TW201925341A - Polycarbonate composition - Google Patents

Abstract

The present invention relates to a polycarbonate composition and the process for the production thereof and molded articles. The polycarbonate composition provided in the present invention comprises (A) 8-70 wt.% of a polycarbonate component, (B) 25-90 wt.% of a polysiloxane-polycarbonate copolymer component, (C) a flame retardant component, which comprises 0.5-6 wt.% of a cyclic phosphazene of formula (X) and (D) an impact modifier component, which comprises 0.5-6 wt.% of methyl methacrylate-butadiene-styrene, with the above weight percentages based on said polycarbonate composition as 100 wt.%. The polycarbonate composition provided in the present invention has a high flame-retardant level, an excellent low-temperature impact-resistant property and good heat resistance, and is suitable for the use requirement of casings for electrical devices which have relatively high flame-retardant levels (such as UL94 5VB) and require an excellent low-temperature impact-resistant property.

Description

 Polycarbonate composition  

The present invention pertains to the field of polycarbonates, and more particularly to polycarbonate compositions having improved impact resistance, methods for their manufacture, and uses thereof.

In general, the electronics housing should provide external barrier protection and meet the requirements for heat resistance and flame retardancy, as the electronics themselves generate a lot of heat during operation or in high temperature environments. Polycarbonate materials have good toughness and high heat resistance and good flame retardancy at room temperature. It can therefore be used to make a housing for many electronic devices, such as power adapters, chargers, and the like. Polycarbonate materials used in general electronic device housings typically must have flame retardancy (FR) in accordance with UL94 V0 performance requirements.

In order to meet higher application requirements, there is still a need to improve the low temperature impact resistance of polycarbonate materials, particularly notched impact strength. The addition of an impact modifier to the polycarbonate material helps to improve low temperature impact resistance, but at the same time sacrifices some flame retardancy. The addition of a flame retardant provides better flame retardancy while reducing low temperature impact resistance. Therefore, how to weigh the flame retardancy and impact resistance of polycarbonate materials is a major challenge in industrial applications.

In order to improve low temperature impact resistance while maintaining good flame retardancy, the prior art solution is to add a polyoxyalkylene-polycarbonate copolymer to a polycarbonate material. The polyoxyalkylene-polycarbonate copolymer has good low-temperature impact resistance, and its addition does not affect the flame retardancy of the polycarbonate composition.

WO 2015/022676 discloses the use of a polycarbonate-polyoxyalkylene copolymer (an opaque resin having a siloxane content of 20%) when a flame retardant polycarbonate composition is filled with an impact-resistant modifier-modified mineral . The addition of a mineral filler and a phosphate flame retardant can improve the flame retardancy, but the impact resistance of the polycarbonate composition is deteriorated, and the addition of the polycarbonate-polyoxyalkylene copolymer can improve the impact resistance while Does not reduce flame retardancy. US 2009/0088514 discloses transparent polyoxyalkylene-polycarbonate copolymers for use in PC/ABS/talc powder mixtures and diphenyl phosphate (BDP) as flame retardants to provide better impact resistance and resistance to articles. Flammability and surface quality. US 8,841,367 B2 discloses that the incorporation of polyoxyalkylene-polycarbonate copolymers with branched polycarbonates in glass fiber reinforced flame retardant polycarbonates provides better impact resistance and flame retardancy. US 8,927,661 B2 discloses that the synergistic effect of a polyoxyalkylene-polycarbonate copolymer and a phosphazene can be achieved by combining a branched polycarbonate during the growth of a transparent flame-retardant polycarbonate material. US 2016/194495 A1 discloses polycarbonate compositions comprising polycarbonate, an impact modifier, phosphazene and a small amount of polyoxyalkylene-polycarbonate. This document does not provide any low temperature impact strength data. US 2014/107264 A1 is directed to compositions comprising polycarbonate, polycarbonate-polyoxyalkylene and phosphazene. US 2017/247539 A1 discloses compositions comprising polycarbonate, polycarbonate-polyoxyalkylene oxide, impact modifiers and linear phosphazenes.

While the prior art solutions described above provide polycarbonate materials that are quite flame retardant, it is difficult to meet the requirements of the higher flame retardant class UL94 5VB while having low temperature impact resistance at temperatures as low as -40 °C. Since some electronic devices or components and outer casings of outdoor electronic devices (such as network devices, projectors, and electric power packs for electric vehicles) release a lot of heat during operation, polycarbonate materials should meet higher flame retardancy levels ( Such as UL94 5VB) and good low temperature impact resistance.

Therefore, this industry needs to develop a new polycarbonate composition that combines a high flame retardancy rating with excellent low temperature impact resistance.

It is an object of the present invention to provide a polycarbonate composition comprising: A) from 8 to 70% by weight of a polycarbonate component; B) from 25 to 90% by weight of a polyoxyalkylene-polycarbonate copolymer component; C) a flame retardant component comprising 0.5 to 6% by weight of a cyclic phosphazene of formula (X) Wherein k represents an integer of 1 or 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, and the content of the terpolymer (k = 1) is 60 to 98 based on the component C). Ear %, wherein R is the same or different in each case, and represents an amine group; C ₁ - to C ₈ -alkyl, preferably methyl, ethyl, propyl or butyl, each selectively halogenated, Halogenated by fluorine; C ₁ - to C ₈ -alkoxy, preferably methoxy, ethoxy, propoxy or butoxy; C ₅ - to C ₆ -cycloalkyl, each selectively Alky (preferably C ₁ - to C ₄ -alkyl) and/or halogen (preferably chlorine and/or bromine) substituted; C ₆ - to C ₂₀ -aryloxy, preferably phenoxy, Naphthyloxy, each optionally substituted by an alkyl group (preferably C ₁ - to C ₄ -alkyl) and/or halogen (preferably chlorine, bromine) and/or hydroxy; C ₇ - to C ₁₂ -aryl Alkyl groups, preferably phenyl-C ₁ -C ₄ -alkyl groups, each optionally being alkyl (preferably C ₁ - to C ₄ -alkyl) and/or halogen (preferably chlorine and/or a bromine) group; or a halogen group, preferably chlorine; or an OH group; and D) an impact modifier component comprising 0.5 to 6% by weight of methyl methacrylate-butadiene-styrene, The percentage by weight of the polycarbonate composition is 100% by weight.

Another object of the present invention is to provide a process for the preparation of a polycarbonate composition comprising the steps of mixing components for preparing the polycarbonate composition, the components comprising: A) from 8 to 70% by weight of polycarbonate a component, B) 25 to 90% by weight of a polyoxyalkylene-polycarbonate copolymer component, C) a flame retardant component comprising 0.5 to 6% by weight of a cyclic phosphazene of the formula (X) Wherein k represents an integer of 1 or 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, and the terpolymer content (k = 1) is 60-98 by weight of component C) Ear %, wherein R is the same or different in each case, and represents an amine group; C ₁ - to C ₈ -alkyl, preferably methyl, ethyl, propyl or butyl, each selectively halogenated, Halogenated by fluorine; C ₁ - to C ₈ -alkoxy, preferably methoxy, ethoxy, propoxy or butoxy; C ₅ - to C ₆ -cycloalkyl, each selectively Alky (preferably C ₁ - to C ₄ -alkyl) and/or halogen (preferably chlorine and/or bromine) substituted; C ₆ - to C ₂₀ -aryloxy, preferably phenoxy, Naphthyloxy, each optionally substituted by an alkyl group (preferably C ₁ - to C ₄ -alkyl) and/or halogen (preferably chlorine, bromine) and/or hydroxy; C ₇ - to C ₁₂ -aryl Alkyl groups, preferably phenyl-C ₁ -C ₄ -alkyl groups, each optionally being alkyl (preferably C ₁ - to C ₄ -alkyl) and/or halogen (preferably chlorine and/or a bromine) group; or a halogen group, preferably a chlorine; or an OH group; and D) an impact modifier component comprising 0.5 to 6% by weight of methyl methacrylate-butadiene-styrene, Take The weight percent of the polycarbonate composition is 100% by weight.

A further object of the invention is a molded article comprising the polycarbonate composition provided by the present invention.

The polycarbonate composition and the molded article provided according to the present invention have high flame retardant grade, excellent low temperature impact resistance and good heat resistance, and are suitable for use in electronic device casings, and have high flame retardant grade (such as UL94 5VB). And it requires excellent low temperature impact resistance.

The description of the present invention is intended to be illustrative only and not limiting. Unless otherwise stated or indicated otherwise, all numbers expressing quantities, percentages, and the like, are to be understood as the term "about" in all instances.

In the present invention, the inventive composition using a polycarbonate component, a polyoxyalkylene-polycarbonate copolymer component, a methyl methacrylate-butadiene-styrene component and a phosphazene compound can achieve polymerization. The carbonate composition has high flame retardancy and high impact resistance. The polycarbonate composition provided by the invention has a flame retardant rating of UL94 5VB (test conditions: 1.5 mm, 2 days, 23 ° C) and flame retardancy V0 (test conditions: 1.0 mm, 2 days, 23 °C), while meeting the low temperature impact strength requirements at temperatures as low as -40 ° C (Izod test conditions: -40 ° C, 3 mm, 5.5 joules).

The present invention provides a polycarbonate composition, a method for producing the same, and a molded article. The polycarbonate composition has good low temperature impact resistance (e.g., notched impact strength at temperatures as low as -20 ° C and -40 ° C) while achieving a higher flame retardant rating (e.g., UL 94 5 VB).

The polycarbonate composition provided according to the present invention comprises: A) from 8 to 70% by weight of the polycarbonate component; B) from 25 to 90% by weight of the polyoxyalkylene-polycarbonate copolymer component; a fuel component comprising 0.5 to 6% by weight of a cyclic phosphazene of formula (X) Wherein k represents an integer of 1 or 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, and the terpolymer content (k = 1) is 60-98 by weight of component C) Ear %, wherein R is the same or different in each case, and represents an amine group; C ₁ - to C ₈ -alkyl, preferably methyl, ethyl, propyl or butyl, each selectively halogenated, Halogenated by fluorine; C ₁ - to C ₈ -alkoxy, preferably methoxy, ethoxy, propoxy or butoxy; C ₅ - to C ₆ -cycloalkyl, each selectively Alky (preferably C ₁ - to C ₄ -alkyl) and/or halogen (preferably chlorine and/or bromine) substituted; C ₆ - to C ₂₀ -aryloxy, preferably phenoxy, Naphthyloxy, each optionally substituted by an alkyl group (preferably C ₁ - to C ₄ -alkyl) and/or halogen (preferably chlorine, bromine) and/or hydroxy; C ₇ - to C ₁₂ -aryl Alkyl groups, preferably phenyl-C ₁ -C ₄ -alkyl groups, each optionally being alkyl (preferably C ₁ - to C ₄ -alkyl) and/or halogen (preferably chlorine and/or a bromine) group; or a halogen group, preferably a chlorine; or an OH group; and D) an impact modifier component comprising 0.5 to 6% by weight of methyl methacrylate-butadiene-styrene, Take The weight percent of the polycarbonate composition is 100% by weight.

Component A: Polycarbonate component

Component A is a polycarbonate component. The content of the polycarbonate component is from 8 to 70% by weight, preferably from 10 to 65% by weight, more preferably from 10 to 60% by weight, based on 100% by weight of the polycarbonate composition.

Suitable polycarbonates include aromatic polycarbonates and/or aromatic polyester carbonates prepared according to known literature or which 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 2 232 877, DE-A 2 703 376, DE-A 2 714 544, DE-A 3 000 610, DE-A 3 832 396; in the preparation of aromatic polyester carbonates, see, for example, DE-A 3 007 934).

The preparation of the aromatic polycarbonate can be carried out, for example, according to a phase interface method, optionally using a chain terminator such as a monophenol, and optionally using a branching agent having a functionality of three or more, such as trisphenol or tetraphenol, The phenol is reacted with a carbonic acid halide (preferably phosgene) and/or with an aromatic dicarboxylic acid halide (preferably a phthalic acid dihalide). It can also be prepared by a melt polymerization method by reacting a diphenol with, for example, diphenyl carbonate.

The diphenol used for the preparation of the aromatic polycarbonate and/or the aromatic polyester carbonate is preferably those having the formula (1) Wherein A is a single bond, C ₁ - to C ₅ -alkylene, C ₂ - to C ₅ -alkylidene, C ₅ - to C ₆ -cycloalkylidene, -O-, -SO-, -CO -, -S-, -SO ₂ -, C ₆ - to C ₁₂ - extended aryl, optionally fused to other aromatic rings containing a hetero atom, or a group of formula (2) or (3),

B is, in each case, a C ₁ - to C ₁₂ -alkyl group, preferably a methyl group, a halogen, preferably chlorine and/or bromine, each of which is independently 0, 1 or 2, p is 1 or 0, and R ⁵ and R ⁶ may be selected individually for each X ¹ and each independently is hydrogen or C ₁ - to C ₆ -alkyl, preferably hydrogen, methyl or ethyl, X ¹ -based carbon, and m-based 4 to 7 An integer of 4 or 5, provided that at least one atom, X ¹ , R ⁵ and R ^{6 are} simultaneously an alkyl group.

Preferred diphenols are hydroquinone, resorcinol, dihydroxydiphenol, bis(hydroxyphenyl)-C ₁ -C ₅ -alkane, bis(hydroxyphenyl)-C ₁ -C ₅ -cycloalkane , bis(hydroxyphenyl)ether, bis(hydroxyphenyl)hydrazine, bis(hydroxyphenyl)ketone, bis(hydroxyphenyl)anthracene, and α,α'-bis(hydroxyphenyl)diisopropylbenzene, And brominated and/or chlorinated derivatives thereof.

Tetradiol is 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'-di Hydroxydiphenyl hydrazine, and its di- and tetra-brominated 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 B) is especially preferred.

Diphenols can be used singly or in combination. Diphenols are known in the literature or can be obtained according to methods known in the literature.

Chain terminators suitable for the preparation of thermoplastic, aromatic polycarbonates are, for example, phenol, p-chlorophenol, p-tertiary butyl phenol or 2,4,6-tribromophenol, and also long-chain alkyl phenols, such as 4-[ 2-(2,4,4-trimethylpentyl)]phenol, 4-(1,3-tetramethylbutyl)phenol according to DE-A 2 842 005, or a total of 8 in the alkyl substituent a monoalkylphenol or a dialkylphenol of -20 carbon atoms, such as 3,5-di-tributylphenol, p-octylphenol, p-trioctylphenol, p-dodecylphenol, 2-( 3,5-Dimethylheptyl)phenol and 4-(3,5-dimethylheptyl)phenol. The amount of the chain terminator is usually from 0.5 mol% to 10 mol% based on the total of the diphenol moie in each case.

The average molecular weight (weight average M, measured by GPC (gel permeation chromatography) and polycarbonate standard) of the thermoplastic aromatic polycarbonate is from 15,000 to 80,000 g/mole, preferably from 19,000 to 32,000 g/mole. More preferably 22,000 to 30,000 g/mole.

The thermoplastic aromatic polycarbonates may be branched in a known manner, preferably 0.05 to 2.0 mole% incorporated (by the sum of the diphenols used) and tri- or more functionality of three compounds, such as phenols having three or more Base. It is preferred to use a linear polycarbonate, more preferably a bisphenol A-based polycarbonate.

Both homopolycarbonates and copolycarbonates are suitable. In the preparation of the copolycarbonate suitable for the component A of the invention, it is also possible to use from 1 to 25% by weight, preferably from 2.5 to 25% by weight, of the polydiorgano group having a hydroxyaryloxy end group, based on the total amount of the diphenol used. Oxane. It is known (US 3,419,634) and can be prepared according to methods known in the literature. Also suitable are copolycarbonates containing polydiorganotoxiranes; preparations of copolycarbonates containing polydiorganotoxiranes are described, for example, in DE-A 3 334 782.

Aromatic dicarboxylic acid dihalides for the preparation of aromatic polyester carbonates is preferably isophthalic acid, terephthalic acid, diphenyl ether 4,4'-dicarboxylic acid and naphthalene-2,6 two acyl dicarboxylic acid dichloride.

A mixture of isophthalic acid and dioxonium diphthalate is preferred from 1:20 to 20:1. In the preparation of the polyester carbonate, a carbonate halide is additionally used as the difunctional acid derivative, preferably phosgene.

In addition to the aforementioned monophenols, chain terminators suitable for the preparation of aromatic polyester carbonates are also chlorocarbonates and aromatic monocarboxyfluorenes which are optionally substituted by C ₁ -C ₂₂ -alkyl or halogen atoms. And aliphatic C ₂ -C ₂₂ -monocarboxylic acid chloride.

In the case of the phenolic chain terminator, in the case of the diphenol morol, and in the case of the monocarboxylic hydrazine chain terminator, the chain termination dose is 0.1 to 10 in each case in terms of dicarboxy hydrazine dichloromole. ear%.

One or more aromatic hydroxycarboxylic acids are additionally useful in the preparation of aromatic polyester carbonates.

The aromatic polyester carbonates can be linear and branched in a known manner (cf. DE-A 2 940 024 and DE-A 3 007 934), and linear polyester carbonates are preferred.

Branching agents may be used, for example, carboxyfluorene chloride having a functionality of three or more, such as symmetrical phthalic acid trichloride, melamine trichloride, 3,3',4,4'-benzophenone tetracarboxy fluorene tetra chloro, 1,4,5,8-naphthalene tetracarboxylic 2carboxamide tetrachlorosilane or pyromellitic tetrachloro acyl, an amount of 0.01 to 1.0 mole% (as used by the meter dicarboxylic acyl-dichlorophenyl), or as a functionality of Three or more phenols such as phloroglucinol, 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)hept-2-ene, 4,6-dimethyl-2, 4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, three ( 4-hydroxyphenyl)phenylmethane, 2,2-bis[4,4-bis(4-hydroxyphenyl)cyclohexyl]propane, 2,4-bis(4-hydroxyphenylisopropyl)phenol, Tetrakis(4-hydroxyphenyl)methane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, 2-(4-hydroxyphenyl)-2-(2,4 -dihydroxyphenyl)propane, tetrakis(4-[4-hydroxyphenyl]isopropyl]phenoxy)methane or 1,4-bis([4,4'-dihydroxytriphenyl]methyl) The amount of benzene is from 0.01 to 1.0 mol% (based on the diphenol used). The phenolic branching agent can be placed in advance in a container containing diphenol; the hydrazine chloride branching agent can be introduced together with hydrazine dichloride.

The carbonate structural unit content of the thermoplastic aromatic polyester carbonate can be varied as desired. The content of the carbonate group is preferably at most 100 mol%, particularly up to 80 mol%, particularly preferably up to 50 mol%, based on the total of the ester group and the carbonate group. Both the ester and carbonate moieties of the aromatic polyester carbonate may be present in the polycondensation product in a block or random distribution.

The thermoplastic aromatic polyester carbonate and the polyester carbonate may be used singly or in combination.

Component B: Polyoxyalkylene-polycarbonate copolymer component

Component B is a polyoxyalkylene-polycarbonate copolymer in an amount of 25 to 90% by weight, preferably 25 to 85% by weight, more preferably 26% by weight based on 100% by weight of the polycarbonate composition. 80% by weight, more preferably 27-70% by weight, still more preferably 28-60% by weight, most preferably 29-50% by weight.

Suitable polyoxyalkylene-polycarbonate copolymers are known in the art in accordance with the present invention or may be prepared by methods known in the prior art.

The polydiorganotoxime (also referred to herein as "heloxane") block of the polyoxyalkylene-polycarbonate copolymer comprises a polydiorganotoxime block of formula (4): Wherein each R is individually a C _1-13 monovalent organic group. For example, R may be C ₁ -C ₁₃ -alkyl, C ₁ -C ₁₃ -alkoxy, C ₂ -C ₁₃ -alkenyl, C ₂ -C ₁₃ -alkenyloxy, C ₃ -C ₆ -ring Alkyl, C ₃ -C ₆ -cycloalkoxy, C ₆ -C ₁₄ -aryl, C ₆ -C ₁₀ -aryloxy, C ₇ -C ₁₃ -aralkyl, C ₇ -C ₁₃ -aryl Alkoxy, C ₇ -C ₁₃ -alkylaryl or C ₇ -C ₁₃ -alkaryloxy. The above groups may be fully or partially halogenated from fluorine, chlorine, bromine or iodine or a combination thereof. The above R group composition can be used for the same copolymer.

The value of E in the formula (4) varies widely depending on factors such as the type and relative content of the polycarbonate composition of the present invention and the predetermined properties of the composition. Usually, the average value of E is from 2 to 1,000, preferably from 3 to 500, more preferably from 5 to 100. In one embodiment, the average value of E is from 10 to 75, preferably from 10 to 40. In another embodiment, the average value of E is from 40 to 60. In the case where E is a small value, for example, less than 40, a relatively large amount of polyoxyalkylene-polycarbonate copolymer is used. Conversely, where E is a large value, such as greater than 40, a smaller amount of polyoxyalkylene-polycarbonate copolymer can be used.

Component B may also be a composition comprising a first polyoxyalkylene-polycarbonate copolymer and a second polyoxyalkylene-polycarbonate copolymer, wherein the first polyoxyalkylene-polycarbonate copolymer The average value of E is smaller than the average value of the E of the second polyoxyalkylene-polycarbonate copolymer.

In one embodiment, the polyoxyalkylene block is of formula (5): Wherein E is as defined above; each R may be the same or different and as defined above; Ar may be the same or different and is a substituted or unsubstituted C ₆ -C ₃₀ -exylaryl group, wherein the chain is directly attached to the aromatic moiety. The Ar group in the formula (5) may be derived from a C ₅ -C ₃₀ -dihydroxy extended aryl compound.

In another embodiment, the polyoxyalkylene block is of formula (6): Wherein R and E are as defined above, each R ^{5 is} individually a divalent C ₁ -C ₃₀ -organic group, wherein the polymeric polyoxyalkylene block corresponds to the reaction residue of the dihydroxy compound. In a specific embodiment, the polyoxyalkylene block is of formula (7): Wherein R and E are as defined above. The R ⁶ in the formula (7) is a divalent C ₂ -C ₈ -aliphatic group. Each M in formula (7) may be the same or different and may be halogen, amine, nitro, C ₁ -C ₈ -alkylthio, C ₁ -C ₈ -alkyl, C ₁ -C ₈ - Alkoxy, C ₂ -C ₈ -alkenyl, C ₂ -C ₈ -alkenyloxy, C ₃ -C ₈ -cycloalkyl, C ₁ -C ₈ -cycloalkoxy, C ₆ -C ₁₀ - Aryl, C ₆ -C ₁₀ -aryloxy, C ₇ -C ₁₂ -aralkyl, C ₇ -C ₁₂ -aryloxy, C ₇ -C ₁₂ -alkylaryl or C ₇ -C ₁₂ -alkane An aryloxy group in which each n is independently 0, 1, 2, 3 or 4.

In one embodiment, M is bromo or chloro, alkyl (such as methyl, ethyl or propyl), alkoxy (such as methoxy, ethoxy or propoxy) or aryl (such as phenyl) , chlorophenyl or tolyl); R ⁶ is dimethylene, trimethylene or tetramethylene; R is C _1-8 -alkyl, haloalkyl (such as trifluoropropyl), cyanoalkyl Or an aryl group (such as phenyl, chlorophenyl or tolyl). In another embodiment, R is methyl, or methyl and trifluoropropyl compositions, or methyl and phenyl compositions. In still another embodiment, M is a methoxy group, n is a 1, R ⁶ is a divalent C ₁ -C ₃ -aliphatic group, and R is a methyl group.

The specific polydiorganotoxime blocks are of the following formulas (8), (9), (10):

Or a composition comprising at least one of the above, wherein the E average is 2-200, 2-125, 5-125, 5-100, 5-50, 20-80 or 5-20.

In one embodiment, the block of formula (4) is derived from the corresponding dihydroxy polyoxane (11): Wherein R, E, M, R ⁶ and n are as described above. Dihydroxy polyoxyalkylene can be prepared by platinum-catalyzed addition in a hydrazine hydride of formula (12): Wherein R and E are as defined above as aliphatic unsaturated monohydric phenols. Exemplary aliphatic unsaturated monohydric phenols include eugenol, 2-alkylphenol, 4-allyl-2-methylphenol, 4-allyl-2-phenylphenol, 4-allyl-2 -bromophenol, 4-allyl-2-tris-butoxyphenol, 4-phenyl-2-phenylphenol, 2-methyl-4-propylphenol, 2-allyl-4,6 - dimethyl phenol, 2-allyl-4-bromo-6-methyl phenol, 2-allyl-6-methoxy-4-methyl phenol and 2-allyl-4,6- Dimethylphenol. Compositions comprising at least one of the above may also be used.

In a preferred embodiment, the helioxane block of the polyoxyalkylene-polycarbonate copolymer is derived from the corresponding dihydroxy polyoxane (I): Wherein in the formula (I), R _{1 each} independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group or an aryl group, preferably a hydrogen atom; and R _{2 is} individually represented by 1 a hydrocarbon group or a hydroxyl group of 13 carbon atoms, preferably a methyl group; R _{3 each} independently represents an alkylene group having 2-8 carbon atoms, preferably 3 carbon atoms; and m each represents an integer of 0-4, preferably 0; n each represents an integer of 1 to 200, preferably the above E value; A represents a structure having the following chemical formula (II): X represents a polynuclear aryl group which has 6 to 30 carbon atoms and is unsubstituted or substituted by a halogen atom, an alkyl group, an alkoxy group, an aryl group or a carboxyl group, preferably an unsubstituted extended aryl group.

The polyoxyalkylene-polycarbonate copolymer may comprise from 50% to 99% by weight of carbonate units and from 1% to 50% by weight of decane units. Within this range, the polyoxyalkylene-polycarbonate copolymer comprises preferably from 70 to 98% by weight, more preferably from 75 to 97% by weight, of the carbonate unit and preferably from 2 to 30% by weight, more preferably from 3 to 25 parts by weight. More preferably, 4 to 10% by weight, most preferably 5 to 9% by weight of the oxoxane unit. In an exemplary embodiment, the polyoxyalkylene-polycarbonate copolymer is capped with p-cumyl.

In one embodiment, an exemplary polyoxyalkylene-polycarbonate copolymer is a block copolymer having the structure shown by the following formula (13): Wherein the polyoxyalkylene block is capped with eugenol, wherein x is from 1 to 100, preferably from 5 to 85, more preferably from 10 to 70, still more preferably from 15 to 65, most preferably from 40 to 60. In one embodiment, y is 1 to 90 and z is 1 to 600. The polyoxyalkylene blocks can be randomly distributed or controlled to be distributed between the polycarbonate blocks. In one embodiment, x is 30 to 50, y is 10 to 30, and z is 450 to 600.

In one embodiment, the polyoxyalkylene-polycarbonate copolymer comprises from 4 to 10% by weight, preferably from 5 to 9% by weight, more preferably from 6 to the total weight of the polyoxyalkylene-polycarbonate copolymer. 9 wt% polyoxyalkylene. Polyoxyalkylene-polycarbonate copolymers containing 10% by weight or less of polyoxyalkylene are generally optically clear.

In one embodiment, the polyoxyalkylene-polycarbonate copolymer comprises 10% by weight or more, specifically 12% by weight or more, more specifically, based on the total weight of the polyoxyalkylene-polycarbonate copolymer. It is 14% by weight or more of polyoxyalkylene. Polyoxyalkylene-polycarbonate copolymers containing 10% by weight or more of polydecane are generally optically opaque.

Measured by gel permeation chromatography using a crosslinked styrene-divinylbenzene column, the sample concentration is, for example, 1 mg/ml, and corrected by polycarbonate standards, the weight of the polyoxyalkylene-polycarbonate copolymer. The average molecular weight is from 2,000 to 100,000 Daltons, specifically from 5,000 to 50,000 Daltons.

The melt volume flow rate of the polyoxyalkylene-polycarbonate copolymer measured at 300 ° C / 1.2 kg is from 1 to 50 cubic centimeters (cm ³ ) / 10 minutes (cc / 10 minutes), preferably 2 to 30cc/10 minutes. Polyoxane-polycarbonate copolymer mixtures having different flow characteristics can be used to achieve overall predetermined flow characteristics.

Component C: Flame retardant component

Component C is a flame retardant component comprising 0.5 to 6% by weight, preferably 1 to 6% by weight, more preferably 2 to 6% by weight, most preferably 2 to 4% by weight of the cyclic phosphazene of formula (X): Wherein k represents an integer of 1 or 1-10, preferably an integer of 1-8, more preferably an integer of 1-5, and the terpolymer content (k = 1) is 60-98 moles per component C. %, wherein R is the same or different in each case, and represents an amine group; a C ₁ - to C ₈ -alkyl group, preferably a methyl group, an ethyl group, a propyl group or a butyl group, each of which is selectively halogenated, preferably Halogenated by fluorine; C ₁ - to C ₈ -alkoxy, preferably methoxy, ethoxy, propoxy or butoxy; C ₅ - to C ₆ -cycloalkyl, each selectively alkane Substituted (preferably C ₁ - to C ₄ -alkyl) and/or halogen (preferably chlorine and/or bromine); C ₆ - to C ₂₀ -aryloxy, preferably phenoxy, naphthalene Oxyl groups, each optionally substituted by an alkyl group (preferably C ₁ - to C ₄ -alkyl) and/or halogen (preferably chlorine, bromine) and/or a hydroxyl group; C ₇ - to C ₁₂ -aralkyl Preferred are phenyl-C ₁ -C ₄ -alkyl groups, each of which is optionally alkyl (preferably C ₁ - to C ₄ -alkyl) and/or halogen (preferably chlorine and/or bromine) And a halogen group, preferably chlorine; or an OH group, the weight percentage being 100% by weight of the polycarbonate composition.

The cyclophosphazene is preferably a propoxyphosphazene, a phenoxyphosphazene, a methylphenoxyphosphazene, an aminophosphazene, and a fluoroalkylphosphazene, and a phosphazene having the following structure:

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

Preferably, the phenoxyphosphazene (all R = phenoxy) and the oligomer content (C1) of k = 1 is from 60 to 98 mol%.

In the case where the phosphazene according to formula (X) is halogen-substituted on phosphorus, for example, due to an incompletely reacted starting material, the halogen-substituted phosphazene content on phosphorus is preferably less than 1000 ppm (parts per million). More preferably, it is less than 500 ppm.

The phosphazenes may be used singly or in combination, that is, the R groups may be the same, or two or more groups in the formula (X) may be different. The R groups of the phosphazene are preferably the same.

In another preferred embodiment, only phosphazenes having the same R are used.

Preferably, according to the invention, any terpolymer (k = 1), tetramer (k = 2), oligomeric phosphazene (k = 3, 4, 5, 6 and / or 7) and / or k The arsenic content of the phosphazene oligomer of 8 is the same as that of the cyclophosphazene of the formula (X).

In a preferred embodiment, the tetramer content (C2) of k=2 is from 2 to 50 mol%, more preferably from 5 to 40 mol%, even more preferably from 10 to 30 mol, based on the component C. % of ear, particularly preferably 10 to 20 mol%.

In a preferred embodiment, the higher oligomeric phosphazene content (k = 3, 4, 5, 6, 7) (C3) is from 0 to 30 mol%, more preferably from 2.5 to 25, based on component C. Mole%, preferably 5 to 20 mol%, and particularly preferably 6 to 15 mol%.

In a preferred embodiment, based on component C, k The oligomer content (C4) of 8 is from 0 to 2.0 mol%, more preferably from 0.10 to 1.00 mol%.

In another preferred embodiment, the phosphazene of component C satisfies all three conditions associated with the above levels (C2-C4).

Component C preferably comprises, more preferably, phenoxyphosphazene, and in terms of component C, the terpolymer content (k = 1) is from 65 to 85 mol%, and the tetramer content (k = 2) is 10 to 20 mol%, the advanced oligophosphazene content (k = 3, 4, 5, 6, 7) is 5-20 mol%, k The phosphazene oligomer content of 8 is from 0 to 2 mol%.

Component C particularly preferably comprises, more preferably, phenoxyphosphazene, and in terms of component C, the terpolymer content (k = 1) is 70 to 85 mol%, and the tetramer content (k = 2) is 10 to 20 mol%, the advanced oligophosphazene content (k = 3, 4, 5, 6, 7) is 6 to 15 mol%, k The phosphazene oligomer content of 8 is from 0.1 to 1 mol%.

In still another particularly preferred embodiment, component C comprises, preferably phenoxyphosphazene, and in terms of component C, the terpolymer content (k = 1) is from 65 to 85 mol%, tetramer The content (k=2) is 10 to 20 mol%, and the high-grade oligophosphazene content (k=3, 4, 5, 6, 7) is 5 to 15 mol%, k The phosphazene oligomer content of 8 is 0-1 mol%.

As described above, in these specific examples, the trimer content (k = 1), the tetramer content (k = 2), and the oligomeric phosphazene content (k = 3, 4, 5, 6, and / are more preferable). Or 7) and / or k The phosphazene oligomer content of 8 is based on the cyclic phosphazene of formula (X).

According to the following formula, n defines the weighted arithmetic mean of k: Wherein x _i is the content of the oligomer k _i , so the sum of all x _i is 1.

In an alternative embodiment, n is from 1.10 to 1.75, preferably from 1.15 to 1.50, more preferably from 1.20 to 1.45, and even more preferably from 1.20 to 1.40 (including range limits).

Phosphazene and its preparation are described, for example, in EP-A 728 811, DE-A 1 961 668 and WO 97/40092.

After compounding, ³¹ P NMR (chemical shift; δ trimer: 6.5 to 10.0 ppm; δ tetramer: -10 to -13.5 ppm; δ advanced oligomer: -16.5 to -25.0 ppm) can also be utilized. The phosphazene oligomer composition in the blended sample is measured and quantified.

Component C may also include other flame retardants commonly used in the industry.

Component D: Impact modifier

Component D is an impact-resistant modifier comprising 0.5 to 6% by weight of methyl methacrylate-butadiene-styrene (MBS) based on 100% by weight of the polycarbonate composition.

The methyl methacrylate-butadiene-styrene has a butadiene or butadiene-styrene copolymer as a rubber phase, and the methyl methacrylate-butadiene-styrene is 100% by weight. It is 60 to 85% by weight, preferably 65 to 80% by weight, more preferably 70 to 80% by weight. The methyl methacrylate-butadiene-styrene preferably has a PMMA or PMMA-styrene copolymer as a graft layer.

The methyl methacrylate-butadiene-styrene impact modifier suitable for component D comprises a butadiene or butadiene-styrene rubber core-shell impact modifier, preferably with methyl Methyl acrylate or methyl methacrylate-styrene copolymer grafted butadiene or butadiene-styrene rubber impact modifiers such as Kane Ace M732 from Kaneka, Paraloid from Dow Chemicals EXL2650J, EXL2690, EXL2691J, etc.

Component D may also include other impact-resistant modifiers commonly used in the industry.

Component E: anti-drip agent

The polycarbonate composition according to the present invention may further comprise an anti-drip agent. The anti-drip agent may preferably be a polytetrafluoroethylene (PTFE) or a PTFE-containing composition such as a PTFE masterbatch plus a polymer or copolymer containing styrene or methyl methacrylate.

The anti-drip agent is used in an amount of from 0.05 to 1% by weight, preferably from 0.2 to 0.9% by weight, more preferably from 0.3 to 0.8% by weight, wherein the polycarbonate composition is 100% by weight.

The fluorinated polyolefin used as an anti-drip agent has a high molecular weight and has a glass transition temperature of more than -30 ° C, usually more than 100 ° C, and the fluorine content is preferably 65 to 76% by weight, particularly 70 to 76% by weight (of which fluorine The polyolefin is 100% by weight), and the average particle diameter d ₅₀ is from 0.05 to 1000 μm, preferably from 0.08 to 20 μm. Typically, the fluorinated polyolefin has a density of from 1.2 to 2.3 grams per cubic centimeter (g/cm ³ ). Preferred fluorinated polyolefins are polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene/hexafluoropropylene copolymers and ethylene/tetrafluoroethylene copolymers. Fluorinated polyolefins are known (see "Vinyl and Related Polymers"; Schildknecht, John Wiley & Sons, Inc., New York, 1962, pp. 484-494", "Fluoropolymers"; Wall, Wiley-Interscience, John Wiley & Sons, Inc., New York, Volume 13, 1970, pp. 623-654, "Modern Plastics Encyclopedia", 1970-1971, Volume 47, No. 10 A, October 1970, McGraw-Hill, Inc New York, pages 134 and 774", "Modern Plastics Encyclopaedia", 1975-1976, October 1975, Volume 52, No. 10 A, McGraw-Hill, Inc., New York, pages 27, 28 and 472" And US-PS 3,671,487, 3,723,373 and 3,838,092).

It can be prepared by known methods, for example, by applying tetrafluoroethylene to an aqueous medium and a radical-forming catalyst such as sodium peroxodisulfate, potassium or ammonium at a pressure of from 7 to 71 kg/cm 2 (kg/cm ² ). Polymerization is carried out at temperatures of from 0 to 200 ° C (preferably from 20 to 100 ° C) (for further details see, for example, US 2,393,967). The material density may be 1.2 to 2.3 g/cm ³ and the average particle diameter may be 0.05 to 1000 μm depending on the form of use.

According to the present invention, it is preferred that the fluorinated polyolefin has an average particle diameter of from 0.05 to 20 μm, more preferably from 0.08 to 10 μm, and a density of from 1.2 to 1.9 g/cm ³ .

Suitable fluorinated polyolefins which can be used in powder form are tetrafluoroethylene polymers having an average particle size of from 100 to 1000 μm and a density of from 2.0 g/cm ³ to 2.3 g/cm ³ . It is suitable for commercial products of tetrafluoroethylene polymer powder, such as the product Teflon ^® supplied by DuPont.

Other additives

The polycarbonate composition according to the present invention may further comprise suitable additives commonly used in the industry, such as lubricants and mold release agents (such as pentaerythritol tetrastearate), nucleating agents, stabilizers (such as UV/light stabilizers, heat). Stabilizers, antioxidants, lactide inhibitors, hydrolysis stabilizers), antistatic agents (such as conductive carbon black, carbon fiber, carbon nanotubes and organic antistatic agents, such as polyalkylene ethers, alkyl sulfonates) Or polyamine-containing polymers), and dyes, pigments, fillers and reinforcing materials, in particular glass fibers, mineral strengthening materials and carbon fibers. In addition to this, the composition may also comprise other conventional polymeric additives such as flame retardant synergists.

Available stabilizer is preferably steric hindrance phenol and phosphite or mixtures thereof, for example, ^{Irganox ® B900 (Ciba Speciality Chemicals)} . Pentaerythritol tetrastearate is preferably used as a release agent. Further, it is preferred to add a black pigment such as Blackpearls.

In addition to the optional other additives, the particularly preferred molding composition further comprises a release agent, preferably pentaerythritol tetrastearate, in an amount of from 0.1 to 1.5 parts by weight, preferably from 0.2 to 1.0 part by weight, more preferably 0.3. Up to 0.8 parts by weight.

In addition to containing selective additives, particularly preferred molding composition further comprises at least one stabilizer selected from the group consisting of, for example, steric hindrance phenol, phosphite group consisting of and mixtures thereof, Irganox ^® B900 preferred, in an amount of from 0.01 to 0.5 parts by weight, preferably 0.03 to 0.4 parts by weight, more preferably 0.06 to 0.3 parts by weight.

The polycarbonate composition provided according to the invention comprises, in addition to components A), B), C), D) or A), B), C), D), E) and other additives listed in the present invention, It may comprise components which are commonly used in the industry for the preparation of polycarbonate materials, the total weight of all components being 100% by weight, wherein a preferred solution comprises a total of 100% by weight of components A), B), C), D) Or the sum of components A), B), C), D), E) is 100% by weight, or the sum of components A), B), C), D) and other additives is 100% by weight, or The sum of components A), B), C), D), E) and other additives is 100% by weight.

The polycarbonate composition according to the present invention can be prepared and used according to methods known to those skilled in the art, for example, by a method comprising the following steps: 1) premixed impact modifier, flame retardant and other additives (e.g. Molding agent, stabilizer), to obtain a premix; 2) mixing the premix with other components, such as a polycarbonate component, a polyoxyalkylene-polycarbonate copolymer component; 3) using, for example, a twin screw The extruder granulated to obtain pellets of the polycarbonate composition.

Example

The following examples are intended to be illustrative, and not limiting.

The components used in the examples and their profiles are as follows.

In the comparative examples and the inventive examples, the percentage by weight of each component means the weight percentage of the component relative to the obtained polycarbonate composition, wherein the polycarbonate composition is 100% by weight, unless otherwise specified.

The polycarbonate compositions of the comparative examples and inventive examples of the invention were prepared in the following manner: 1) using a high speed mixer (Reimelt Henschel mixer, model FML40), premixed impact modifier, flame retardant and Other additives, about 2 minutes, to obtain a premix; 2) in a twin-screw extruder (equipment and model Coperion ZSK26), mixing the premix with other components, such as polycarbonate components, polyoxynitride - a polycarbonate copolymer component, and granulated to obtain granules.

Test samples corresponding to the obtained polycarbonate composition particles were produced according to the test standard requirements of Tables 1 to 4, and corresponding tests were carried out according to the corresponding test standards.

The weight average molecular weight of the polycarbonate used in the examples was measured by GPC (gel permeation chromatography) and polycarbonate standards.

 Comparative Examples 1 to 7:  

Table 1 lists Comparative Examples 1 to 7. In the comparative examples listed in Table 1, phosphazene (FR-110) was used as the main flame retardant in the polycarbonate composition.

As shown in Table 1, the amount of phosphazene added from Comparative Example 1 to Comparative Example 3 was increased from 2.5% by weight to 4.5% by weight, although the Vicat softening temperature of the polycarbonate composition was maintained at a higher temperature (not low) At 134 ° C), but the flame retardant rating was raised from V1 (test conditions: 1.0 mm, 2 days, 23 ° C) to V0 (test conditions: 1.0 mm, 2 days, 23 ° C). However, the flame retardant rating has not yet reached the requirements of UL94 5VB (test conditions: 2.0 mm, 2 days, 23 ° C). Meanwhile, at a low temperature of -20 ° C to -40 ° C, the notched impact strength is 8.1 to 9.3 kJ / m ² (kJ / m ² ), which means that the polycarbonate composition exhibits brittleness, and the notched impact strength is not Very ideal.

In Comparative Examples 4 to 5, the amount of phosphazene added was maintained at 2.5% by weight, and 1% by weight and 2% by weight of methyl methacrylate-butadiene-styrene impact modifier Kane Ace M732 were added, respectively. To increase the impact strength, wherein the weight percentage is 100% by weight based on the polycarbonate composition. As shown in Table 1, although the polycarbonate compositions of Comparative Examples 4-5 passed the UL94 5VB standard, the flame retardancy was lowered from V1 (test conditions: 1.0 mm, 2 days, 23 ° C) to V2 (test conditions: 1.0 mm, 2 days, 23 ° C), at a low temperature of -20 ° C to -40 ° C, the notched impact strength increased, but did not significantly improve, only 12-16kJ / m ² .

In Comparative Examples 6 to 7, 40% by weight of a polydecane-polycarbonate copolymer (ST6-3022PJ(1)) was added to increase the low-temperature notched impact strength, wherein the weight percentage was based on the polycarbonate composition. It is 100% by weight. As shown in Table 1, the low-temperature impact resistance of the polycarbonate compositions prepared in Comparative Examples 6-7 was remarkably improved, which reached 58 kJ/m ² and 51 kJ/m ² at -20 ° C, respectively, and the flame retardancy was from V ² . (Test conditions: 1.0 mm, 2 days, 23 ° C) Raised to V0 (test conditions: 1.0 mm, 2 days, 23 ° C), but no longer meet the flame retardant rating UL94 5VB (test conditions: 2.0 mm, 2 days, 23 °C) requirements.

Table 2 lists inventive examples 1-6 of the polycarbonate compositions according to the present invention.

Comparative Examples 1 to 7, surprisingly, by adding 1% by weight of a methyl methacrylate-butadiene-styrene impact modifier to a polycarbonate, polyoxyalkylene-polycarbonate copolymer Incorporation with phosphazene wherein the weight percentage is 100% by weight based on the polycarbonate composition, Inventive Example 1 allows the polycarbonate composition to achieve a flame retardant rating of UL94 5VB (test condition: 1.5 mm, 2 days, 23 ° C) requirements. At the same time, at a low temperature of -20 ° C to -40 ° C, the notch impact strength can reach 59-51 kJ / m ² . Low temperature impact resistance is improved.

In Inventive Example 2, the content of the methyl methacrylate-butadiene-styrene impact modifier was increased to 2% by weight, wherein the weight percentage was 100% by weight based on the polycarbonate composition, and the resulting poly The carbonate composition can achieve a flame retardant rating of UL94 5VB (test conditions: 1.5 mm, 2 days, 23 ° C). At the same time, at a low temperature of -20 ° C to -40 ° C, the notched impact strength can reach 61-54 kJ / m ² . Low temperature impact resistance is improved.

In view of the flame retardant UL94 5VB test, the main failure mode is test material burning and dripping, and inventive examples 3 and 4 demonstrate that methyl methacrylate-butadiene-styrene resistance is obtained under the condition of reducing the drip-proof dose. The effect of the impact modifier on the flame retardancy of the polycarbonate composition. As shown in Table 2, in Inventive Examples 3 and 4, the amount of the anti-drip agent (PTFE) was reduced from 0.8% by weight to 0.3% by weight, wherein the weight percentage was 100% by weight based on the polycarbonate composition. The obtained polycarbonate composition can still meet the requirements of flame retardant grade UL94 5VB (test conditions: 1.5 mm, 2 days, 23 ° C), and the notched impact strength can reach 60 kJ/m ² (test condition: -20 ° C, 3 mm) , 5.5 joules). Low temperature impact resistance is improved.

In Inventive Examples 5, 6, the higher molecular weight M2600 polycarbonate component was replaced with a lower molecular weight M2400. Further, in Inventive Example 6, the content of the polyoxyalkylene-polycarbonate copolymer was reduced to 30% by weight relative to Inventive Example 1-5, wherein the weight percentage was 100% by weight based on the polycarbonate composition. The polycarbonate composition can still meet the requirements of flame retardant UL94 5VB (test conditions: 1.5 mm, 2 days, 23 ° C), and the notched impact strength can reach 54-56 kJ/m ² (test condition: -20 ° C, 3 mm, 5.5 joules). Low temperature impact resistance is improved.

Comparative Example 7, which uses a phosphate flame retardant AKD STAB FP-800, inventive Example 1 shows that the phosphazene flame retardant is in combination with a polyoxyalkylene-polycarbonate copolymer and methyl methacrylate-butyl The synergistic effect of the diene-styrene impact modifier allows the polycarbonate composition to achieve a flame retardant rating of UL94 5VB (test conditions: 1.5 mm, 2 days, 23 ° C and 2.0 mm, 2 days, 23 ° C) Requirements.

As shown in Inventive Examples 1 to 6 of Table 2, a polycarbonate comprising a polycarbonate component, a polyoxyalkylene-polycarbonate copolymer, a phosphazene, and a methyl methacrylate-butadiene-styrene The composition simultaneously exhibits good impact resistance, flame retardancy and heat resistance.

Table 3 lists Comparative Examples 8 to 11 of the present invention. In Comparative Examples 8 to 11, an impact modifier other than methyl methacrylate-butadiene-styrene was used for the polycarbonate composition without using methyl methacrylate-butadiene- Styrene, such as acrylic rubber-based impact modifiers Paraloid EXL 2300, Paraloid EXL 2311, Paraloid EXL 2313. The results of Comparative Examples 8 to 11 show that the flame retardancy of the polycarbonate composition will be far less than that required to achieve a flame retardant rating of UL94 5VB (test conditions: 2.0 mm, 2 days, 23 ° C). From UL94 V0 (test conditions: 1.0 mm, 2 days, 23 ° C) of Inventive Examples 1 and 2 to UL94 V1 of Comparative Examples 8 to 11 (test conditions: 1.0 mm, 2 days, 23 ° C), also observed Low temperature impact resistance is reduced.

Table 4 lists Inventive Examples 7 to 18 according to the present invention. As shown in Table 4, in Inventive Examples 7 to 18, the amount of phosphazene was 1.5% by weight to 5% by weight; the amount of methyl methacrylate-butadiene-styrene was 1% by weight to 5% by weight; The amount of the siloxane-polycarbonate copolymer is from 40% by weight to 80% by weight; wherein the weight percentage is based on 100% by weight of the polycarbonate composition. Inventive Examples 1 to 18 show that the synergy between polycarbonate, polyoxyalkylene-polycarbonate copolymer, phosphazene and methyl methacrylate-butadiene-styrene enables polycarbonate compositions to Good low temperature impact resistance (such as low temperature impact strength at -40 °C) and good flame retardancy (such as UL94 5VB (test conditions: 1.5 mm, 2 days, 23 °C) and UL94 5V0) (Test conditions: 1.0 mm, 2 days, 23 ° C)) and good heat resistance, for example, Vicat softening temperature is higher than 127 °C.

The inventive examples show that, in the present invention, the inventive composition of the polycarbonate component, the polyoxyalkylene-polycarbonate copolymer, the methyl methacrylate-butadiene-styrene and the phosphazene compound can be synergistically realized. The polycarbonate composition has high flame retardancy and high impact resistance.

As is apparent from Table 5, the flame retardancy and mechanical properties are optimal when at least 25% by weight of the polysiloxane-polycarbonate copolymer is used, so that the composition of the present invention can provide an excellent property profile.

While the invention has been described in detail with reference to the embodiments of the present invention, it is understood that change.

Claims (14)

A polycarbonate composition comprising: A) from 8 to 70% by weight of a polycarbonate component; B) from 25 to 90% by weight of a polyoxyalkylene-polycarbonate copolymer component; a fuel component comprising 0.5 to 6% by weight of a cyclic (X) cyclophosphazene Wherein k represents an integer of 1 or 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, and the terpolymer content (k = 1) is 60 based on the component C) Up to 98% by mole, wherein R is the same or different in each case, and represents an amine group; C ₁ - to C ₈ -alkyl, preferably methyl, ethyl, propyl or butyl, each selected Halogenated, preferably halogenated by fluorine; C ₁ - to C ₈ -alkoxy, preferably methoxy, ethoxy, propoxy or butoxy; C ₅ - to C ₆ -cycloalkyl, Each of the substituents is substituted by an alkyl group (preferably C ₁ - to C ₄ -alkyl) and/or a halogen (preferably chlorine and/or bromine); a C ₆ - to C ₂₀ -aryloxy group, preferably a phenoxy group, a naphthyloxy group, each of which is optionally substituted by an alkyl group (preferably a C ₁ - to C ₄ -alkyl group) and/or a halogen (preferably chlorine, bromine) and/or a hydroxyl group; C ₇ - to C ₁₂ -aralkyl, preferably phenyl-C ₁ -C ₄ -alkyl, each optionally being alkyl (preferably C ₁ - to C ₄ -alkyl) and/or halogen (preferably a chlorine and/or bromine) substitution; or a halogen group, preferably chlorine; or an OH group; and D) an impact modifier component comprising from 0.5 to 6% by weight of methyl methacrylate Butadiene-styrene, the above weight percentages based on 100% by weight of the polycarbonate composition.  The polycarbonate composition according to claim 1, wherein the polyoxyalkylene-polycarbonate copolymer comprises 4 to 10% by weight based on 100% by weight of the polyoxyalkylene-polycarbonate copolymer. Preferably, 5 to 9% by weight, more preferably 6 to 9% by weight, of the oxoxane unit.    The polycarbonate composition according to claim 1 or 2, wherein the trimer content (k = 1) is more preferably from 65 to 95 mol%, more preferably from 65 to 90% by mole, preferably 65 to 85% by mole.   According to the polycarbonate composition of claim 3, wherein the trimer content (k = 1) is 65 to 85 mol% and the tetramer content (k = 2), respectively, based on the component C). ) is 10 to 20 mol%, and the higher oligomeric phosphazene content (k = 3, 4, 5, 6, 7) is 5 to 15 mol%, k The phosphazene oligomer content of 8 is 0-1 mol%.  The polycarbonate composition according to claim 1 or 3, wherein the cyclophosphazene is selected from the group consisting of propoxyphosphazene, phenoxyphosphazene, methylphenoxyphosphazene, aminophosphazene and fluorine One or more of the groups consisting of alkylphosphazenes.    The polycarbonate composition according to any one of claims 1 to 5, wherein the methyl methacrylate-butadiene-styrene has a butadiene or butadiene-styrene copolymer as a rubber The phase is 60 to 85% by weight based on 100% by weight of the methyl methacrylate-butadiene-styrene.    The polycarbonate composition according to any one of claims 1 to 6, wherein the methyl methacrylate-butadiene-styrene has a PMMA or PMMA-styrene copolymer as a graft layer.    The scope of the patent in any one of polycarbonate 1 to 7 composition, according to the polycarbonate composition is 100% by weight, and further comprises a set of points E) 0.05 to 1% by weight, preferably 0.2 to 0.9% by weight, more preferably 0.3 to 0.8% by weight of the anti-drip agent.    The polycarbonate composition according to any one of claims 1 to 8, further comprising a selective lubricant, a mold release agent, a nucleating agent, a stabilizer, an antistatic agent, a dye, a pigment, a filler, and a reinforcement Agent.   The polycarbonate composition according to any one of claims 1 to 9, wherein the polyoxyalkylene block of the polyoxyalkylene-polycarbonate copolymer is derived from the corresponding dihydroxy polyoxane (I) ): (I), wherein in the formula (I), R _{1 each} independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group or an aryl group; and R ₂ represents an individual 1 to a hydrocarbon group or a hydroxyl group of 13 carbon atoms; R _{3 each} independently represents an alkylene group having 2 to 8 carbon atoms; m each represents an integer of 0 to 4; n each represents an integer of 1 to 200; and A represents a chemical formula (II) Structure: X represents a polynuclear aryl group having 6 to 30 carbon atoms and is unsubstituted or substituted by a halogen atom, an alkyl group, an alkoxy group, an aryl group or a carboxyl group. A method of preparing a polycarbonate composition comprising the steps of: mixing a plurality of components for preparing the polycarbonate composition, the components comprising: A) from 8 to 70% by weight of a polycarbonate group a B) 25 to 90% by weight of a polyoxyalkylene-polycarbonate copolymer; C) a flame retardant component comprising 0.5 to 6% by weight of a cyclic phosphazene of the formula (X) Wherein k represents an integer of 1 or 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, and the terpolymer content (k = 1) is 60 to 98 based on the component C) Mole %, wherein R is the same or different in each case, and represents an amine group; C ₁ - to C ₈ -alkyl, preferably methyl, ethyl, propyl or butyl, each selectively halogenated , preferably halogenated by fluorine; C ₁ - to C ₈ -alkoxy, preferably methoxy, ethoxy, propoxy or butoxy; C ₅ - to C ₆ -cycloalkyl, each selected Substituted by an alkyl group (preferably C ₁ - to C ₄ -alkyl) and/or halogen (preferably chlorine and/or bromine); C ₆ - to C ₂₀ -aryloxy, preferably phenoxy a group, a naphthyloxy group, each of which is optionally substituted by an alkyl group (preferably a C ₁ - to C ₄ -alkyl group) and/or a halogen (preferably chlorine, bromine) and/or a hydroxyl group; C ₇ - to C ₁₂ An aralkyl group, preferably a phenyl-C ₁ -C ₄ -alkyl group, each optionally being alkyl (preferably C ₁ - to C ₄ -alkyl) and/or halogen (preferably chlorine and And/or bromine); or a halogen group, preferably chlorine; or an OH group; and D) an impact modifier component comprising 0.5 to 6% by weight of methyl methacrylate-butyl Alkene Styrene, the above weight percentages are based on 100% by weight of the polycarbonate composition.  Use of a polycarbonate composition according to any one of claims 1 to 10 for the preparation of injection molded or thermoformed molded articles.    A molded article prepared by the polycarbonate composition according to any one of claims 1 to 10.   The polycarbonate composition according to any one of claims 1 to 10, or the method according to claim 11, wherein in the component C), the terpolymer content (k = 1), Tetramer content (k=2), higher oligomeric phosphazene content (k=3, 4, 5, 6, 7) and/or k The phosphazene oligomer content of 8 is expressed in mol%, respectively, and is based on the cyclophosphazene of the formula (X).