydrolytic stability and excellent low-temperature impact strength, such as network antennas, electric vehicle charging gun closures, photovoltaic junction boxes, electric scooter battery housings, etc.

[0024] Other subjects, features, aspects, and advantages of the invention will become clearer upon reading the following description and examples. Invention Details

[0026] In the following text and unless otherwise specified, the limits of the numerical range are included within this range, especially in the expressions “between” and “...to…”.

[0027] As used herein, the term "includes" is interpreted to encompass all specifically mentioned elements as well as optional, additional, or unspecified elements.

[0028] The term "at least one" as used in this article refers to one or more.

[0029] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. Where the definitions of terms in this specification conflict with the meanings commonly understood by one of ordinary skill in the art to which this invention pertains, the definitions set forth herein shall prevail.

[0030] Unless otherwise specified, all numerical values ​​used in the specification and claims to indicate quantities of ingredients, etc., shall be understood to be modified by the term “about”.

[0031] Unless otherwise specified, all percentages in this application refer to weight percentages.

[0032] The technical features described for each component in the composition according to the invention may be combined in any manner without conflict.

[0033] Component A

[0034] According to a first aspect, the polycarbonate composition according to the invention comprises at least one aromatic polycarbonate as component A.

[0035] According to the present invention, the aromatic polycarbonate suitable as component A is known in the literature or can be prepared by methods known in the literature (for the preparation of aromatic polycarbonates, see, for example, Schnell, "Chemistry and Physics of Polycarbonates", Interscience Publishers, 1964, and DE-AS 1 495 626, DE-A 2 232877, DE-A 2 703 376, DE-A 2 714 544, DE-A 3 000 610, DE-A 3 832 396; and DE-A 3 007934).

[0036] Aromatic polycarbonates are prepared, for example, by reacting bisphenols with carbonyl halides, preferably phosgene, and / or with dihalogens of aromatic dicarboxylic acids, preferably dihalogens of phthalic acid, via an interfacial method, optionally using chain terminators, such as monophenols, and optionally using trifunctional or greater branching agents, such as triphenols or tetraphenols. They can also be prepared by melt polymerization via the reaction of bisphenols with, for example, diphenyl carbonate.

[0037] The bisphenols used to prepare aromatic polycarbonates are preferably those of formula (I):

[0038]

[0039] in

[0040] A is a single bond, C1-C5-alkylene, C2-C5-alkylidene, C5-C6-cycloalkyl, -O-, -SO-, -CO-, -S-, -SO2-, and may be fused with other aromatic rings optionally containing heteroatoms. 12 -Aspartic acid

[0041] Groups of formula (II) or (III):

[0042]

[0043] B is C1-C in every case. 12 -alkyl, preferably methyl, or halogen, preferably chlorine and / or bromine,

[0044] x is 0, 1, or 2 independently in each case.

[0045] p is 1 or 0, and

[0046] R 5 and R6 Can be targeted at each X 1 Independently selected, and independently of each other, are hydrogen or C1-C6-alkyl, preferably hydrogen, methyl, or ethyl, X 1 It is carbon and

[0047] m is an integer from 4 to 7, preferably 4 or 5.

[0048] The condition is R 5 and R 6 In at least one atom X 1 The upper part is also an alkyl group.

[0049] Preferred bisphenols include hydroquinone, resorcinol, dihydroxydiphenol, bis(hydroxyphenyl)-C1-C5-alkane, bis(hydroxyphenyl)-C5-C6-cycloalkane, bis(hydroxyphenyl) ether, bis(hydroxyphenyl) sulfoxide, bis(hydroxyphenyl) ketone, bis(hydroxyphenyl) sulfone, and α,α-bis(hydroxyphenyl)diisopropylbenzene, as well as their cyclo-brominated and / or cyclo-chlorinated derivatives.

[0050] Particularly preferred bisphenols are 4,4'-dihydroxybiphenyl, 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, 4,4'-dihydroxydiphenyl sulfone, and their di- and tetrabrominated or chlorinated derivatives, such as 2,2-bis(3-chloro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, or 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane. 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) is particularly preferred.

[0051] Bisphenols can be used alone or as part of any desired mixture. Bisphenols are known in the literature or can be obtained by methods known in the literature.

[0052] Examples of suitable chain terminators for the preparation of thermoplastic aromatic polycarbonates are phenol, p-chlorophenol, p-tert-butylphenol, or 2,4,6-tribromophenol, as well as long-chain alkylphenols such as 4-[2-(2,4,4-trimethylpentyl)]phenol and 4-(1,3-tetramethylbutyl)phenol according to DE-A 2 842 005, or monoalkylphenols or dialkylphenols having a total of 8 to 20 carbon atoms in the alkyl substituents, such as 3,5-di-tert-butylphenol, p-isooctylphenol, p-tert-octylphenol, p-dodecylphenol, 2-(3,5-dimethylheptyl)phenol, and 4-(3,5-dimethylheptyl)phenol. The amount of chain terminator used is typically from 0.5 mol% to 10 mol% based on the total molar amount of the particular bisphenol used.

[0053] The thermoplastic aromatic polycarbonate can be branched in a known manner, preferably by incorporating 0.05 to 2.0 mol% of a trifunctional or greater trifunctional compound, such as a compound having three or more phenolic groups, based on the total amount of bisphenol used.

[0054] Both homopolymers and copolymers are suitable. In the case where a copolymer is used as component A, this copolymer is different from the polysiloxane-polycarbonate copolymer used as component B, as described in detail below.

[0055] The preferred aromatic dicarboxylic acid dihalogens used to prepare aromatic polycarbonates are isophthalic acid, terephthalic acid, diphenyl ether 4,4'-dicarboxylic acid, and naphthal-2,6-dicarboxylic acid diacyl dichloroisophthalic acid.

[0056] A mixture of isophthalic acid dichlorodi ...

[0057] In the preparation of polycarbonate, carbonyl halides are also used simultaneously, preferably phosgene as a bifunctional acid derivative.

[0058] Besides the monophenols already mentioned, suitable chain terminators for the preparation of aromatic polycarbonates include their chlorocarbonates and those optionally converted to C1-C2. 22 Acyl chlorides of aromatic monocarboxylic acids substituted with alkyl or halogen atoms, and aliphatic C2-C 22 - Monocarboxylic acid chloride.

[0059] The amount of chain terminator is 0.1 to 10 mol% in each case, based on the number of moles of bisphenol in the case of phenolic chain terminators, and based on the number of moles of dichlorodicarboxylic acid in the case of monocarboxylic acid chlorine chain terminators.

[0060] One or more aromatic hydroxycarboxylic acids may be used in the preparation of aromatic polycarbonates.

[0061] Aromatic polycarbonates can be linear or branched in a known manner (see DE-A 2 940 024 and DE-A 3 007 934 in this regard), with linear polycarbonates being preferred.

[0062] Examples of usable branching agents are (based on the dicarboxylic acid dichloro used) 0.01 to 1.0 mol% of trifunctional or greater trifunctional carboxylic acid chlorides, such as pyromellitic trichloro, cyanuric trichloro, benzophenone-3,3',4,4'-tetracarboxylic acid tetrachloro, naphthyl-1,4,5,8-tetracarboxylic acid tetrachloro, or pyromellitic tetrachloro, or 0.05 to 2.0 mol% of trifunctional or greater trifunctional phenols based on the diphenol used, such as phloroglucinol, 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)-2-heptene, 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)-2-heptene, etc. Alkane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, tris(4-hydroxyphenyl)phenylmethane, 2,2-bis[4,4-bis(4-hydroxyphenyl)cyclohexyl]propane, 2,4-bis(4-hydroxyphenyl isopropyl)phenol, tetra(4-hydroxyphenyl)methane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, 2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl)propane, tetra(4-[4-hydroxyphenyl isopropyl]phenoxy)methane, or 1,4-bis[4,4'-(dihydroxytriphenyl)methyl]benzene. Phenolic branching agents can be used with bisphenols; acyl chloride branching agents can be introduced together with diacyl chlorides.

[0063] The proportion of carbonate structural units in thermoplastic aromatic polycarbonates can be freely varied. The proportion of carbonate groups is preferably at most 100 mol%, particularly at most 80 mol%, and especially preferably at most 50 mol%, based on the sum of ester groups and carbonate groups. Both the ester and carbonate portions of the aromatic polycarbonate can exist in the condensation product in block or random form.

[0064] The polycarbonate used is preferably linear, and more preferably based on bisphenol A.

[0065] Preferably, the aromatic polycarbonate has a weight-average molecular weight (M0) of 15,000 to 80,000 g / mol, more preferably 20,000 to 32,000 g / mol, more preferably 23,000 to 28,000 g / mol, and even more preferably 24,000 to 26,000 g / mol. w It was determined by GPC (gel permeation chromatography in dichloromethane using bisphenol A-based polycarbonate as a standard).

[0066] As an example of an aromatic polycarbonate suitable for use in this invention, reference can be made to Covestro Co., Ltd. 2600 The kind sold under the name 2400.

[0067] Aromatic polycarbonates can be used alone or in any desired mixture.

[0068] Advantageously, the aromatic polycarbonate is present in the polycarbonate composition in an amount of 35% to 70% by weight, preferably 35% to 66% by weight, relative to the total weight of the polycarbonate composition.

[0069] Component B

[0070] According to a first aspect, the polycarbonate composition according to the invention comprises at least one polysiloxane-polycarbonate block copolymer (also referred to as "SicoPC" in the context of this application) as component B.

[0071] The polysiloxane-polycarbonate copolymer comprises a polydiorganosiloxane (also referred to as "siloxane" in the context of this application) block and a polycarbonate block.

[0072] In particular, the polysiloxane-polycarbonate copolymer contains structural units (IVs).

[0073]

[0074] Where R1 is a divalent or unsubstituted aryl, divalent straight-chain, or cyclic aliphatic group.

[0075] Alternatively, structural unit (IV) is a mixture of units, wherein R1 is a divalent or unsubstituted aryl group or a divalent linear or cyclic aliphatic group, and the proportion of aromatic R1 groups is 60-100% by weight and the proportion of aliphatic groups is 0-40% by weight, based on the total amount of bisphenols of formula (I') used below.

[0076] and structural unit (V)

[0077]

[0078] R2 is independently C each time it appears. 1- C 13 Monovalent organic groups, such as C1-C 13 Alkyl, C1-C 13 Alkoxy, C2-C 13 alkenyl, C2-C 13 Alkenyloxy, C3-C6 cycloalkyl, optionally fully or partially halogenated with fluorine, chlorine, bromine or iodine, or a combination thereof.

[0079] R2 is preferably C1-C independently each time it occurs. 12 Alkyl groups, particularly C1-C4 alkyl groups, especially methyl or phenyl groups.

[0080] The most particularly preferred structural unit (V) is a dimethylsiloxane unit or a diphenylsiloxane unit, a methyl / phenylsiloxane unit, or a mixture of dimethylsiloxane and diphenylsiloxane units.

[0081] Component B preferably contains 2% to 20% by weight, more preferably 3% to 10% by weight, of the structural unit of formula (V), which is also referred to below as a siloxane block, based on the weight of component B.

[0082] In structural unit (IV), R1 is preferably a dihydroxyaryl compound derived from formula (I'):

[0083]

[0084] A is a single bond, C1-C5-alkylene, C2-C5-alkylidene, C5-C6-cycloalkylidene, -O-, -SO-, -CO-, -S-, -SO2-, and may be fused with other aromatic rings optionally containing heteroatoms. 12 -Aspartic acid

[0085] Groups of formula (II') or (III'):

[0086]

[0087] B is C1-C in every case. 12 -alkyl, preferably methyl, or halogen, preferably chlorine and / or bromine,

[0088] x is 0, 1, or 2 independently in each case.

[0089] p is 1 or 0, and

[0090] R 5 and R 6 Can be targeted at each X 1 Independently selected, and independently of each other, are hydrogen or C1-C6-alkyl, preferably hydrogen, methyl, or ethyl, X 1 It is carbon and

[0091] m is an integer from 4 to 7, preferably 4 or 5.

[0092] The condition is R 5 and R 6 At the same time, it is at least one atom X 1 Alkyl groups on the surface.

[0093] Examples of diphenols of formula (I') suitable for producing SiCoPC according to the present invention include hydroquinone, resorcinol, bis(hydroxyphenyl)alkanes, bis(hydroxyphenyl)sulfides, bis(hydroxyphenyl) ethers, bis(hydroxyphenyl) ketones, bis(hydroxyphenyl) sulfones, bis(hydroxyphenyl) sulfoxides, [α],[α]'-bis(hydroxyphenyl)diisopropylbenzene, and their alkylated, cyclo-alkylated, and cyclo-halogenated compounds.

[0094] More preferred bisphenols of formula (I') are 4,4'-dihydroxybiphenyl, 2,2-bis(4-hydroxyphenyl)-1-phenylpropane, 1,1-bis(4-hydroxyphenyl)phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene (bisphenol M), 2,2-bis(3-methyl-4-hydroxyphenyl)propane Alkane, bis(3,5-dimethyl-4-hydroxyphenyl)methane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, bis(3,5-dimethyl-4-hydroxyphenyl)sulfone, 2,4-bis(3,5-dimethyl-4-hydroxyphenyl)-2-methylbutane, 1,3-bis[2-(3,5-dimethyl-4-hydroxyphenyl)-2-propyl]benzene, 1,1-bis(4-hydroxyphenyl)cyclohexane and 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane.

[0095] Particularly preferred diols of formula (I') are 2,2-bis(4-hydroxyphenyl)propane (BPA), hydroquinone, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane and 2,2-bis(3-methyl-4-hydroxyphenyl)propane.

[0096] These and other suitable bisphenols are commercially available and described, for example, in “H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York 1964, pp. 28 and thereafter; pp. 102 and thereafter” and “D. G. G. Egerand, J. T. B. Endler, Handbook of Polycarbonate Science and Technology, Marcel Dekker, New York 2000, pp. 72 and thereafter”.

[0097] Preferably, the siloxane block has the following structure (VI).

[0098]

[0099] R2 is defined above for structural unit (V).

[0100] n represents an average of 10 to 400, preferably 10 to 100, and particularly preferably 15 to 50, determined in each case by 1H-NMR spectroscopy.

[0101] k represents 0 or 1,

[0102] R3 independently contains either the following structural element (VII) or (VIII) each time it appears:

[0103]

[0104] R4 is independently hydrogen, halogen, and / or C1-C each time it appears. 10 Preferably, it is a C1-C4, straight-chain or branched, unsubstituted or mono- to tetrasubstituted alkyl or alkoxy group, wherein the alkyl and alkoxy groups are preferably unsubstituted, and R4 is particularly preferably hydrogen, e is 0 or 2 to 12, preferably a natural number from 2 to 6, wherein when e is 0, k is 1.

[0105]

[0106] where R 6 and R 7 They represent H and C1-C independently. 18 -alkyl, C1-C 18 -alkoxy, halogen such as Cl or Br, or optionally substituted aryl or aralkyl groups in each case, preferably representing H or C1-C independently of each other. 12 -alkyl, particularly preferably H or C1-C8-alkyl, and very particularly preferably H or methyl, which are independently represented by each other.

[0107] and

[0108] X represents -CO-, -O-, -S-, C1-C6-alkylene, C2- to C5-alkylidene, C6-C 10 - Cycloalkylidene or optionally fused with other aromatic rings containing heteroatoms, C6-C 12 -Aspartic acid.

[0109] Preferably, X represents C1-C5-alkylene, C2-C5-alkylidene, C6-C9-cyclohexylidene, -O-, -SO-, -CO-, -S-, -SO2-, and is particularly preferred to be isopropylidene, 3,3,5-trimethylcyclohexylidene or oxygen, especially isopropylidene.

[0110] For example, and preferably, the siloxane block is derived from structure (IX) or structure (X):

[0111]

[0112] In formulas (IX) and (X), a represents an average of 10 to 400, preferably 10 to 100, and particularly preferably 15 to 50, determined by 1H-NMR spectroscopy in each case.

[0113] The 1H-NMR spectra of all siloxane blocks and the whole component B shown here can be performed in deuterated chlorinated solvents, preferably in deuterated chloroform or deuterated dichloromethane. The appropriate signals are integrated and compared in each case.

[0114] In structures IX and X, for example, a is determined by using the integral of the SiCH3 proton between 0 and 0.5 ppm chemical shifts and the integral of the adjacent CH2 at a chemical shift of about 2.6 ppm.

[0115] In a further embodiment, the above-mentioned siloxane blocks may be linked once or multiple times via terephthalic acid or isophthalic acid to provide the following exemplary structural elements:

[0116]

[0117] Where p represents 0 or 1,

[0118] R2, R3, n, and k are as defined above for the structuring element (VI).

[0119] The corresponding siloxane blocks used for reactions with polycarbonate or with bisphenols of formula (I'), phosgene, or diaryl carbonates each have terminal phenolic OH groups, i.e.

[0120]

[0121] R2, R3, n, k, and p are as defined for structuring element (XI).

[0122] Particularly preferred are (poly)siloxanes whose siloxane blocks are hydroxyaryl-terminated (XII) groups.

[0123]

[0124] In general formula (XII), R5 represents hydrogen or C1-C4-alkyl, C1-C4-alkoxy, preferably hydrogen or methyl, methoxy, and particularly preferably hydrogen.

[0125] R 6 and R 7 Each can be independently represented by an aryl group, preferably a phenyl group, a C1-C4 alkyl group, preferably a methyl group, especially a methyl group.

[0126] Y represents a single bond, -CO-, -O-, C1- to C5-alkylene, C2-C5-alkylidene, or a C5-C6-cycloalkylidene that can be mono- or poly-substituted by C1-C4-alkyl, preferably a single bond, -O-, isopropylidene, or a C5-C6-cycloalkylidene that can be mono- or poly-substituted by C1-C4-alkyl, especially isopropylidene.

[0127] V represents oxygen, C1-C6 alkylene or C2-C5 alkylidene, preferably a single bond, oxygen, C3 alkylene, especially oxygen or isopropylidene.

[0128] W represents a single bond, S, C1-C6-alkylene or C2-C5-alkylidene, preferably a single bond, C3-alkylene or isopropylidene, wherein W is not a single bond when q represents 1.

[0129] p and q each represent 0 or 1 independently.

[0130] o represents the average number of repeating units from 10 to 400, preferably from 10 to 100, and particularly preferably from 15 to 50, which is determined by 1H-NMR spectroscopy in each case.

[0131] For example, the integral of the central Si-CH3 proton (at a chemical shift of about 0.1 ppm) relative to the two terminal siloxane units of the block, namely the integral of O-Si(CH3)2 (at a chemical shift of about 0.2 ppm), is determined.

[0132] m represents the average number of repeating units from 1 to 10, preferably from 1 to 6, and particularly preferably from 1.5 to 5, which is determined by 1H-NMR spectroscopy in each case.

[0133] The most particularly preferred are siloxanes of formulas (XIII) and (XIV).

[0134]

[0135] in

[0136] R1 independently represents hydrogen, Cl, Br, or C1-C4-alkyl, preferably hydrogen or methyl, and especially hydrogen.

[0137] R2 independently represents aryl or C1-C. 13 Alkyl groups, preferably C1-C4-alkyl groups,

[0138] X represents a single bond, -O-, -SO-, -CO-, -S-, -SO2-, C1-C6-alkylene, C2-C5-alkylidene, C5-C 12 -Cycloalkylidene groups or C6-C groups optionally fused with aromatic rings containing other heteroatoms 12-arylene, preferably representing a single bond, -O-, -SO-, -CO-, -S-, -SO2-, C1-C5-alkylene, C2-C5-alkylidene, C5-C 12 - Cycloalkylidene group, particularly preferred with single bond, isopropylidene group, C5-C 12 Cycloalkylidene or oxygen, with isopropylidene being particularly preferred.

[0139] n represents an average of 10 to 400, preferably 10 to 100, and particularly preferably 10 to 50, determined in each case by 1H-NMR spectroscopy.

[0140] m represents an average of 1 to 10, preferably 1 to 6, and especially preferably 1.5 to 5, which is determined by 1H-NMR spectroscopy in each case.

[0141] The determination of n in structures XI, XIII, and XIV is performed according to the method described above for o.

[0142] The determination of m uses the integral of the proton at the terminal phenyl group, such as at the terminal bisphenol-A derived unit, and the integral of the central phenyl group, such as at the central bisphenol-A derived unit.

[0143] The preferred choice is the siloxane of formula XIV, because they exhibit particularly good thermal and color stability.

[0144] The weight-average molecular weight Mw of the siloxane component, i.e. the siloxane block, is preferably 3,000 to 20,000 g / mol, as determined by gel permeation chromatography and using BPA (bisphenol A) polycarbonate standards, and is particularly preferably 3,500 to 15,000 g / mol.

[0145] The preparation of siloxanes of formulas (XII) to (XIV) is described, for example, in DE 33 34 782 A1 and DE19710081.

[0146] The siloxane component of formula (XII), (XIII) or (XIV) is used in an amount of 0.5% to 50% by weight, preferably 1% to 40% by weight, particularly preferably 2% to 20% by weight, and very particularly preferably 2.5% to 10% by weight, in each case based on the weight of component B.

[0147] The principles of siloxane block preparation are known, and they can be prepared by methods such as those described in, for example, US20130267665.

[0148] Polysiloxane-polycarbonate copolymers are typically prepared industrially from monomers via an interfacial method with phosgene. The preparation of these polysiloxane-polycarbonate copolymers using bisphenol carbonate via melt transesterification is also known.

[0149] The preparation of polysiloxane-polycarbonate copolymers by interfacial methods is known in the literature and described in, for example, US-A3 189 662, US-A3 419 634, DE-A3 34 782 and EP 0 122 535.

[0150] US 5,227,449 describes the preparation of polysiloxane-polycarbonate copolymers by melt transesterification of bisphenol, diaryl carbonate, silanol-terminated polysiloxanes and catalysts.

[0151] Reactive extrusion methods for preparing polysiloxane-polycarbonate copolymers have also been described. These are disclosed, for example, in US 5414054 and US 5821321.

[0152] The polysiloxane-polycarbonate copolymer used according to the present invention is preferably prepared in a melt transesterification method, more preferably in a reactive extrusion method. The reactive extrusion method preferably comprises mixing and reacting the following components in a melt in an extruder or a high-viscosity reactor.

[0153] a) A polymer containing at least one structural unit of formula (IV), preferably an aromatic polycarbonate.

[0154] b) At least one hydroxyaryl-terminated (poly)siloxane, preferably according to any one of formulas IX, X, XIa, XII, XIII, XIV.

[0155] c) Optionally, at least one additive, such as a catalyst, may be used.

[0156] The extruder or melt reactor can be a single-screw reactor, a twin-screw reactor, or a multi-screw reactor, such as a planetary roll extruder or a ring extruder. Large-capacity kneading reactors may also be involved.

[0157] This method can be carried out in a single unit—such as a twin-screw extruder—or in two stages, i.e., in a reactor assembly. The reactor assembly preferably consists of a pre-reactor (such as a twin-screw extruder) and a high-viscosity reactor.

[0158] The method is preferably carried out at a temperature of 280°C to 400°C, more preferably 290°C to 380°C, more preferably 300°C to 350°C, and at a pressure of 0.001 mbar to 50 mbar, more preferably 0.005 mbar to 40 mbar, particularly preferably 0.02 mbar to 30 mbar, and very particularly preferably 0.03 mbar to 5 mbar, and preferably in the presence of a catalyst.

[0159] Advantageously, the polysiloxane-polycarbonate copolymer is present in the polycarbonate composition according to the invention in an amount of 25% to 60% by weight, preferably 25% to 56% by weight, relative to the total weight of the polycarbonate composition.

[0160] Preferably, the total amount of components A and B is not less than 85% by weight relative to the total weight of the polycarbonate composition.

[0161] Component C

[0162] According to the first aspect, the polycarbonate composition according to the invention comprises at least one cyclophosphonitrile as component C.

[0163] Preferably, the cyclophosphonitrile used according to the present invention is a cyclophosphonitrile of formula (XV):

[0164]

[0165] in

[0166] k is an integer from 1 to 10, preferably from 1 to 8, and especially preferably from 1 to 5.

[0167] The trimer content (k=1) is 60 to 100 mol% based on component C.

[0168] And among them

[0169] R is the same or different in each case and represents

[0170] -amine group,

[0171] - In each case, halogenation is optional, preferably fluorination, and more preferably monohalogenated C1-C8 alkyl groups, preferably methyl, ethyl, propyl, or butyl.

[0172] -C1-C8-alkoxy, preferably methoxy, ethoxy, propoxy, or butoxy.

[0173] -In each case, the alkyl group is optionally selected, preferably C1-C4-alkyl and / or halogen, preferably chlorine- and / or bromine-substituted C5-C6-cycloalkyl.

[0174] -In each case, it may optionally be alkyl, preferably C1-C4-alkyl and / or halogen, preferably chlorine or bromine and / or hydroxyl-substituted C6-C 20 -Aryloxy group, preferably phenoxy or naphthoxy group.

[0175] -In each case, it may optionally be alkyl, preferably C1-C4-alkyl, and / or halogen, preferably chlorine- and / or bromine-substituted C7-C 12 -Aryl group, preferably phenyl-C1-C4-alkyl group

[0176] - Halogen group, preferably chlorine or fluorine, or

[0177] -OH group.

[0178] The following are preferred: propoxyphosphazene, phenoxyphosphazene, methylphenoxyphosphazene, aminophosphazene, and fluoroalkylphosphazene, as well as phosphazenes with the following structures:

[0179]

[0180] In the compounds shown above, k = 1, 2, or 3.

[0181] In the case where the phosphazene of formula (XV) is halogenated on phosphorus (e.g. from an incompletely reacted starting material), the proportion of such halogenated phosphazene on phosphorus is preferably less than 1000 ppm, more preferably less than 500 ppm.

[0182] Phosphazenes can be used alone or as a mixture, i.e., the groups R can be the same or the two or more groups in formula (XV) can be different. Preferably, the groups R of the phosphazenes are the same.

[0183] In a more preferred embodiment, only phosphazenes having the same R are used.

[0184] Preferably, all R = phenoxy.

[0185] The most preferred compound is a phenoxyphosphazene of formula (XVI) having an oligomer content (C1) of 65 mol% to 100 mol% where k = 1.

[0186]

[0187] In one embodiment, phenoxyphosphazene of formula (XVI) is used as component C, wherein the trimer content (k=1) is 85 to 100 mol%, more preferably 98.5 to 100 mol%, and even more preferably 99 to 100 mol%, based on component C.

[0188] Phosphazenes and their preparation are described, for example, in EP-A728 811, DE-A 1 961 668 and WO 97 / 40092.

[0189] It can also be done after mixing. 31 P-NMR (chemical shift; δ trimer: 6.5 to 10.0 ppm; δ tetramer: -10 to -13.5 ppm; δ higher oligomers: -16.5 to -25.0 ppm) is used to detect and quantify the oligomer composition of phosphazenes in each blend sample.

[0190] Advantageously, cyclophosphonitrile is present in the polycarbonate composition in an amount of 1% to 5% by weight, preferably 1.5% to 4.5% by weight, relative to the total weight of the polycarbonate composition.

[0191] Component D

[0192] According to a first aspect, the polycarbonate composition according to the invention comprises at least one silicone-acrylate rubber-based impact modifier as component D.

[0193] This silicone-acrylate rubber-based impact modifier has a core-shell impact structure.

[0194] Preferably, the silicone-acrylate rubber-based impact modifier comprises D.1 on D.2:

[0195] D.1) 5% to 90% by weight, preferably 8% to 80% by weight, particularly 10% to 70% by weight of at least one vinyl monomer,

[0196] D.2) 95% to 10% by weight, preferably 92% to 20% by weight, and especially 90% to 30% by weight, of one or more silicone-acrylate rubbers as the grafting substrate.

[0197] The weight percentage is calculated based on the weight of the impact modifier.

[0198] Vinyl monomers are used to form polymer chains and chemically bond them to the grafted substrate D.2.

[0199] Preferably, the vinyl monomer D.1 is selected from vinyl aromatics and / or nucleus-substituted vinyl aromatics (such as styrene, α-methylstyrene, p-methylstyrene), vinyl cyanides (unsaturated nitriles, such as acrylonitrile and methacrylonitrile), (C1-C8)-alkyl esters of (meth)acrylates, such as methyl methacrylate, ethyl methacrylate, n-butyl acrylate, tert-butyl acrylate, and derivatives of unsaturated carboxylic acids (such as acid anhydrides and imides), such as maleic anhydride and N-phenyl-maleimide.

[0200] More preferably, the at least one vinyl monomer D.1 comprises (meth)acrylate (C1-C8)-alkyl ester or a combination thereof with styrene, α-methylstyrene or p-methylstyrene.

[0201] Preferably, the grafted substrate D.2 may have a glass transition temperature of <10°C, more preferably <0°C, and particularly preferably <-20°C. The glass transition temperature is determined by dynamic differential calorimetry (DSC) according to standard DIN EN 61006 at a heating rate of 10 K / min, where T... g It is defined as the midpoint temperature (tangent method).

[0202] In some embodiments, monomer D.1 is a mixture of the following: D.1.1) 50 to 99, preferably 60 to 80, especially 70 to 80 parts by weight of vinyl aromatics and / or cyclically substituted vinyl aromatics (such as styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene) and / or (C1-C8)-alkyl methacrylates, such as methyl methacrylate, ethyl methacrylate, based on D.1; and D.1.2) 1 to 50, preferably 20 to 40, especially 20 to 30 parts by weight of (C1-C8)-alkyl (meth)acrylates, such as methyl methacrylate, n-butyl acrylate, tert-butyl acrylate, and / or derivatives of unsaturated carboxylic acids (such as anhydrides and imides), such as maleic anhydride and N-phenylmaleimide.

[0203] Preferably, monomer D.1.1 is selected from at least one of styrene, α-methylstyrene, and methyl methacrylate; preferably, monomer D.1.2 is selected from at least one of maleic anhydride and methyl methacrylate. Particularly preferred monomers D.1.1 and D.1.2 are both methyl methacrylate.

[0204] The graft copolymer D is prepared by free radical polymerization, for example by emulsion, suspension, solution or bulk polymerization, preferably by emulsion or bulk polymerization, especially by emulsion polymerization.

[0205] Since it is well known that graft monomers are not necessarily completely grafted onto the graft substrate during the grafting reaction, the graft copolymer D according to the present invention is understood to also include products obtained by (co)polymerization of graft monomers in the presence of the graft substrate and products obtained together during post-processing (workup). These products may accordingly also contain free (co)polymers of graft monomers, i.e., (co)polymers that are not chemically bonded to the rubber.

[0206] Silicone-acrylate composite rubber or mixtures of different silicone-acrylate composite rubbers are used as the grafting substrate D.2. These silicone-acrylate composite rubbers are preferably composite rubbers with grafting active sites, containing: D.2.1) 5%-95% by weight, preferably 20%-80% by weight, particularly preferably 25%-50% by weight of silicone rubber, and

[0207] D.2.2) 95% to 5% by weight, preferably 80% to 20% by weight, particularly preferably 75% to 50% by weight of poly(meth)acrylate rubber.

[0208] These two rubber components are interpenetrated in the composite rubber and are therefore essentially inseparable.

[0209] The particularly preferred ratio of silicone rubber and poly(meth)acrylate rubber results in a particularly advantageous combination of good mechanical properties, good surface finish of components, and good resistance to hydrolytic molecular weight degradation and chemical effects.

[0210] Silicone-acrylate composite rubbers are known and described, for example, in US 5,807,914, EP 430134 and US4888388.

[0211] Suitable silicone rubber components D.2.1 for silicone-acrylate composite rubbers are silicone rubbers with grafted active sites, the preparation methods of which are described, for example, in US 2891920, US 3294725, DE-A 3 631 540, EP 249964, EP430134 and US 4888388.

[0212] The silicone rubber according to D.2.1 is preferably made by emulsion polymerization, wherein siloxane monomer units, crosslinking or branching agents and optional grafting agents are used.

[0213] Examples of preferred siloxane monomers for preparing silicone rubber include, for example, dimethylsiloxanes or cyclic organosiloxanes having at least 3 ring members, preferably 3 to 6 ring members, and preferably hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, and octaphenylcyclotetrasiloxane.

[0214] Organosiloxane monomers can be used alone or in the form of a mixture containing two or more monomers.

[0215] The crosslinking agent is preferably a silane-based crosslinking agent having a functionality of 3 or 4, more preferably 4. Preferred examples include: trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, and tetrabutoxysilane. The crosslinking agent can be used alone or in a mixture of two or more. Tetraethoxysilane is particularly preferred.

[0216] Examples of grafting agents include β-methacryloyloxyethyl dimethoxymethylsilane, γ-ethylacryloyloxypropyl methoxydimethylsilane, γ-methacryloyloxypropyl dimethoxymethylsilane, γ-methacryloyloxypropyl trimethoxysilane, γ-methacryloyloxypropyl ethoxydiethylsilane, γ-methacryloyloxypropyl diethoxymethylsilane, δ-methacryloyloxybutyl diethoxymethylsilane, or mixtures thereof.

[0217] Preferably, 0-20% by weight of grafting agent based on the total weight of silicone rubber is used.

[0218] Silicone rubber can be prepared by emulsion polymerization as described, for example, in US 2891920 and US 3294725.

[0219] Suitable poly(meth)acrylate rubber component D.2.2 of silicone-acrylate composite rubber can be made from alkyl methacrylate and / or alkyl acrylate, crosslinking agent and grafting agent.

[0220] Preferred examples of alkyl methacrylates and / or alkyl acrylates include C1- to C8-alkyl esters, such as methyl, ethyl, n-butyl, tert-butyl, n-propyl, n-hexyl, n-octyl, n-dodecyl, and 2-ethylhexyl esters; haloalkyl esters, preferably halo-C1-C8-alkyl esters, such as ethyl chloride acrylate; and mixtures of these monomers. Particularly preferred is n-butyl acrylate.

[0221] Crosslinking agents for poly(meth)acrylate rubber components of silicone-acrylate rubbers include monomers having more than one polymerizable double bond. Preferred examples of crosslinking monomers are esters of unsaturated monocarboxylic acids having 3 to 8 carbon atoms and unsaturated monohydric alcohols having 3 to 12 carbon atoms, or saturated polyols having 2 to 4 OH groups and 2 to 20 carbon atoms, such as ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, and 1,4-butanediol dimethacrylate. The crosslinking agent can be used alone or in a mixture of at least two crosslinking agents.

[0222] Examples of preferred grafting agents include allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, or mixtures thereof. Allyl methacrylate may also be used as a crosslinking agent. Grafting agents may be used alone or in a mixture of at least two grafting agents.

[0223] The amount of crosslinking agent and grafting agent is 0.1% to 20% by weight of the total weight of the poly(meth)acrylate rubber component based on silicone-acrylate rubber.

[0224] The silicone-acrylate composite rubber is prepared by first preparing a silicone rubber of D.2.1 in the form of an aqueous latex. Then, the latex is supplemented with the desired alkyl methacrylates and / or alkyl acrylates, a crosslinking agent, and a grafting agent, and polymerization is carried out.

[0225] This silicone-acrylate composite grafted rubber is prepared by grafting monomer D.1 onto a rubber substrate D.2. This can be done using polymerization methods described, for example, in EP 249964, EP430134 and US 4888388.

[0226] As for silicone-acrylate rubbers, silicone-C1-C8 alkyl acrylate rubbers can be mentioned. Among particles, silicone-butyl acrylate rubber can be mentioned as an example.

[0227] Preferably, the silicone-acrylate rubber-based impact modifier is selected from (meth)acrylate (C1-C8)-alkyl ester grafted silicone-acrylate C1-C8 alkyl ester rubber.

[0228] More preferably, the silicone-acrylate rubber-based impact modifier is methyl methacrylate-grafted silicone-butyl acrylate rubber.

[0229] As an example of commercially available silicone-acrylate rubber-based impact modifiers that can be used in this invention, examples include Metalatn S-2001, Metalatn S-2030, and others from Mitsubishi Rayon Co., Ltd. S2130.

[0230] In a preferred embodiment, methyl methacrylate-grafted silicone-butyl acrylate rubber is used, for example... S2130 is component D.

[0231] Advantageously, the silicone-acrylate rubber-based impact modifier is present in the polycarbonate composition in an amount of 1% to 4.5% by weight, preferably 1% to 3% by weight, relative to the total weight of the polycarbonate composition.

[0232] Component E

[0233] According to the first aspect, the polycarbonate composition according to the invention comprises kaolin as component E.

[0234] Kaolin is a white, burning aluminum silicate with a high melting point and good fire resistance. It mainly consists of kaolinite [Al2O3.2SiO2.2H2O].

[0235] Preferably, the kaolin used according to the invention is untreated kaolin. Untreated kaolin typically has a layered, lamellar structure, partly due to the presence of tetrahedral rings linked by oxygen atoms and shared with other rings in a two-dimensional plane. Cationic layers connect the lamellar structures. These cationic layers connecting the lamellar structures are referred to hereinafter as intermediate layers. The cations are weakly bonded and surrounded by neutral molecules, such as water molecules. The distance between the lamellar layers is referred to as the “d-spacing”. The silica-oxygen ratio in untreated kaolin is typically from about 1:1 to about 2.5:1. Layered kaolin improves the flame-retardant properties of the overall polycarbonate composition. This layered structure also typically corresponds to particle size; particles with a median particle size of about 1.0 to about 1.3 micrometers have a layered structure.

[0236] For the purposes of this invention, preferably, the kaolin used has a median particle size of about 0.01 micrometers to about 2.0 micrometers.

[0237] In some embodiments, the kaolin used has a median particle size of about 0.4 micrometers to about 1.3 micrometers. It has been found that particle sizes near the lower end of this range tend to maintain the ductility of the polycarbonate composition, while particle sizes near the upper end of this range improve the flame retardant properties of the polycarbonate composition better than those at the lower end of the range.

[0238] As a product of kaolin, POLYFIL from KaMin LLC can be mentioned. TM HG90 has a median particle size of 0.4 micrometers.

[0239] Advantageously, kaolin is present in the polycarbonate composition in an amount of 0.5% to 3% by weight, preferably 0.5% to 2% by weight, and more preferably 0.5% to 1.5% by weight relative to the total weight of the polycarbonate composition.

[0240] It has been found that when kaolin is present in a polycarbonate composition in an amount of 0.5% to 1.5% by weight relative to the total weight of the polycarbonate composition, the impact strength is high even at a temperature of -30°C.

[0241] According to some embodiments, the polycarbonate composition according to the invention does not contain any filler other than kaolin.

[0242] Component F

[0243] According to the first aspect, the polycarbonate composition according to the invention comprises at least one anti-dripping agent as component F.

[0244] Preferably, the anti-dripping agent used is selected from fluorinated polyolefins.

[0245] Fluorinated polyolefins are known (see "Vinyl and Related Polymers", Schildknecht, John Wiley & Sons, Inc., New York, 1962, pp. 484-494; "Fluorpolymers", Wall, Wiley-Interscience, John Wiley & Sons, Inc., New York, Vol. 13, 1970, pp. 623-654; "Modern Plastics Encyclopedia", 1970-1971, Vol. 47, No. 10A, October 1970, McGraw-Hill, Inc., New York, pp. 134 and 774; "Modern Plastics Encyclopedia", 1975-1976, October 1975, Vol. 52, No. 10A, McGraw-Hill, Inc., New York, pp. 27, 28, and 472, and US-PS 3). 671 487, 3 723373 and 3 838 092).

[0246] Preferably, the anti-dripping agent is selected from polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene / hexafluoropropylene copolymer and ethylene / tetrafluoroethylene copolymer.

[0247] More preferably, the anti-dripping agent used is polytetrafluoroethylene (PTFE).

[0248] Polytetrafluoroethylene (PTFE) can be produced by known methods, such as by incubating PTFE in an aqueous medium containing a free radical-forming catalyst, such as sodium peroxydisulfate, potassium peroxydisulfate, or ammonium peroxydisulfate, at a concentration of 7 kg / cm³. 2 Up to 71kg / cm 2 The preparation is carried out under pressure and at a temperature of 0°C to 200°C, preferably at a temperature of 20°C to 100°C. For further details, see, for example, U.S. Patent 2,393,967.

[0249] Preferably, the fluorinated polyolefin has a high molecular weight and a glass transition temperature exceeding -30°C, typically exceeding 100°C, preferably 65% ​​to 76% by weight, particularly 70% to 76% by weight (based on 100% by weight of the fluorinated polyolefin), and an average particle size d from 0.05 μm to 1,000 μm, preferably 0.08 to 20 μm. 50 .

[0250] Preferably, the fluorinated polyolefin has a content of 1.2 g / cm³. 3 Up to 2.3 g / cm 3 The density.

[0251] More preferably, the fluorinated polyolefin used according to the present invention has an average particle size of 0.05 μm to 20 μm, preferably 0.08 μm to 10 μm, and a particle size of 1.2 g / cm³. 3 Up to 1.9 g / cm 3 The density.

[0252] Suitable fluorinated polyolefins that can be used in powder form have an average particle size of 100 to 1000 μm and a particle size of 2.0 g / cm³. 3 Up to 2.3 g / cm 3 The density of tetrafluoroethylene polymer (PTFE).

[0253] PTFE can be used alone or as a masterbatch for homopolymers or copolymers with styrene or methyl methacrylate.

[0254] As an example of a product containing polytetrafluoroethylene, DuPont can be mentioned under the trade name... Those that were sold.

[0255] Alternatively, masterbatches of polytetrafluoroethylene and styrene-acrylonitrile (SAN) in a 1:1 weight ratio can be used, such as ADS 5000 available from Chemical Innovation Co., Ltd. Thailand and POLYB FS-200 available from Han Nanotech Co., Ltd.

[0256] Advantageously, the anti-dripping agent is present in the polycarbonate composition in an amount of 0.2% to 1% by weight, preferably 0.3% to 1% by weight, and preferably 0.5% to 1% by weight relative to the total weight of the polycarbonate composition.

[0257] Component G

[0258] According to a first aspect, the polycarbonate composition according to the invention comprises at least one ultraviolet absorber as component F.

[0259] Ultraviolet absorbers are commonly used in the field of polycarbonate materials.

[0260] Suitable UV absorbers are described, for example, in EP 1 308 084 A1, DE 102007011069 A1 and DE10311063 A1.

[0261] Exemplary ultraviolet absorbers include hydroxybenzophenone; hydroxybenzotriazole; hydroxybenzotriazine; cyanoacrylate; oxaloyl aniline; benzoxazinone; etc., or combinations thereof.

[0262] A particularly suitable UV absorber is hydroxybenzotriazole, such as 2-(3',5'-bis(1,1-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole. 234, BASF SE, Ludwigshafen), 2-(2'-hydroxy-5'-(tert-octyl)phenyl)benzotriazole ( 329, BASF SE, Ludwigshafen), 2-(2'-hydroxy-3'-(2-butyl)-5'-(tert-butyl)phenyl)benzotriazole ( 350, BASF SE, Ludwigshafen), bis(3-(2H-benzotriazolyl)-2-hydroxy-5-tert-octyl)methane ( 360, BASF SE, Ludwigshafen), (2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyloxy)phenol 1577, BASF SE, Ludwigshafen) and 2,4-dihydroxybenzophenone ( 22, BASF SE, Ludwigshafen) and 2-hydroxy-4-(octyloxy)benzophenone ( 81, BASF SE, Ludwigshafen), 2-acrylic acid, 2-cyano-3,3-biphenyl, 2,2-bis[[(2-cyano-1-oxo-3,3-diphenyl-2-propenyl)oxy]methyl]-1,3-propanediol ester (9CI) 3030, BASF SE, Ludwigshafen), hydroxybenzotriazine, such as 2-[2-hydroxy-4-(2-ethylhexyl)oxy]phenyl-4,6-di(4-phenyl)phenyl-1,3,5-triazine ( 1600, BASF SE, Ludwigshafen) or tetraethyl 2,2'-(1,4-phenylene dimethylidene) dimethyl bis(dimethyl)malonate ( B-Cap, Clariant AG). Mixtures of these UV absorbers may also be used.

[0263] Advantageously, the ultraviolet absorber is present in the polycarbonate composition in an amount of 0.2% to 0.8% by weight, preferably 0.25% to 0.6% by weight, and more preferably 0.3% to 0.5% by weight relative to the total weight of the polycarbonate composition.

[0264] Additional additives

[0265] In addition to component AG mentioned above, the polycarbonate composition according to the present invention may optionally contain the balance of one or more conventional additives used in polymer compositions, such as lubricants and release agents (e.g., pentaerythritol tetrastearate), antioxidants, antistatic agents (including inorganic antistatic agents such as conductive carbon black, carbon fibers, carbon nanotubes and organic antistatic agents such as polyalkylene ethers, alkyl sulfonates or polyamide-containing polymers), dyes, pigments, etc.

[0266] As antioxidants, sterically hindered phenols and phosphites, or mixtures thereof, are preferred, for example... B900 (Ciba Specialty Chemicals).

[0267] Those skilled in the art can select the type and amount of additional additives so as not to significantly or adversely affect the desired properties of the polycarbonate composition according to the invention.

[0268] In some embodiments, the polycarbonate composition according to the invention comprises component AG, a release agent, and an antioxidant.

[0269] In some embodiments, the polycarbonate composition according to the invention comprises the following components, relative to the total weight of the composition:

[0270] A) 35-66% by weight of at least one aromatic polycarbonate having a weight-average molecular weight of 23,000 to 28,000 g / mol.

[0271] B) 25-56% by weight of at least one polysiloxane-polycarbonate copolymer,

[0272] C) 1.5-4.5% by weight of at least one cyclophosphinitrogen,

[0273] D) 1-4% by weight of (meth)acrylate (C1-C8)-alkyl ester grafted silicone-acrylate C1-C8 alkyl ester rubber

[0274] E) 0.5-1.5% by weight of kaolin,

[0275] F) 0.5-1% by weight of at least one anti-dripping agent, and

[0276] G) 0.25-0.6% by weight of at least one ultraviolet absorber.

[0277] Preparation of polycarbonate compositions

[0278] The polycarbonate composition according to the invention can be, for example, in pellet form, and can be prepared by various methods involving close mixing of the desired materials in the composition.

[0279] For example, the materials required in the composition are first blended in a high-speed mixer. Other low-shear methods, including but not limited to manual mixing, can also achieve this blending. The blend is then fed via a hopper into the throat of a twin-screw extruder. Alternatively, at least one component can be incorporated into the composition by feeding it directly into the extruder at the throat and / or downstream via a side-filler. Additives can also be compounded with the desired polymer resin to form a masterbatch and fed into the extruder. The extruder is typically operated at a temperature above that necessary to cause the composition to flow. The extrudate is immediately quenched in a water bath and granulated. As described, the pellets can be 1 / 4 inch long or smaller. Such pellets can be used for subsequent molding, shaping, or forming.

[0280] Melt blending is the preferred method due to the availability of melt blending equipment in commercial polymer processing facilities.

[0281] Exemplary examples of equipment used in such melt processing methods include co-rotating and counter-rotating extruders, single-screw extruders, co-kneaders, and various other types of extrusion equipment.

[0282] The melt temperature during processing should preferably be minimized to avoid excessive degradation of the polymer. It is generally desirable to maintain the melt temperature in the molten resin composition between 200°C and 330°C, although higher temperatures may be used as long as the residence time of the resin in the processing equipment remains short.

[0283] In some cases, the molten composition is discharged from the processing equipment, such as an extruder, through a small outlet orifice in the die. The resulting filament is cooled by passing the molten resin through a water bath. The cooled filament can be chopped into small pellets for packaging and further processing.

[0284] Molded products

[0285] The thermoplastic resin composition according to the invention can be used, for example, to produce various types of molded articles.

[0286] According to a second aspect, the present invention provides molded articles made from polycarbonate compositions according to a first aspect of the present invention.

[0287] Examples of molded articles include, for example, films; profiles; various housing components, such as those for household appliances like TVs, juicers, coffee makers, and blenders, or for office equipment like monitors, adapters, flat panel displays, laptops, printers, and copiers; sheets; tubing; electrical conduits; windows, doors, and other profiles for the construction industry (indoor and outdoor applications); electrical and electronic components such as switches, chargers, plugs, and sockets; and body parts or interior trim for commercial vehicles, especially for the motor vehicle industry.

[0288] Specifically, the molded article can be any of the following: interiors of rail vehicles, ships, airplanes, buses and other motor vehicles; housings of electrical equipment containing small transformers; housings of information processing and transmission equipment; housings and covers of medical equipment; housings of safety equipment; molded parts for sanitary and bathroom accessories; vent covers and grilles; and housings of gardening tools.

[0289] Preparation of molded products

[0290] The polycarbonate composition according to the invention can be processed into molded articles by various means of forming molded articles, such as injection molding, extrusion molding, blow molding or thermoforming.

[0291] Therefore, according to a third aspect, the present invention provides a method for preparing a molded article according to a second aspect of the present invention, comprising injection molding, extrusion molding, blow molding or thermoforming a polycarbonate composition according to a first aspect of the present invention.

[0292] The following examples are provided to explain the present invention in more detail. Example

[0293] Materials used

[0294] Component A

[0295] A1: A bisphenol A-based linear polycarbonate resin with a weight-average molecular weight (Mw) of approximately 26,000 g / mol, which can be used as... 2600 was obtained from Covestro, Co., Ltd.

[0296] A2: A bisphenol A-based linear polycarbonate with a weight-average molecular weight (Mw) of approximately 24,000 g / mol, which can be used as... 2400 is from Covestro, Co., Ltd.

[0297] Component B

[0298] A polysiloxane-polycarbonate copolymer (SicoPC) with approximately 6.5% PDMS content can be used as LG PC 8000-05 was obtained from LG Chem Ltd.

[0299] Component C

[0300] The phenoxyphosphazene of formula (VI), wherein the content of oligomers with k=1 is 99.9 mol% and the content of oligomers with k≥2 is 0.1 mol%, can be obtained as HPCTP from Weihai Jinwei Chem Induxtry Company.

[0301]

[0302] Component D

[0303] D1: A methyl methacrylate-grafted silicone-butyl acrylate rubber with a core-shell structure, which can be used as... S2130 was obtained from Mitsubishi Rayon Co., Ltd.

[0304] D2: Methyl methacrylate-butadiene-styrene (MBS) with a core-shell structure, available as Kane AceM732 from Japan Kaneka Chemical Co., Ltd.

[0305] Component E

[0306] E1: Kaolin, can be used as POLYFIL TM HG90 was acquired from KaMin LLC.

[0307] E2: Wollastonite, available as NYGLOS 4W from NYCO Minerals, Inc.

[0308] Component F

[0309] A 1:1 weight ratio of polytetrafluoroethylene and styrene-acrylonitrile (SAN) masterbatch is available as ADS 5000 from IRPC Public Company Limited.

[0310] Component G 2,2'-Methylene-bis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl))phenol, available as UV360 from Rianlon Corporation.

[0311] Component H

[0312] H1: Pentaerythritol tetrastearate (PETS), mold release agent, available from FACIAsia Pacific Pte Ltd. (Singapore).

[0313] H2: Antioxidant, 80% 168 (tris(2,4-di-tert-butylphenyl) phosphite) and 20% 1076 (a mixture of 2,6-di-tert-butyl-4-(octadecyloxycarbonylethyl)phenol, which can be used as...) B900 is from BASF (China) Company Limited.

[0314] Test methods

[0315] The physical properties of the compositions obtained in the following test examples are shown.

[0316] The notched impact strength was measured at 5.5 J according to ISO 180 / 1A:2000 on an 80×10×3 mm notched single-gated specimen conditioned at the test temperature for 2 hours.

[0317] Flame retardancy was measured on specimens measuring 127 × 12.7 × 2.0 mm before and after immersion in water at 82°C for 7 days and conditioning at 23°C for 2 days, according to UL94 5VB.

[0318] The Vicat softening temperature is determined according to DIN 53 460 (ISO 306:2013) on bars with dimensions of 80×10×4mm at a heating rate of 120℃ / hr.

[0319] Hydrolytic stability was assessed based on the change in cantilever beam notched impact strength measured in 80 mm x 10 mm x 3 mm bars before and after immersion in water at 82 °C for 7 days, according to ISO 180 / IA:2000.

[0320] Comparative Examples 1-8 (CE1-CE8) and Examples 1-7 of the present invention (IE1-IE7)

[0321] The materials listed in Tables 1 and 2 were compounded and granulated on a twin-screw extruder (ZSK-25) (Werner and Pfleider) at a rotational speed of 225 rpm, a throughput of 20 kg / h, and a machine temperature of 260–290 °C.

[0322] The granules were processed into corresponding test specimens on an injection molding machine at a melting temperature of 260-300℃ and a mold temperature of 80℃.

[0323] The physical properties of the obtained compositions were tested, and the results are summarized in Tables 1 and 2.

[0324] Table 1

[0325]

[0326] *:P represents partial fracture, implying ductility.

[0327] Comparative Examples 1-4 (CE1-CE4) show that compositions without kaolin cannot achieve a UL level of 5VB at a thickness of 2.0 mm after immersion in water at 82°C for 7 days.

[0328] Comparative Example 5 (CE5) shows that the composition containing MBS instead of silicone-acrylate rubber-based impact modifier cannot achieve a UL level of 5VB at a thickness of 2.0 mm after immersion in water at 82°C for 7 days.

[0329]

[0330]

[0331] *:P represents partial fracture, implying ductility.

[0332] **:C represents complete fracture, which means brittleness.

[0333] As demonstrated in Examples 1-7 (IE1-IE7) of this invention, the compositions according to the invention have a good combination of low-temperature impact resistance, flame retardancy, hydrolytic stability, UV resistance and heat resistance.

[0334] Specifically, the compositions in Examples 1-7 (IE1-IE7) of the present invention have a Vicat softening temperature of 128°C or higher and a strength of 48 KJ / m³ at -30°C. 2 Or higher cantilever beam notched impact strength, and can achieve a UL level of 5VB at a thickness of 2.0 mm after immersion in water at 82°C for 7 days. It can maintain the cantilever beam notched impact strength at 23°C after immersion in water at 82°C for 7 days.

[0335] Comparative Example 6 (CE6) shows that when the kaolin content is 5% by weight relative to the total weight of the composition, the composition has a high cantilever beam notched impact strength at -30°C.

[0336] Comparative Example 7 (CE7) shows that when the kaolin content is 7% by weight relative to the total weight of the composition, the composition has low low-temperature (-20°C and -30°C) impact strength and impact strength after immersion in water for 7 days.

[0337] Comparative Example 8 (CE8) shows that the composition containing wollastonite instead of kaolinite has a low cantilever beam notched impact strength at -30°C.

Claims

1. A flame-retardant polycarbonate composition comprising the following components, relative to the total weight of the composition: A) 30-70% by weight of at least one aromatic polycarbonate, B) 20-60% by weight of at least one polysiloxane-polycarbonate copolymer, C) 0.5-5% by weight of at least one cyclophosphinitrogen, D) 1-5% by weight of at least one silicone-acrylate rubber-based impact modifier, E) 0.3-3% by weight of kaolin, F) 0.1-1% by weight of at least one anti-dripping agent, and G) 0.1-1% by weight of at least one ultraviolet absorber.

2. The composition according to claim 1, wherein the polysiloxane-polycarbonate copolymer comprises siloxane blocks derived from structures (XIII) and / or (XIV): in R1 can independently represent hydrogen, Cl, Br, or C1-C4-alkyl. R2 independently represents aryl or C1-C. 13 alkyl, X represents a single bond, -O-, -SO-, -CO-, -S-, -SO2-, C1-C6-alkylene, C2-C5-alkylidene, C5-C 12 -C6-C cycloalkane groups or optionally fused with an aromatic ring containing other heteroatoms 12 -Aspartic acid n represents 10 to 400, determined by 1H-NMR spectroscopy in each case, and m represents 1 to 10, and is determined by 1H-NMR spectroscopy in each case.

3. The composition according to claim 2, wherein R2 independently represents C1-C4-alkyl groups.

4. The composition according to claim 2, wherein X represents a single bond, an isopropylidene group, or a C5-C bond. 12 -Cycloalkylidene group.

5. The composition according to claim 2, wherein n represents an average number from 10 to 50, determined by 1H-NMR spectroscopy in each case.

6. The composition according to claim 2, wherein m represents an average number of 1.5 to 5, determined by 1H NMR spectroscopy in each case.

7. The composition of claim 1, wherein the polysiloxane-polycarbonate copolymer comprises 2% to 20% by weight of siloxane blocks relative to the weight of the polysiloxane-polycarbonate copolymer.

8. The composition according to claim 1, wherein the cyclophosphonitrile is selected from cyclophosphonitriles of formula (V): in k is an integer from 1 to 10. The trimer content, i.e., k=1, is 60 to 100 mol% based on component C. And among them R is the same or different in each case and represents -amine group, -In each case, the C1-C8-alkyl group may be optionally halogenated. -C1-C8-alkoxy, -In each case, the C5-C6-cycloalkyl group may be optionally alkylated and / or substituted. - In each case, the C6-C atoms are optionally substituted with alkyl and / or halogen and / or hydroxyl groups. 20 -Aryloxy, - C7-C, optionally substituted with alkyl and / or halogen in each case 12 -Aryl group, - halogen group, or -OH group.

9. The composition according to claim 8, wherein k is an integer from 1 to 5.

10. The composition according to claim 8, wherein R is the same or different in each case and represents -amino group, -In each case, the methyl, ethyl, propyl, or butyl groups are optionally fluorohalogenated. -Methoxy, ethoxy, propoxy, or butoxy -Optionally C1-C4-alkyl and / or C5-C6-cycloalkyl substituted with chlorine and / or bromine in each case, -In each case, optionally substituted with C1-C4-alkyl and / or chlorine or bromine and / or hydroxyl groups, phenoxy or naphthoxy groups. - Phenyl-C1-C4-alkyl optionally substituted with C1-C4-alkyl and / or chlorine and / or bromine in each case, -Chlorine or fluorine, or -OH group.

11. The composition according to claim 8, wherein the cyclophosphonitrile is selected from propoxyphosphonitrile, phenoxyphosphonitrile, methylphenoxyphosphonitrile, aminophosphonitrile and fluoroalkylphosphonitrile.

12. The composition of claim 1, wherein the silicone-acrylate rubber-based impact modifier comprises D.1 on D.

2. D.1) 5% to 95% by weight of at least one vinyl monomer, D.2) 95% to 5% by weight of one or more silicone-acrylate rubbers as the grafting substrate. The weight percentage is calculated based on the weight of the impact modifier.

13. The composition of claim 1, wherein the silicone-acrylate rubber-based impact modifier comprises D.1 on D.

2. D.1) 8% to 90% by weight of at least one vinyl monomer, D.2) 92% to 10% by weight of one or more silicone-acrylate rubbers as the grafting substrate. The weight percentage is calculated based on the weight of the impact modifier.

14. The composition of claim 1, wherein the silicone-acrylate rubber-based impact modifier comprises D.1 on D.

2. D.1) 20% to 85% by weight of at least one vinyl monomer, D.2) 80% to 15% by weight of one or more silicone-acrylate rubbers as the grafting substrate. The weight percentage is calculated based on the weight of the impact modifier.

15. The composition according to claim 12, wherein The vinyl monomer D.1 is selected from vinyl aromatics and / or nucleus-substituted vinyl aromatics, vinyl cyanides, C1-C8 alkyl esters of (meth)acrylates, and unsaturated carboxylic anhydrides and imides; and / or The silicone-acrylate rubber D.2 is selected from composite rubbers having grafted active sites, containing 5% to 95% by weight of silicone rubber and 95% to 5% by weight of poly(meth)acrylate alkyl rubber relative to the total weight of the composite rubber.

16. The composition according to claim 12, wherein Vinyl monomer D.1 is selected from styrene, α-methylstyrene, p-methylstyrene, acrylonitrile, methacrylonitrile, methyl methacrylate, ethyl methacrylate, n-butyl acrylate, tert-butyl acrylate, maleic anhydride, and N-phenyl-maleimide; and / or Silicone-acrylate rubber D.2 is selected from composite rubbers having grafted active sites, which contain 20% to 80% by weight of silicone rubber and 80% to 20% by weight of poly(meth)acrylate rubber relative to the total weight of the composite rubber.

17. The composition according to claim 12, wherein The vinyl monomer comprises C1-C8 alkyl esters of (meth)acrylate or combinations thereof with styrene, α-methylstyrene or p-methylstyrene; and / or The silicone-acrylate rubber D.2 is selected from composite rubbers having grafted active sites, and contains 25% to 50% by weight of silicone rubber and 75% to 50% by weight of poly(meth)acrylate alkyl rubber relative to the total weight of the composite rubber.

18. The composition according to claim 1, wherein the silicone-acrylate rubber-based impact modifier is methyl methacrylate-grafted silicone-butyl acrylate rubber.

19. The composition according to claim 1, comprising the following components relative to the total weight of the composition: A) 35-66% by weight of at least one aromatic polycarbonate having a weight-average molecular weight of 23,000 to 28,000 g / mol. B) 25-56% by weight of at least one polysiloxane-polycarbonate copolymer, C) 1.5-4.5% by weight of at least one cyclophosphinitrogen, D) 1-4% by weight of (meth)acrylate C1-C8-alkyl ester grafted silicone-acrylate C1-C8 alkyl ester rubber E) 0.5-1.5% by weight of kaolin, F) 0.5-1% by weight of at least one anti-dripping agent, and G) 0.25-0.6% by weight of at least one ultraviolet absorber.

20. The composition according to claim 1, wherein the anti-dripping agent is selected from fluorinated polyolefins.

21. The composition according to claim 1, wherein the anti-dripping agent is selected from polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene / hexafluoropropylene copolymer and ethylene / tetrafluoroethylene copolymer.

22. The composition of claim 1, further comprising one or more additional additives selected from lubricants and release agents, antioxidants, antistatic agents, dyes and pigments.

23. A molded article made of the composition according to any one of claims 1 to 22.

24. A method for preparing a molded article according to claim 23, comprising injection molding, extrusion molding, blow molding or thermoforming of a polycarbonate composition according to any one of claims 1 to 22.

Images