WO2020118478A1 - Compositions de polycarbonate - Google Patents

Compositions de polycarbonate Download PDF

Info

Publication number
WO2020118478A1
WO2020118478A1 PCT/CN2018/119970 CN2018119970W WO2020118478A1 WO 2020118478 A1 WO2020118478 A1 WO 2020118478A1 CN 2018119970 W CN2018119970 W CN 2018119970W WO 2020118478 A1 WO2020118478 A1 WO 2020118478A1
Authority
WO
WIPO (PCT)
Prior art keywords
polycarbonate
polysiloxane
copolymer
compositions
polycarbonate compositions
Prior art date
Application number
PCT/CN2018/119970
Other languages
English (en)
Inventor
Zhenyu Huang
Hao HAN
Original Assignee
Covestro Deutschland Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Covestro Deutschland Ag filed Critical Covestro Deutschland Ag
Priority to CN201880100048.6A priority Critical patent/CN113366061B/zh
Priority to PCT/CN2018/119970 priority patent/WO2020118478A1/fr
Publication of WO2020118478A1 publication Critical patent/WO2020118478A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/445—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences
    • C08G77/448—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences containing polycarbonate sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Definitions

  • the present invention relates to polycarbonate compositions that have increased flame retardance while maintains good Vicat performance and high modulus performances. Furthermore the present invention relates to molded articles with the polycarbonate compositions, in particular to luggage support racks in high speed trains.
  • thermoplastic materials are usually adopted, such as polycarbonate compositions, for their many desired properties, for example, enhanced impact resistance, high modulus (stiffness) , and ductility at room temperature or below.
  • thermoplastic materials In some industry applications, such as housings of mobile communication devices or interior parts of high speed trains, thermoplastic materials must have high flame retardance, heat resistance and stiffness for restricted safety needs. Usually the flame retardance standard of UL94 vertical burning test (V0) is adopted in most electronic and electrical device housing products.
  • glass fiber reinforced flame retardant polycarbonate compositions could meet general applications requirements on high heat resistance and good flame retardance.
  • US7,994,248 B2 discloses polycarbonate compositions comprising an optional polycarbonate polymer, a polycarbonate-polysiloxane copolymer, a phosphorous-containing flame retardant, and a reinforced agent, and the polycarbonate compositions have an improved combination of properties, particularly Vicat softening temperature and high flame retardance in thin walls.
  • the introduction of polycarbonate-polysiloxane copolymer into the polycarbonate compositions improves its flame retardance performance, and increasing the loading of polycarbonate-polysiloxane copolymer while reducing the content of the flame retardant bis (diphenyl) phosphate (BDP) maintains the same FR performance level.
  • BDP flame retardant bis (diphenyl) phosphate
  • US9,023,923 B2 discloses a flame retardant composition
  • a flame retardant composition comprising a polycarbonate composition comprising a polycarbonate composition, glass fibers, and a flame retardant that comprises a phenoxyphosphazene compound
  • the polycarbonate compositions comprises a polysiloxane-carbonate copolymer and copolyester carbonate copolymer.
  • phosphazene compound is used as flame retardant.
  • One of the objects of the present invention is to provide polycarbonate compositions, comprising
  • Another object of this invention is to provide a process for preparing polycarbonate compositions, comprising the step of blending a group of components comprising
  • Another object of this invention is to provide articles manufactured from the polycarbonate compositions provided by this invention.
  • the polycarbonate compositions reach a good balanced strict application requirements of good impact performance, high flame retardance and high stiffness.
  • the polycarbonate compositions could be used for many applications with strict application requirements, in particularly in the application of producing the luggage support racks used in high speed trains.
  • This invention provides discloses polycarbonate compositions and the method for preparing the same as well as articles manufactured made from the polycarbonate compositions.
  • the polycarbonate compositions provided in this invention comprises
  • Component A a polycarbonate
  • polycarbonate is understood to mean both homopolycarbonates and copolycarbonates. These polycarbonates may be linear or branched in the familiar manner. Mixtures of polycarbonates may also be used according to the invention.
  • the polycarbonates present in the compositions are produced in a known manner from dihydroxyaryl compounds, carbonic acid derivatives, optionally chain terminators and branching agents.
  • Aromatic polycarbonates are produced for example by reaction of dihydroxyaryl compounds with carbonyl halides, preferably phosgene, and/or with aromatic dicarbonyl dihalides, preferably benzenedicarbonyl dihalides, by the interfacial process, optionally with use of chain terminators and optionally with use of trifunctional or more than trifunctional branching agents. Another possibility is production by way of a melt polymerization process via reaction of dihydroxyaryl compounds with, for example, diphenyl carbonate.
  • Suitable carbonic acid derivatives include phosgene or diphenyl carbonate.
  • Suitable chain terminators that may be employed in the production of polycarbonates are monophenols.
  • Suitable monophenols are for example phenol itself, alkylphenols such as cresols, p-tert-butylphenol, cumylphenol and mixtures thereof.
  • Suitable branching agents are the trifunctional or more than trifunctional compounds familiar in polycarbonate chemistry, in particular those having three or more than three phenolic OH groups.
  • Polycarbonates can be the homopolycarbonate based on bisphenol A, the homopolycarbonate based on 1, 1-bis (4-hydroxyphenyl) -3, 3, 5-trimethylcyclohexane and the copolycarbonates based on the two monomers bisphenol A and 1, 1-bis (4-hydroxyphenyl) -3, 3, 5-trimethylcyclohexane and also homo-or copolycarbonates derived from the dihydroxyaryl compounds of formulae (I) , (II) and (III)
  • R'in each case is C 1 -to C 4 -alkyl, aralkyl or aryl, preferably methyl or phenyl, more preferably methyl.
  • Preferred polycarbonate is the homopolycarbonate based on bisphenol A.
  • component A is preferably employed in the form of powders, pellets or mixtures of powders and pellets.
  • the polycarbonate employed may also be a mixture of different polycarbonates.
  • polycarbonate compositions comprise, as component A, a copolycarbonate comprising one or more monomer units of formula (1)
  • R 1 is hydrogen or C 1 -to C 4 -alkyl radicals, preferably hydrogen
  • R 2 is C 1 -to C 4 -alkyl radicals, preferably a methyl radical
  • n 0, 1, 2 or 3, preferably 3,
  • R 4 is H, linear or branched C 1 -to C 10 -alkyl radicals, preferably linear or branched C 1 -to C 6 -alkyl radicals, more preferably linear or branched C 1 -to C 4 -alkyl radicals, most preferably H or a C 1 -alkyl radical (methyl radical) , and
  • R 5 is linear or branched C 1 -to C 10 -alkyl radicals, preferably linear or branched C 1 -to C 6 -alkyl radicals, more preferably linear or branched C 1 -to C 4 -alkyl radicals, most preferably a C 1 -alkyl radical (methyl radical) ;
  • the monomer unit (s) of general formula (1) is/are introduced via one or more corresponding dihydroxyaryl compounds of general formula (1') :
  • R 1 is hydrogen or a C 1 -to C 4 -alkyl radical, preferably hydrogen
  • R 2 is a C 1 -to C 4 -alkyl radical, preferably methyl radical
  • n 0, 1, 2 or 3, preferably 3.
  • the copolycarbonate may contain one or more monomer unit (s) of formula (3) :
  • R 6 and R 7 are independently H, C 1 -to C 18 -alkyl-, C 1 -to C 18 -alkoxy, halogen such as Cl or Br or respectively optionally substituted aryl or aralkyl, preferably H,
  • Y is a single bond, -SO 2 -, -CO-, -O-, -S-, C 1 -to C 6 -alkylene or C 2 -to C 5 -alkylidene, and also C 6 -to C 12 -arylene, which may optionally be fused with further heteroatom-comprising aromatic rings.
  • the monomer unit (s) of general formula (3) is/are introduced via one or more corresponding dihydroxyaryl compounds of general formula (3a) :
  • dihydroxyaryl compounds of formula (3a) are dihydroxyaryl compounds of general formula (3b) ,
  • R 8 is H, linear or branched C 1 -to C 10 -alkyl radicals, preferably linear or branched C 1 -to C 6 -alkyl radicals, more preferably linear or branched C 1 -to C 4 -alkyl radicals, most preferably H or a C 1 -alkyl radical (methyl radical) , and
  • R 9 is linear or branched C 1 -to C 10 -alkyl radicals, preferably linear or branched C 1 -to C 6 -alkyl radicals, more preferably linear or branched C 1 -to C 4 -alkyl radicals, most preferably a C 1 -alkyl radical (methyl radical) .
  • Dihydroxyaryl compound (3c) in particular is very particularly preferred here.
  • the dihydroxyaryl compounds of the general formula (3a) may be used either alone or else in admixture with one another.
  • the dihydroxyaryl compounds are known from the literature or producible by literature methods (see for example H.J. Buysch et al., Ullmann's Encyclopedia of Industrial Chemistry, VCH, New York 1991, 5th Ed., Vol. 19, p. 348) .
  • Copolycarbonates may be present in the form of block or random copolycarbonates. Random copolycarbonates are particularly preferred. The ratio of the frequency of the diphenoxide monomer units in the copolycarbonate is calculated from the molar ratio of the dihydroxyaryl compounds employed.
  • the homo-or copolycarbonate which is optionally additionally present may contain one or more monomer units of formula (3) as previously described for the copolycarbonate.
  • Component B a polysiloxane-polycarbonate copolymer
  • the polycarbonate compositions provided in this present invention comprise, as component B) , 10-40 wt. %, preferably 15-35 wt. %, more preferably 18-32 wt. % of a polysiloxane-polycarbonate copolymer, based on the total weight of the polycarbonate compositions, the polysiloxane-polycarbonate copolymer comprising 5-12 wt. %, preferably 6-10 wt. %of polysiloxane unit based on the total weight of polysiloxane-polycarbonate copolymer.
  • suitable polysiloxane-polycarbonate copolymers are known in the prior art, or can be prepared by processes known in the prior art literature.
  • Polydiorganosiloxane (also named as “siloxane” or “polysiloxane” in the present text) block of the polysiloxane-polycarbonate copolymer includes polydiorganosiloxane blocks as in formula (4) :
  • each R is independently a C 1-13 monovalent organic group.
  • R may be C 1 -C 13 alkyl, C 1 -C 13 alkoxy, a C 2 -C 13 alkenyl group, C 2 -C 13 alkenyloxy, C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkoxy, C 6 -C 14 aryl, C 6 -C 10 aryloxy, C 7 -C 13 arylalkyl, C 7 -C 13 aralkoxy, C 7 -C 13 alkylaryl, or C 7 -C 13 alkylaryloxy.
  • the above groups can be fully or partly halogenated by fluorine, chlorine, bromine or iodine or combinations thereof.
  • the combination of the above R groups can be used in the same copolymers.
  • E in formula (4) can vary widely depending on factors like the type and the relative content of each component in the polycarbonate compositions of the present invention, and the desired property of the composition, etc.
  • E has an average value of 2 to 1,000, preferably 3 to 500, more preferably, 5 to 100.
  • E has an average value of 10 to 75, preferably of 10 to 40, and in still another embodiment, E has an average value of 40 to 60.
  • E is a relatively low value, e.g., less than 40, it may be desired to use a relatively large amount of a polysiloxane-polycarbonate copolymer.
  • E is a relatively high value, e.g., larger than 40, a relatively small amount of a polysiloxane-polycarbonate copolymer can be used.
  • Component B may also be a combination comprising a first polysiloxane-polycarbonate copolymer and a second polysiloxane-polycarbonate copolymer, wherein the average value of E in the first polysiloxane-polycarbonate copolymer is smaller than the average value of E in the second polysiloxane-polycarbonate copolymer.
  • polysiloxane blocks are of formula (5) :
  • Ar group in formula (5) may be derived from a C 5 -C 30 dihydroxyarylene compound.
  • polysiloxane blocks are of formula (6) :
  • R and E-1 are as defined above, and each R 5 is independently a divalent C 1 -C 30 organic group, and wherein, the polymerized polysiloxane block is the reaction residue of the corresponding dihydroxy compound.
  • polysiloxane blocks are of formula (7) :
  • R 6 in formula (7) is a divalent C 2 -C 8 aliphatic group.
  • Each M in formula (7) can be identical or different, and can be halogen, amino, 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 group, C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkoxy, C 6 -C 10 aryl, C 6 -C 10 aryloxy, C 7 -C 12 arylalkyl, C 7 -C 12 aralkoxy, C 7 -C 12 alkylaryl, or C 7 -C 12 alkylaryloxy, wherein, each n is independently 0, 1, 2, 3 or 4.
  • M is bromine or chlorine, an alkyl group such as methyl, ethyl or propyl, an alkoxyl group such as methoxyl, ethoxyl, or propoxyl, or an aryl group such phenyl, chlorophenyl or tolyl;
  • R 6 is a dimethylene, trimethylene or tetramethylene group; and
  • R is C 1-8 alkyl, haloalkyl such as trifluoropropyl, cyanoalkyl, or aryl such as phenyl, chlorophenyl or tolyl.
  • R is methyl, or a combination of methyl and trifluoropropyl, or a combination of methyl and phenyl.
  • M is methoxyl, n is 1, R 6 is a divalent C 1 -C 3 aliphatic group, and R is methyl.
  • Specific polydiorganosiloxane blocks are of the following formula (8) , (9) , (10) :
  • E-1 has an average value of 2-200, 2-125, 5-125, 5-100, 5-50, or 5-20.
  • blocks of formula (4) can be derived from the corresponding dihydroxy polysiloxane (11) :
  • Such dihydroxy polysiloxane can be prepared by effecting a platinum-catalyzed addition in a siloxane hydride of formula (12) :
  • R and E-1 are as defined above, being an aliphatic unsaturated monohydric phenol.
  • exemplary aliphatic unsaturated monohydric phenols include eugenol, 2-alkylphenol, 4-allyl-2-methylphenol, 4-allyl-2-phenylphenol, 4-allyl-2-bromophenol, 4-allyl-2-tert-butoxyphenol, 4-phenyl-2-phenylphenol, 2-methyl-4-propylphenol, 2-allyl-4, 6-dimethylphenol, 2-allyl-4-bromo-6-methylphenol, 2-allyl-6-methoxy-4-methylphenol, and 2-allyl-4, 6-dimethylphenol.
  • a combination comprising at least one of the above may also be used.
  • siloxane blocks of the polysiloxane-polycarbonate copolymer can be derived from the corresponding dihydroxy polysiloxane (I) :
  • R1 independently represents hydrogen atom, halogen atom, hydroxy group, alkyl group having 1 to 20 carbon atoms, alkoxy group or aryl group, preferably a hydrogen atom;
  • R2 independently represents hydrocarbon group having 1 to 13 carbon atoms or hydroxy group, preferably a methyl group
  • R3 independently represents alkylene group having 2 to 8 carbon atoms, preferably 3 carbon atoms
  • n independently represents an integer of 0 to 4, preferably 0;
  • n independently represents an integer of 1 to 200, preferably the values of E as given above;
  • A represents a structure of the following chemical formula (II) :
  • X represents polynuclear arylene group which has 6 to 30 carbon atoms and is unsubstituted or substituted with halogen atom, alkyl group, alkoxy group, aryl group or carboxy group, preferably an unsubstituted arylene group.
  • the most preferred polydiorganosiloxane in this invention is polydimethylsiloxane.
  • the polysiloxane-polycarbonate copolymer may comprise 50 wt. %to 99 wt. %of carbonate units and 1-50 wt. %of siloxane units. Within this range, the polysiloxane-polycarbonate copolymer may comprise preferably 70-98 wt. %, more preferably 75-97 wt. %of carbonate units and preferably 2-30 wt. %, more preferably 3-25 wt. %, still more preferably 5 to 12 wt. %and most preferably 6 to 10 wt. %of siloxane units. In an exemplary embodiment, the polysiloxane-polycarbonate copolymer is end capped with p-cumylphenol.
  • an exemplary polysiloxane-polycarbonate copolymer is a block copolymer having the structure as shown in the following formula (13) :
  • the polysiloxane blocks are end capped with eugenol, wherein, x is 1-100, preferably 5-85, more preferably 10-70, particularly preferably 15-65, and more preferably 40-60. In an embodiment, y is 1-90, and z is 1-600.
  • the polysiloxane block can be distributed randomly or distributed in control among the polycarbonate blocks. In an embodiment, x is 30-50, y is 10-30, and z is 450-600.
  • the polysiloxane-polycarbonate copolymer comprises 4-12 wt. %, preferably 5-12 wt. %, more preferably 6-10 wt. %of polysiloxane unit, based on the total weight of the polysiloxane-polycarbonate copolymer.
  • Polysiloxane-polycarbonate copolymers comprising 10 wt. %or less of polysiloxane unit are generally optically transparent based on the total weight of the polysiloxane-polycarbonate copolymer.
  • the polysiloxane-polycarbonate copolymer can have a weight average molecular weight of 2,000-100,000 Dalton, specifically, 5,000 to 50,000 Dalton measured by gel permeation chromatography using cross-linked styrene-divinyl benzene column at a sample concentration of, e.g., 1 mg/ml, and calibrating with polycarbonate standard.
  • the polysiloxane-polycarbonate copolymer can have a melt volume flow rate of 1-50 cm 3 /10 min, preferably 2-30 cm 3 /10 min measured at 300 °C/1.2 kg.
  • a mixture of polysiloxane-polycarbonate copolymers having different flow features may be used for obtaining an overall desired flow feature.
  • Component C glass fibers
  • the polycarbonate compositions provided in this present invention comprise, as component C) , 20-30 wt. %, preferably 22-28 wt. %, more preferably 24-26 wt. %of glass fibers, based on the total weight of the polycarbonate compositions.
  • the glass fibers may be flat or round fibers.
  • Flat glass fibers have an elliptical cross-sectional area, while round fibers have a circular cross-sectional area, where the cross-sectional areas are measured perpendicular to the longitudinal axis of the fiber.
  • the glass fibers may be manufactured from “E-glass” , “A-glass” , “C-glass” , “D-glass” , “R-glass” , or “6-glass” as well as E-glass derivatives that are fluorine-free and/or boron-free.
  • the preferred glass fibers are preferably manufactured from E-glass.
  • the glass fibers may be woven or nonwoven.
  • the glass fibers can have a diameter of about 3 micrometers to about 25 micrometers, specifically about 4 micrometers to about 20 micrometers, and more specifically about 8 micrometers to about 15 micrometers.
  • Component D) a phosphazene compound
  • the polycarbonate composition provided in this present invention comprises, as component D) , 1-5 wt. %, preferably 2-4 wt. %, more preferably 2-3 wt. %of a phosphazene compound, based on the total weight of the polycarbonate compositions.
  • Component D) can be a cyclic phosphazene of formula (III )
  • R is in each case identical or different and represents an amine group; C 1 -to C 8 -alkyl, preferably methyl, ethyl, propyl or butyl, each optionally halogenated, preferably halogenated with fluorine; C 1 -to C 8 -alkoxy, preferably methoxy, ethoxy, propoxy or butoxy; C 5 -to C 6 - cycloalkyl, each optionally substituted by alkyl, preferably C 1 -C 4 -alkyl, and/or by halogen, preferably chlorine and/or bromine; C 6 -to C 20 -aryloxy, preferably phenoxy, naphthoxy, each optionally substituted by alkyl, preferably C 1 -C 4 -alkyl, and/or by halogen, preferably chlorine, bromine, and/or by hydroxy; C 7 -to C 12 -aralkyl, preferably phenyl-C 1 -C 4 -alky
  • Said cyclic phosphazene is preferably:
  • phosphazene propoxyphosphazene, phenoxyphosphazene, methylphenoxyphosphazene, aminophosphazene and fluoroalkylphosphazenes, as well as phosphazenes having the following structures:
  • k 1, 2 or 3.
  • the content of this phosphazene halo-substituted on the phosphorus is preferably less than 1,000 ppm, more preferably less than 500 ppm.
  • the phosphazenes can be used alone or in the form of a mixture, that is to say the group R can be identical, or two or more groups in formula (III) can be different.
  • the groups R of a phosphazene are preferably identical.
  • the content of oligomers with k ⁇ 8 (C4) is from 0 to 2.0 mol%, based on component D, and preferably from 0.10 to 1.00 mol%.
  • the phosphazenes of component D fulfil all three conditions mentioned above as regards the contents (C2-C4) .
  • n defines the weighted arithmetic mean of k according to the following formula:
  • x i is the content of the oligomer k i , and the sum of all x i is accordingly 1.
  • n is in the range from 1.10 to 1.75, preferably from 1.15 to 1.50, more preferably from 1.20 to 1.45, and particularly preferably from 1.20 to 1.40 (including the limits of the ranges) .
  • the oligomer compositions of the phosphazenes in the blend samples can also be detected and quantified, after compounding, by means of 31 P NMR (chemical shift; ⁇ trimer: 6.5 to 10.0 ppm; ⁇ tetramer: -10 to -13.5 ppm; ⁇ higher oligomers: -16.5 to -25.0 ppm) .
  • Component D) may also include other flame retardants usually used in the industry.
  • Component E an impact modifier
  • the polycarbonate compositions provided in this present invention comprise, as component E) , 1-5 wt. %, preferably 1-4 wt. %, more preferably 2-4 wt. %of an impact modifier, based on the total weight of the polycarbonate compositions.
  • the impact modifier component E) can be a graft polymer comprising
  • the graft copolymers E are generally prepared by radical polymerization, for example by emulsion, suspension, solution or mass polymerization, preferably by emulsion polymerization.
  • the graft chain of the graft copolymers E is made from PMMA, PMMA-styrene copolymer or SAN.
  • Suitable monomers E. 1 are vinyl monomers such as vinyl aromatic compounds and/or vinyl aromatic compounds substituted on the ring (such as styrene, ⁇ -methylstyrene, p-methylstyrene, p-chlorostyrene) , methacrylic acid (C 1 -C 8 ) -alkyl esters (such as methyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, allyl methacrylate) , acrylic acid (C 1 -C 8 ) -alkyl esters (such as methyl acrylate, ethyl acrylate, n-butyl acrylate, tert-butyl acrylate) , organic acids (such as acrylic acid, methacrylic acid) and/or vinyl cyanides (such as acrylonitrile and methacrylonitrile) and/or derivatives (such as anhydrides and imides) of unsaturated carboxylic acids
  • Preferred monomers E. 1 are selected from at least one of the monomers styrene, methyl methacrylate, n-butyl acrylate and acrylonitrile. Particular preference is given to the use of methyl methacrylate or a mixture of styrene and acrylonitrile as the monomer E. 1.
  • the glass transition temperature of the graft base E. 2 is ⁇ 10°C, preferably ⁇ 0°C, particularly preferably ⁇ -20°C.
  • the graft base E. 2 generally has a mean particle size (d 50 value) of from 0.05 to 10 ⁇ m, preferably from 0.06 to 5 ⁇ m, particularly preferably from 0.1 to 1 ⁇ m.
  • the mean particle size (d 50 value) is the diameter above and below which in each case 50 wt. %of the particles lie. It can be determined by means of ultracentrifuge measurement (W. Scholtan, H. Lange, Kolloid-Z. und Z. Polymere 250 (1972) , 782-796) .
  • the graft base E. 2) is composite rubbers of silicone rubber and acrylate rubber, these two types of rubber being present, for example, in the form of a physical mixture or the silicone rubber and the acrylate rubber, for example, forming an interpenetrating network as a result of their preparation or, for example, the silicone rubber and the acrylate rubber forming a graft base that has a core-shell structure.
  • Preferred graft bases E. 2) are composite rubbers of from 10 to 70 wt. %, particularly preferably from 20 to 60 wt. %, silicone rubber and from 90 to 30 wt. %, particularly preferably from 80 to 40 wt. %, butyl acrylate rubber (the indicated wt. %is here based in each case on the graft base E. 2) .
  • the silicone-acrylate rubbers are preferably composite rubbers having graft-active sites, the silicone rubber and the acrylate rubber interpenetrating in the composite rubber so that they cannot substantially be separated from one another.
  • Silicone-acrylate rubbers are known and described, for example, in US 5,807,914, EP 430134 and US 4888388.
  • Silicone rubber components of the silicone-acrylate rubber according to E. 2 are preferably prepared by emulsion polymerisation, in which the siloxane monomer structural units, crosslinkers or branching agents (IV) and optionally grafting agents (V) are used.
  • siloxane monomer structural units for example and preferably, dimethylsiloxane or cyclic organosiloxanes having at least 3 ring members, preferably from 3 to 6 ring members, such as, for example and preferably, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyl-triphenyl-cyclotrisiloxane, tetramethyl-tetraphenyl-cyclotetrasiloxane, octaphenylcyclotetrasiloxane.
  • dimethylsiloxane or cyclic organosiloxanes having at least 3 ring members, preferably from 3 to 6 ring members, such as, for example and preferably, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, deca
  • the organosiloxane monomers can be used on their own or in the form of mixtures of 2 or more monomers.
  • the silicone rubber preferably contains not less than 50 wt. %and particularly preferably not less than 60 wt. %organosiloxane, based on the total weight of the silicone rubber component.
  • crosslinkers or branching agents (IV) there are preferably used silane-based crosslinkers having a functionality of 3 or 4, particularly preferably 4.
  • Preferred examples which may be mentioned include: trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane and tetrabutoxysilane.
  • the crosslinker can be used on its own or in a mixture of two or more. Tetraethoxysilane is particularly preferred.
  • the crosslinker is used in an amount in the range from 0.1 to 40 wt. %, based on the total weight of the silicone rubber component.
  • the amount of crosslinker is so chosen that the degree of swelling of the silicone rubber, measured in toluene, is from 3 to 30, preferably from 3 to 25 and particularly preferably from 3 to 15.
  • the degree of swelling is defined as the weight ratio of the amount of toluene absorbed by the silicone rubber when it is saturated with toluene at 25°C and the amount of silicone rubber in the dry state. The determination of the degree of swelling is described in detail in EP 249964.
  • Tetrafunctional branching agents are preferred to trifunctional branching agents because the degree of swelling can then more easily be controlled within the above-described limits.
  • Suitable grafting agents (V) are compounds that are capable of forming structures of the following formulae:
  • CH 2 CH-SiR 1 n O (3-n) /2 (V-2) or
  • R 1 represents C 1 -C 4 -alkyl, preferably methyl, ethyl or propyl, or phenyl,
  • R 2 represents hydrogen or methyl
  • n denotes 0, 1 or 2 and
  • p denotes an integer from 1 to 6.
  • Acryloyl-or methacryloyl-oxysilanes are particularly suitable for forming the above-mentioned structure (V-1) and have a high grafting efficiency. Effective formation of the graft chains is thereby ensured, and the impact strength of the resulting resin composition is accordingly promoted.
  • Preferred examples which may be mentioned include: ⁇ -methacryloyloxy-ethyldimethoxymethyl-silane, ⁇ -methacryloyloxy-propyl-methoxydimethyl-silane, ⁇ -methacryloyloxy-propyldimethoxymethyl-silane, ⁇ -meth-acryloyloxy-propyltrimethoxy-silane, ⁇ -methacryloyloxy-propylethoxydiethyl-silane, ⁇ -methacryloyloxy-propyldiethoxymethyl-silane, ⁇ -methacryloyl-oxy-butyldiethoxy-methyl-silane or mixtures thereof.
  • the silicone rubber can be prepared by emulsion polymerisation, as described, for example, in US 2891920 and US 3294725.
  • the silicone rubber is thereby obtained in the form of an aqueous latex.
  • a mixture containing organosiloxane, crosslinker and optionally grafting agent is mixed with water, with shearing, for example by means of a homogeniser, in the presence of an emulsifier based, in a preferred embodiment, on sulfonic acid, such as, for example, alkylbenzenesulfonic acid or alkylsulfonic acid, the mixture polymerising completely to give the silicone rubber latex.
  • An alkylbenzenesulfonic acid is particularly suitable because it acts not only as an emulsifier but also as a polymerisation initiator.
  • a combination of the sulfonic acid with a metal salt of an alkylbenzenesulfonic acid or with a metal salt of an alkylsulfonic acid is advantageous because the polymer is thereby stabilised during the subsequent graft polymerisation.
  • the reaction is ended by neutralising the reaction mixture by adding an aqueous alkaline solution, for example by adding an aqueous sodium hydroxide, potassium hydroxide or sodium carbonate solution.
  • an aqueous alkaline solution for example by adding an aqueous sodium hydroxide, potassium hydroxide or sodium carbonate solution.
  • Suitable polyalkyl (meth) acrylate rubber components of the silicone-acrylate rubbers according to E. 2 can be prepared from methacrylic acid alkyl esters and/or acrylic acid alkyl esters, a crosslinker and a grafting agent.
  • methacrylic acid alkyl esters and/or acrylic acid alkyl esters include the C 1 -to C 8 -alkyl esters, for example methyl, ethyl, n-butyl, tert-butyl, n-propyl, n-hexyl, n-octyl, n-lauryl and 2-ethylhexyl esters; haloalkyl esters, preferably halo-C 1 -C 8 -alkyl esters, such as chloroethyl acrylate, and mixtures of these monomers. n-Butyl acrylate is particularly preferred.
  • crosslinkers for the polyalkyl (meth) acrylate rubber component of the silicone-acrylate rubber there can be used monomers having more than one polymerizable double bond.
  • Preferred examples of crosslinking monomers are esters of unsaturated monocarboxylic acids having from 3 to 8 carbon atoms and unsaturated monohydric alcohols having from 3 to 12 carbon atoms, or saturated polyols having from 2 to 4 OH groups and from 2 to 20 carbon atoms, such as ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1, 3-butylene glycol dimethacrylate and 1, 4-butylene glycol dimethacrylate.
  • the crosslinkers can be used on their own or in mixtures of at least two crosslinkers.
  • grafting agents examples include allyl methacrylate, triallyl cyanurate, triallyl isocyanurate or mixtures thereof. Allyl methacrylate can also be used as crosslinker.
  • the grafting agents can be used on their own or in mixtures of at least two grafting agents.
  • the amount of crosslinker and grafting agent is from 0.1 to 20 wt. %, based on the total weight of the polyalkyl (meth) acrylate rubber component of the silicone-acrylate rubber.
  • the silicone-acrylate rubber is prepared by first preparing the silicone rubber according to E. 2.1 in the form of an aqueous latex.
  • the latex is then enriched with the methacrylic acid alkyl esters and/or acrylic acid alkyl esters that are to be used, the crosslinker and the grafting agent and a polymerisation is carried out.
  • Preference is given to an emulsion polymerisation initiated by radicals, for example by a peroxide, an azo or a redox initiator.
  • a redox initiator system especially of a sulfoxylate initiator system prepared by combination of iron sulfate, disodium ethylenediaminetetraacetate, rongalite and hydroperoxide.
  • the grafting agent that is used in the preparation of the silicone rubber has the effect of bonding the polyalkyl (meth) acrylate rubber component covalently to the silicone rubber component.
  • the two rubber components interpenetrate and thus form the composite rubber, which can no longer be separated into its constituents of silicone rubber component and polyalkyl (meth) acrylate rubber component after the polymerisation.
  • the monomers E. 1 are grafted on to the rubber base E. 2.
  • the graft polymerisation is carried out according to the following polymerisation method:
  • the desired vinyl monomers E. 1 are polymerised on to the graft base, which is present in the form of an aqueous latex.
  • the grafting efficiency should thereby be as high as possible and is preferably greater than or equal to 10%.
  • the grafting efficiency is significantly dependent on the grafting agent that is used.
  • the aqueous latex is added to hot water, in which metal salts, such as, for example, calcium chloride or magnesium sulfate, have previously been dissolved.
  • the silicone (acrylate) graft rubber thereby coagulates and can subsequently be separated.
  • Component E) may be selected from impact modifiers usually used in the industry, and silicone-acrylic rubber or silicone rubber based with grafted shell of methyl methacrylate (MMA) or MMA styrene copolymer are preferred, for example Metablen SX-005 and Metablen S-2030 from Mitsubishi Chemicals.
  • MMA methyl methacrylate
  • MMA styrene copolymer grafted shell of methyl methacrylate (MMA) or MMA styrene copolymer
  • Component F mineral fillers
  • the polycarbonate compositions provided in this present invention comprise, as component F) , 1-7 wt. %, preferably 2-6 wt. %, more preferably 2-5 wt. %of mineral fillers, based on the total weight of the polycarbonate compositions.
  • the polycarbonate compositions comprise mineral fillers as component F.
  • mineral fillers are mica, talc, calcium carbonate, dolomite, wollastonite, barium Sulfate, silica, kaolin, feldspar, barytes, or the like, or a combination comprising at least one of the foregoing mineral fillers, and preferably the mineral fillers are selected from the group of kaolin and talc. Kaolin is more preferred as mineral fillers in this invention.
  • the mineral fillers may have an average particle size (d 50 value) of 0.1 to 20 micrometers, specifically 0.5 to 10 micrometers, and more specifically 1 to 3 micrometers.
  • An exemplary mineral filler is talc having an average particle size (d50 value) of 1 to 3 micrometers.
  • the average particle size (d50 value) of the mineral fillers can be determined by means of ultracentrifuge measurement (W. Scholtan, H. Lange, Kolloid, Z. und Z. Polymere 250 (1972) , 782-l796) .
  • the mineral filler are present in amounts of 1-7 wt. %, preferably 2-6 wt. %, more preferably 2-5 wt. %, based on the total weight of the polycarbonate composition.
  • An exemplary mineral filler of talc in the present invention is 2-6 wt. %, based on the total weight of the polycarbonate composition.
  • An exemplary mineral filler of kaolin in the present invention is 2-5 wt. %, based on the total weight of the polycarbonate composition.
  • the polycarbonate compositions can comprise further conventional polymer additives, such as flame-retardant synergists, lubricants and demoulding agents (for example pentaerythritol tetrastearate) , nucleating agents, stabilizers (for example UV/light stabilizers, heat stabilizers, antioxidants, transesterification inhibitors, hydrolytic stabilizers) , antistatics (for example conductive blacks, carbon fibres, carbon nanotubes as well as organic antistatics such as polyalkylene ethers, alkyl sulfonates or polyamide-containing polymers) as well as colourants, and pigments.
  • flame-retardant synergists for example pentaerythritol tetrastearate
  • nucleating agents for example UV/light stabilizers, heat stabilizers, antioxidants, transesterification inhibitors, hydrolytic stabilizers
  • antistatics for example conductive blacks, carbon fibres, carbon nanotubes as well as
  • sterically hindered phenols and phosphites or mixtures thereof such as, for example, B900 (Ciba Specialty Chemicals) .
  • Pentaerythritol tetrastearate is preferably used as the demoulding agent.
  • Carbon black is further preferably used as a black pigment (e.g. Blackpearls) .
  • particularly preferred moulding compositions comprise a demoulding agent, particularly 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, particularly preferably from 0.3 to 0.8 parts by weight.
  • particularly preferred moulding compositions comprise at least one stabilizer, for example selected from the group of the sterically hindered phenols, phosphites and mixtures thereof and particularly preferably B900, in an amount of from 0.01 to 0.5 part by weight, preferably from 0.03 to 0.4 part by weight, particularly preferably from 0.06 to 0.3 part by weight.
  • PTFE pentaerythritol tetrastearate and Irganox B900 with a phosphorus-based flame retardant is also particularly preferred.
  • Another object of this invention is to provide a process for preparing polycarbonate compositions, comprising the step of blending a group of components comprising
  • the components can be blended with following steps:
  • Component F can be added either in step 1) or in step 2) .
  • This present invention also provides articles manufactured from the polycarbonate compositions provided by this invention.
  • the polycarbonate compositions reach a good balanced strict application requirements of good impact performance, high flame retardance and high stiffness.
  • the polycarbonate compositions could be used for many applications with strict application requirements, in particularly in the application of producing the luggage support racks used in high speed trains.
  • polycarbonate compositions in the comparative Examples and the inventive Examples in the present invention were prepared according to the following process:
  • melt temperature 300°C melt temperature 300°C, mold temperature 80°C, injection pressure 1000-2400 bar
  • the amount in percent of each component refers to the weight percent of the component relative to the resulting polycarbonate composition, with the total weight of polycarbonate compositions as being 100 wt. %.
  • Test samples corresponding to the resulting polycarbonate composition granules were produced according to the requirements of the test standards in Tables 1-3, and the corresponding tests were carried out according to the corresponding test standards listed in Tables 1-3.
  • comparative examples C1-C7 comprise no component E (i.e. impact modifiers) and comprise no component F (i.e. mineral filler) .
  • comparative examples C1-C3 comprise no component B (i.e. polysiloxane-polycarbonate copolymer) .
  • Comparative example C7 comprises no component D (i.e. FR agent phosphazene) .
  • comparative examples C8-C11 comprise no component F.
  • Comparative examples C12-C13 comprise no component B and E.
  • Comparative examples C14-C15 comprise no component D.
  • Comparative examples C16 comprises 6%of impact modifier which is more than that required in the present invention.
  • Comparative examples C17 comprises 8%of mineral fillers which is more than that required in the present invention.
  • the polycarbonate compositions by combining 37.05 wt. %of polycarbonate, 30 wt. %of polysiloxane-polycarbonate copolymer, 25wt. %of glass fibers, 2.5wt. %of phosphazene compound, 2 wt. %of impact modifier, and 3 wt. %of mineral filler, as well as other components of anti-dropping agent and mold release agent, reached the flame-retardant level of both UL94 5VB@2.0mm and V0@1.0mm &1.5mm requirements (testing conditions: 23 °C and 2 days) . Meanwhile, its flexural modulus reached 6.72 ⁇ 10 3 MPa (2mm/min, according to ISO178: 2010) and its Izod notched impact strength reached 14 kJ/m 2 (23 °C, 3mm, 5.5J) .
  • inventive example E2 As shown in Table 3, by changing the mineral filler from kaolin in inventive example 1 to talc, the polycarbonate compositions also reached good performances in flame retardance, high modulus and impact performances. Compared to comparative examples C10 and C11, inventive examples E1 and E2 showed the unique effect of mineral fillers on the FR performance. Comparing with comparative examples C14 and C15, inventive examples E1 and E2 exhibited the advantage of FR agent phosphazene over other phosphorus solid FR agents (PX-200 and Sol-DP) on the FR performance.
  • inventive examples E3-E5 the contents of polycarbonate, polysiloxane-polycarbonate copolymer, and phosphazene compound were changed within the scope of this invention and all of polycarbonate compositions had shown good performances in flame retardance, high modulus and impact performances.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne des compositions de polycarbonate et des articles moulés avec celles-ci. Les compositions de polycarbonate selon la présente invention comprennent : A) 25 à 60 % en poids d'un polycarbonate, B) 10 à 40 % en poids d'un copolymère polysiloxane-polycarbonate, C) 20 à 30 % en poids de fibres de verre, D) 1 à 5 % en poids d'un composé phosphazène, E) 1 à 5 % en poids d'un agent antichoc, et F) 1 à 7 % en poids d'une charge minérale, tous les pourcentages en poids sauf indication contraire étant basés sur le poids total de la composition de polycarbonate. Les compositions de polycarbonate selon la présente invention atteignent des exigences d'application strictes bien équilibrées de bonnes performances d'impact lors d'une application stricte, une grande résistance à la flamme et une grande rigidité et peuvent être utilisées pour de nombreuses applications avec des exigences d'application strictes, en particulier dans l'application de la production des porte-bagages utilisés dans des trains à grande vitesse.
PCT/CN2018/119970 2018-12-10 2018-12-10 Compositions de polycarbonate WO2020118478A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201880100048.6A CN113366061B (zh) 2018-12-10 2018-12-10 聚碳酸酯组合物
PCT/CN2018/119970 WO2020118478A1 (fr) 2018-12-10 2018-12-10 Compositions de polycarbonate

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2018/119970 WO2020118478A1 (fr) 2018-12-10 2018-12-10 Compositions de polycarbonate

Publications (1)

Publication Number Publication Date
WO2020118478A1 true WO2020118478A1 (fr) 2020-06-18

Family

ID=71076689

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2018/119970 WO2020118478A1 (fr) 2018-12-10 2018-12-10 Compositions de polycarbonate

Country Status (2)

Country Link
CN (1) CN113366061B (fr)
WO (1) WO2020118478A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3929248A1 (fr) * 2020-06-26 2021-12-29 SHPP Global Technologies B.V. Compositions de polycarbonate dotées de propriétés ignifuges à paroi mince et article façonné associé
US11634578B2 (en) * 2018-11-29 2023-04-25 Covestro Intellectual Property Gmbh & Co. Kg SiCoPC blend containing phosphazene and silicone/acrylate impact modifier

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115746535B (zh) * 2022-12-08 2024-04-12 无锡赢同新材料科技有限公司 一种高模量高韧性薄壁阻燃聚碳酸酯复合材料及其制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014195874A1 (fr) * 2013-06-04 2014-12-11 Sabic Innovative Plastics Ip B.V. Mélanges de compositions thermoplastiques ayant une résistance au choc et un écoulement améliorés
WO2016174592A1 (fr) * 2015-04-30 2016-11-03 Sabic Global Technologies B.V. Composition ignifuge, procédé pour la fabriquer et articles la comprenant

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8552096B2 (en) * 2009-07-31 2013-10-08 Sabic Innovative Plastics Ip B.V. Flame-retardant reinforced polycarbonate compositions
US9018286B2 (en) * 2012-05-24 2015-04-28 Sabic Global Technologies B.V. Flame retardant polycarbonate compositions, methods of manufacture thereof and articles comprising the same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014195874A1 (fr) * 2013-06-04 2014-12-11 Sabic Innovative Plastics Ip B.V. Mélanges de compositions thermoplastiques ayant une résistance au choc et un écoulement améliorés
WO2016174592A1 (fr) * 2015-04-30 2016-11-03 Sabic Global Technologies B.V. Composition ignifuge, procédé pour la fabriquer et articles la comprenant

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11634578B2 (en) * 2018-11-29 2023-04-25 Covestro Intellectual Property Gmbh & Co. Kg SiCoPC blend containing phosphazene and silicone/acrylate impact modifier
EP3929248A1 (fr) * 2020-06-26 2021-12-29 SHPP Global Technologies B.V. Compositions de polycarbonate dotées de propriétés ignifuges à paroi mince et article façonné associé
WO2021260621A1 (fr) * 2020-06-26 2021-12-30 Shpp Global Technologies B.V. Compositions de polycarbonate dotées de propriétés ignifuges pour paroi mince et article façonné associé

Also Published As

Publication number Publication date
CN113366061B (zh) 2023-06-13
CN113366061A (zh) 2021-09-07

Similar Documents

Publication Publication Date Title
KR101726455B1 (ko) 방염 충격 강도 개질된 폴리카르보네이트 조성물
TWI466946B (zh) 阻燃的經衝擊性改質之聚碳酸酯組成物
KR102136909B1 (ko) 난연성 폴리카르보네이트 성형 물질 vi
KR101908170B1 (ko) 충격 인성, 유동성 및 내화학약품성이 우수한 난연성 pc/abs 조성물
CN100408629C (zh) 阻燃的聚碳酸酯模塑组合物
RU2448993C2 (ru) Ударопрочная огнестойкая термопластичная формовочная композиция
KR101531073B1 (ko) 내충격성 난연성 열가소성 성형 조성물
CN111133053B (zh) 聚碳酸酯组合物
CN113366061B (zh) 聚碳酸酯组合物
EP4153681B1 (fr) Composition de polycarbonate ignifuge
CN111465652B (zh) 具有良好阻燃性的聚碳酸酯组合物
JP2022510884A (ja) ホスファゼン及びシリコーン／アクリレート耐衝撃性改質剤を含有するＳｉＣｏＰＣブレンド
KR102136908B1 (ko) 난연성 폴리카르보네이트 성형 물질 iv
KR101614559B1 (ko) 내충격-개질된 폴리카르보네이트 조성물
KR20180056678A (ko) 난연성 폴리카보네이트 조성물, 이의 제조 및 사용 방법
KR20120101656A (ko) 폴리카보네이트 수지 조성물
EP4153682B1 (fr) Composition de polycarbonate ignifuge
EP4093823A1 (fr) Compositions de polycarbonate
KR20150126848A (ko) 난연성 폴리카르보네이트

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18942839

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18942839

Country of ref document: EP

Kind code of ref document: A1