WO2016197906A1 - 一种聚碳酸酯组合物及其制备方法 - Google Patents

一种聚碳酸酯组合物及其制备方法 Download PDF

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WO2016197906A1
WO2016197906A1 PCT/CN2016/085077 CN2016085077W WO2016197906A1 WO 2016197906 A1 WO2016197906 A1 WO 2016197906A1 CN 2016085077 W CN2016085077 W CN 2016085077W WO 2016197906 A1 WO2016197906 A1 WO 2016197906A1
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parts
polycarbonate
copolymer
island structure
flame retardant
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French (fr)
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董相茂
岑茵
佟伟
艾军伟
李明昆
何继辉
孙东海
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Kingfa Science and Technology Co Ltd
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Kingfa Science and Technology Co Ltd
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    • 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
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • 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
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • 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
    • 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
    • C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods

Definitions

  • the invention relates to the technical field of engineering plastics, in particular to a polycarbonate composition and a preparation method thereof.
  • Polycarbonate PC has high impact resistance and heat resistance. In order to improve its processing properties and sensitivity to notch impact, it is usually added to rubber-modified polymers such as ABS, MBS, etc., especially PC.
  • PC/ABS alloy with ABS as the main raw material is an important engineering plastic, which can improve the heat resistance and tensile strength of ABS, on the other hand, it can reduce the viscosity of PC melt, improve the processing performance and reduce the stress inside the product. And the sensitivity of the impact strength to the thickness of the product.
  • Patent US20130079443A1 discloses a method for improving a PC/ABS resin alloy.
  • the use of maleic anhydride grafted ethylene propylene rubber improves the impact strength of the mixture, but the use of the toughening agent affects the strength of the material and increases the material cost.
  • the addition of rubber also has a negative impact on flame retardancy.
  • the polybutadiene copolymer structure in the butadiene copolymer component in the polycarbonate composition exhibits a large island structure rubber phase, and there are further 1 to 50 inside the large island structure rubber phase.
  • the effect of the small island structure, in which 90% and 90% of the large island structure rubber phase and its inner smallest long-path small island structure have a length-to-diameter ratio of 1.01-80 on the impact strength of the polycarbonate composition has not been reported.
  • a butadiene copolymer component is selected in the polycarbonate composition formulation, in which the polybutadiene copolymer structure exhibits a large island structure rubber phase in the large island structure. There are further 1 to 50 small island structures inside the rubber phase, 90% and 90% of the sea.
  • the aspect ratio of the island structure rubber phase to the inner smallest long diameter small island structure is 1.01-80, the rubber phase can well induce the silver streak and terminate the silver streak, thereby further improving the toughness of the polycarbonate composition.
  • the impact strength can significantly improve the impact strength of the polycarbonate composition without affecting its flame retardancy, fluidity, and heat resistance, and is particularly suitable for applications where the use environment is relatively high.
  • Another object of the present invention is to provide a process for the preparation of the above polycarbonate composition.
  • a polycarbonate composition comprising, by weight, the following composition
  • the sum of the weight components of the four components a, b, c, and d is 100 parts.
  • a polycarbonate composition by weight, comprises the following composition:
  • the structure of polybutadiene copolymer in the butadiene copolymer component exhibits a large island structure rubber phase, and there are further 1 to 50 small island structures in the rubber phase of the large island structure, of which 90% and 90% are large and small.
  • the long-diameter ratio of the large island structure rubber phase to the inner smallest long-path small island structure in the island structure is 1.01-80.
  • a polycarbonate composition by weight, comprises the following composition:
  • the structure of the polybutadiene copolymer in the butadiene copolymer component exhibits a large island structure rubber phase, and there are further 1 to 50 small island structures in the rubber phase of the large island structure, of which 90% and 90% are large.
  • the aspect ratio of the island structure rubber phase to its inner smallest long diameter small island structure is 1.01-80.
  • the sea-island structure having a long-diameter ratio of the large island structure rubber phase to the inner smallest long-path small island structure of 1.01-80 is 92% or more, and more preferably 94% or more in all sea-island structures.
  • the large island structure rubber phase means that the polybutadiene structure (ie rubber phase) in the butadiene copolymer component is dyed by the dye ruthenium tetroxide (RuO 4 ) or osmium tetroxide (OsO 4 ) in a transmission electron micrograph. It exhibits a large island structure with a long diameter range of 50 nm to 2000 nm, which is a rubber phase dyed by a dyeing agent, exhibiting a large island structure as shown in FIG.
  • RuO 4 ruthenium tetroxide
  • OsO 4 osmium tetroxide
  • the small island structure rubber phase means that the polybutadiene structure (ie rubber phase) in the butadiene copolymer component is dyed by the dye ruthenium tetroxide (RuO 4 ) or osmium tetroxide (OsO 4 ) in a transmission electron micrograph. It presents 1 to 50 small island structures in the large island structure, with a long diameter ranging from 10 nm to 1500 nm. It is a non-rubber phase in the large island structure (ie rubber phase) that cannot be dyed by the dye.
  • the carbonate phase or other copolymer grafted with the polybutadiene rubber exhibits a small island structure as shown in FIG.
  • the test method for the aspect ratio of the large island structure rubber phase and the smallest long-path small island structure in the butadiene copolymer component is dyed by the dyeing agent ruthenium tetroxide (RuO 4 ) or osmium tetroxide (OsO 4 ).
  • RuO 4 ruthenium tetroxide
  • OsO 4 osmium tetroxide
  • the transmission electron micrograph the small island structure existing in the large island structure is presented.
  • the TEM image is imported into Photoshop or Nano measurer image processing software, and the software is tested by comparing the scale scale in the transmission electron microscope image.
  • the long diameter of the specific large island rubber phase and the smallest long diameter small island long diameter are obtained. Dividing the measured long diameter of the large island structure by the longest diameter of the small island structure is the ratio of the specific long diameter of the rubber phase of the large island structure to the specific long diameter of the smallest long diameter small island structure in the interior.
  • the test method for the ratio of the size of the island to the length to diameter ratio of 1.01-80 refers to the use of transmission electron microscopy to photograph the butadiene copolymer treated by the above method, and randomly obtains a transmission electron micrograph of a plurality of different regions.
  • the length-to-diameter ratio of each size of the island structure in the transmission electron microscope is measured one by one, and the length-to-diameter ratio of the island structure with 500 specific sizes is obtained by random measurement, and the aspect ratio is 1.01-80.
  • the number of island structures divided by 500 is the ratio of the size of the island structure to the fixed aspect ratio range.
  • the large island structure rubber phase has a long diameter of 50 nm to 2000 nm.
  • the butadiene copolymer is selected from the group consisting of bulk, emulsion, and bulk-suspension polymerization. One or several of the copolymers.
  • the butadiene copolymer in parts by weight, is selected from the group consisting of the following graft copolymers of b.1 on b.2:
  • B.1.1 50 parts - 95 parts of styrene, styrene derivatives such as ⁇ -methylstyrene, p-benzyl styrene, divinyl styrene, C1-C8-alkyl methacrylate, acrylic acid One or more of a C1-C8-alkyl ester, a dimethylsiloxane, a phenylsiloxane, a polyalkylsiloxane;
  • the butadiene copolymer is selected from the group consisting of styrene-butadiene-styrene block copolymer SBS, acrylonitrile-butadiene-styrene graft copolymer ABS, methyl methacrylate-acrylonitrile
  • SBS styrene-butadiene-styrene block copolymer
  • MABS acrylonitrile-butadiene-styrene graft copolymer
  • MBS methyl methacrylate-butadiene-styrene graft copolymer
  • ABS more preferably acrylonitrile-butadiene-styrene graft copolymerization ABS
  • the particle size of MBS is preferably 0.1 um to 0.5 um
  • the bulk particle size ABS particle size is preferably 0.1 um to 2 um
  • ABS particle size is preferably 0.05 um to 0.2 um.
  • ABS resin acrylonitrile-butadiene-styrene copolymer
  • ABS resin thermoplastic graft copolymer obtained by graft-polymerizing a butadiene rubber component with acrylonitrile and styrene, and acrylonitrile. a mixture of styrene copolymers.
  • the polycarbonate is selected from the group consisting of a polycarbonate prepared by an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer. Or several. A particularly preferred method thereof will be described in detail below.
  • a method of producing a polycarbonate resin by an interfacial polymerization method will be described.
  • a dihydroxy compound and a carbonate precursor preferably phosgene
  • an inert organic solvent and an aqueous alkali solution Usually, the pH is maintained at 9 or more, and then interfacial polymerization is carried out in the presence of a polymerization catalyst to obtain a polycarbonate resin.
  • a molecular weight modifier (chain terminator) and an antioxidant which prevents oxidation of the dihydroxy compound may also be present in the reaction system as needed.
  • phosgene Dihydroxy compounds and carbonate precursors have been listed above.
  • the use of phosgene as a carbonate precursor is Particularly preferred, and such a method in which phosgene is used is particularly referred to as phosgene process.
  • inert organic solvent examples include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene and dichlorobenzene; and aromatic hydrocarbons such as benzene, toluene and xylene.
  • chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene and dichlorobenzene
  • aromatic hydrocarbons such as benzene, toluene and xylene.
  • An organic solvent may be used, or two or more kinds thereof may be used together in a desired combination and ratio.
  • alkali compound contained in the aqueous alkali solution examples include alkali metal compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and sodium hydrogencarbonate; and alkaline earth metal compounds. Sodium hydroxide and potassium hydroxide are preferred. An alkali compound may be used, or two or more kinds thereof may be used together in a desired combination and ratio.
  • the concentration of the alkali compound in the aqueous alkali solution is not limited herein, it is usually used in an amount of from 5 wt% to 10 wt% to control the pH of the aqueous alkali solution during the reaction to be 10-12.
  • the molar ratio of the bisphenol compound to the alkali compound is usually set to 1:1.9 or more, and preferably 1:2.0 or more, but 1:3.2 or less, and preferably 1:2.5 or less.
  • the pH of the aqueous phase is controlled to be 10-12, preferably 10-11.
  • polymerization catalyst examples include aliphatic tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, and trihexylamine; and alicyclic tertiary amines such as N,N'-dimethylcyclohexylamine and N , N'-diethylcyclohexylamine, etc.; aromatic tertiary amines such as N, N'-dimethylaniline and N, N'-diethylaniline; quaternary ammonium salts such as trimethylbenzyl chloride Ammonium, tetramethylammonium chloride and triethylbenzylammonium chloride; pyridine; guanine; A polymerization catalyst may be used, or two or more kinds thereof may be used together in a desired combination and ratio.
  • aliphatic tertiary amines such as trimethylamine, triethylamine, tributylamine
  • the molecular weight modifier examples include aromatic phenols having a monovalent phenolic hydroxyl group; aliphatic alcohols such as methanol and butanol; mercaptans; and phthalimides; and the like, and among these, aromatic A phenol is preferred.
  • aromatic phenols include alkyl-substituted phenols such as m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, p-tert-butylphenol, and p-long-chain alkyl-substituted phenol.
  • Etc. a vinyl group-containing phenol such as isopropenyl phenol; an epoxy group-containing phenol; and a carboxyl group-containing phenol such as o-hydroxybenzoic acid and 2-methyl-6-hydroxyphenylacetic acid.
  • a vinyl group-containing phenol such as isopropenyl phenol
  • an epoxy group-containing phenol such as isopropenyl phenol
  • a carboxyl group-containing phenol such as o-hydroxybenzoic acid and 2-methyl-6-hydroxyphenylacetic acid.
  • One type of molecular weight modifier may be used, or two or more kinds thereof may be used together in a desired combination and ratio.
  • the amount of the molecular weight modifier is usually 0.5 mol or more, and preferably 1 mol or more, per 100 mol of the dihydroxy compound, but is usually 50 mol or less, and preferably 30 mol or less. Setting the amount of the molecular weight modifier to this range can improve the thermal stability and hydrolysis resistance of the polycarbonate resin composition.
  • reaction substrate, reaction medium, catalyst, additives, and the like may be mixed together in any desired order during the reaction as long as the desired polycarbonate resin can be obtained, and a suitable order can be established as needed.
  • the molecular weight regulator can be used in the dihydroxy compound.
  • the phosgene reaction (phosgenation) is added at any desired timing between the time of the polymerization reaction and the start of the polymerization reaction.
  • the reaction temperature is usually set to 0 to 40 ° C, and the reaction time is usually in the range of several minutes (for example, 10 minutes) to several hours (for example, 6 hours).
  • examples of the carbonic acid diester include a dialkyl carbonate compound such as dimethyl carbonate, diethyl carbonate, and di-tert-butyl carbonate; diphenyl carbonate; and substituted diphenyl carbonate such as ditolyl carbonate. Wait. Among these, diphenyl carbonate and substituted diphenyl carbonate are preferred, and in particular, diphenyl carbonate is even more preferable.
  • One type of carbonic acid diester may be used, or two or more types thereof may be used together in a desired combination and ratio.
  • a desired ratio of the dihydroxy compound to the carbonic acid diester may be used, provided that the target polycarbonate resin can be obtained, but it is preferred to use 1 or more molar equivalents of diester carbonate per 1 mole of the dihydroxy compound, and 1.01 is used.
  • the above molar equivalents are even more preferred.
  • the upper limit is usually a molar equivalent of 1.30 or less.
  • the amount of terminal hydroxyl groups can be adjusted to a preferred range by setting the ratio of the two compounds within such a range.
  • the amount of terminal hydroxyl groups in the polycarbonate resin tends to greatly affect thermal stability, hydrolysis resistance, color tone, and the like.
  • the amount of terminal hydroxyl groups can be adjusted as desired by any well-known desired method.
  • a polycarbonate resin in which the amount of the terminal hydroxyl group is adjusted can be usually obtained by adjusting the mixing ratio between the carbonic acid diester and the aromatic dihydroxy compound, the degree of pressure reduction, and the like during the reaction. Further, the molecular weight of the obtained polycarbonate resin can usually also be adjusted by this process.
  • the above mixing ratio is used in the case where the amount of the terminal hydroxyl group is adjusted by adjusting the mixing ratio of the dicarbonate and the dihydroxy compound.
  • a method in which a chain terminator is separately added during the reaction can be mentioned as a more aggressive adjustment method.
  • the chain terminator during the process include, for example, a monovalent phenol, a monovalent carboxylic acid, a carbonic acid diester, and the like.
  • a chain terminator may be used, or two or more kinds thereof may be used together in a desired combination and ratio.
  • a transesterification catalyst is usually used. Any desired transesterification catalyst can be used. Among these, for example, the use of an alkali metal compound and/or an alkaline earth metal compound is preferred. Further, as the auxiliary compound, for example, a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, a basic amine compound or the like can be used. A transesterification catalyst may be used, or two or more kinds thereof may be used together in a desired combination and ratio.
  • the reaction temperature in the melt transesterification method is usually from 100 ° C to 320 ° C. Further, the reaction is usually carried out under reduced pressure of 2 mmHg or less.
  • the detailed procedure should be a process in which the melt polycondensation reaction is carried out under the above conditions while removing by-products such as aromatic hydroxy compounds and the like.
  • the melt polycondensation reaction can be carried out by a batch process or a continuous process.
  • the reaction substrate, the reaction medium, the catalyst, the additives and the like may be mixed together in any desired order as long as the target aromatic polycarbonate resin can be obtained, and a suitable order can be established as needed.
  • the catalyst deactivator can be used as needed in the melt transesterification process. Any desired compound that neutralizes the transesterification catalyst can be used as a catalyst deactivating agent. Examples include sulfur-containing organic compounds and derivatives thereof and the like. A catalyst deactivator may be used, or two or more kinds thereof may be used together in a desired combination and ratio.
  • the amount of the catalyst deactivator to be used is usually 0.5 parts by weight or more and preferably 1 part by weight or more, based on the alkali metal or alkaline earth metal contained in the transesterification catalyst, but should be usually 10 parts by weight or less, and preferably 5 parts by weight or less. Further, the concentration thereof is usually 1 ppm or more with respect to the aromatic polycarbonate resin, but is usually 100 ppm or less, and preferably 20 ppm or less.
  • the polycarbonate is selected from one or more of an aromatic polycarbonate, an aliphatic polycarbonate, an aromatic-aliphatic polycarbonate, and a branched polycarbonate; preferably an aromatic polycarbonate .
  • the aromatic polycarbonate is an aromatic polycarbonate having a viscosity average molecular weight of 13,000 to 40,000, more preferably an aromatic polycarbonate having a viscosity average molecular weight of 16,000 to 28,000, further preferably a viscosity average molecular weight of 17,000 to 24,000. Aromatic polycarbonate.
  • the viscosity average molecular weight is within the above range, the mechanical strength is good and excellent moldability can be maintained.
  • the viscosity average molecular weight was calculated by using a solution of dichloromethane as a solvent at a test temperature of 25 ° C.
  • the concentration of the terminal hydroxyl group in the polycarbonate resin is arbitrary, and can be selected and determined as needed, but is usually 1,000 ppm or less, preferably 800 ppm or less, and more preferably 600 ppm or less.
  • the lower limit of the concentration, in particular, in the case of a polycarbonate resin produced by a melt transesterification method is usually 10 ppm or more, preferably 30 ppm or more, and more preferably 40 ppm or more. The decrease in molecular weight can be prevented, whereby the mechanical properties of the polycarbonate resin composition can be further improved.
  • the unit of the terminal hydroxyl group concentration is expressed herein as ppm based on the mass of the terminal hydroxyl group relative to the mass of the polycarbonate resin. Colorimetric analysis by the carbon tetrachloride/acetic acid process is used as a measurement method (see Macromol. Chem., 88, 215, 1965).
  • the molecular weight of the polycarbonate resin is arbitrary, and may be appropriately selected and determined, but the viscosity average molecular weight [Mv] calculated from the viscosity of the liquid is usually from 13,000 to 40,000, preferably from 16,000 to 28,000, more preferably 17000-24000.
  • the mechanical strength of the polycarbonate resin composition of the present invention can be further improved by setting the viscosity average molecular weight to be at least the lower limit of the above range, and this is even more desirable when the composition is used for applications requiring high mechanical strength.
  • the viscosity average molecular weight is lower than the upper limit of the above range, the decrease in fluidity of the polycarbonate resin composition of the present invention can be controlled or improved, which improves moldability and promotes the thin wall molding method.
  • Two or more polycarbonate resins having different viscosity average molecular weights may be mixed and used together, and in this case, a polycarbonate resin having a viscosity average molecular weight outside the above preferred range may also be included in the mixture.
  • the concentration of the terminal hydroxyl group in the polycarbonate resin is arbitrary, and can be selected and determined as needed, but is usually 1,000 ppm or less, preferably 800 ppm or less, and more preferably 600 ppm or less. Therefore, the residual thermal stability and color tone of the polycarbonate resin composition of the present invention can be further improved.
  • the lower limit of the concentration in particular, in the case of a polycarbonate resin produced by a melt transesterification method, is usually 10 ppm or more, preferably 30 ppm or more, and more preferably 40 ppm or more. The decrease in molecular weight can be prevented, whereby the mechanical properties of the polycarbonate resin composition can be further improved.
  • the unit of the terminal hydroxyl group concentration is expressed herein as ppm based on the mass of the terminal hydroxyl group relative to the mass of the polycarbonate resin. Colorimetric analysis by a carbon tetrachloride/acetic acid process was used as a measurement method (see Macromol. Chem., 88, 215, 1965).
  • the polycarbonate resin can be used as a sole polycarbonate resin (wherein the term "single polycarbonate resin” is not limited to a mode including only one polycarbonate resin, for example, including a plurality of different monomer formulations and The mode of the polycarbonate resin of molecular weight), or it may be combined and used as an alloy (mixture) of a polycarbonate resin and different thermoplastic resins.
  • the polycarbonate resin can be constructed to have a copolymer of a polycarbonate resin as a main component thereof, such as a copolymer comprising an oligomer or a polymer containing a siloxane structure for the purpose of further improving flame retardancy and impact resistance; in order to further improve thermal oxidation stability
  • a copolymer of a monomer, an oligomer or a polymer containing a phosphorus atom include a copolymer of a monomer, an oligomer or a polymer containing a phosphorus atom; a monomer, an oligomer or a polymer comprising a dihydroxyanthracene structure for the purpose of improving thermal oxidative stability or a polymer; a copolymer comprising an olefin-based oligomer or polymer as represented by polystyrene; and a polyester resin oligomer for the purpose of improving chemical resistance for the purpose of improving optical properties; Or a copoly
  • the polycarbonate resin may also contain a polycarbonate oligomer for the purpose of improving the appearance of the molded article and improving fluidity.
  • the polycarbonate oligomer has a viscosity average molecular weight [Mv] of usually 1,500 or more, and preferably 2,000 or more, but is usually 9,500 or less, and preferably 9,000 or less. Further, it is preferable that the content of the polycarbonate oligomer contained is set to 30% by weight or less of the polycarbonate resin (including the polycarbonate oligomer).
  • the polycarbonate resin may be a polycarbonate resin (so-called recycled material polycarbonate resin) which is regenerated from a used manufactured product rather than an unused raw material.
  • used manufactured products include optical recording media such as optical disks, etc.; light guide plates; transparent automotive parts such as automobile window glass, automobile headlight glass and windshield, etc.; containers such as water bottles, etc.; spectacle lenses; and building materials such as baffles , glass windows, corrugated sheets; and so on.
  • a pulverized product or a molten pellet obtained from a defective product, a slag, a runner, or the like can also be used.
  • the recycled polycarbonate resin is preferably 80% by weight or less, and more preferably 50% by weight or less, of the polycarbonate resin contained in the polycarbonate resin composition of the present invention.
  • the recycled polycarbonate resin will most likely undergo deterioration due to heat or aging, and if such a polycarbonate resin is used in an amount larger than the above range, color tone and mechanical properties may be adversely affected.
  • the flame retardant is selected from the group consisting of a halogen-based flame retardant or a halogen-free flame retardant, preferably a halogen-free flame retardant;
  • the halogen-based flame retardant is selected from the group consisting of brominated polystyrene, brominated polyphenylene ether, and bromine Bisphenol A type epoxy resin, brominated styrene-maleic anhydride copolymer, brominated epoxy resin, brominated phenoxy resin, decabromodiphenyl ether, decabromobiphenyl, brominated polycarbonate Or one or more of perfluorotricyclopentadecane or brominated aromatic crosslinked polymer, preferably brominated polystyrene;
  • the halogen-free flame retardant is selected from the group consisting of nitrogen-containing flame retardants and phosphorus-containing resistors
  • One or more of a flammant or a flame retardant containing nitrogen and phosphorus is
  • the phosphorus-containing flame retardant is selected from the group consisting of monomers and oligomeric phosphates and phosphonates, phosphonate amines and phosphazenes, wherein one or more groups selected from the group may also be used.
  • a mixture of compounds preferably phosphorus Triphenyl acid ester, tricresyl phosphate, tolyl diphenyl phosphate, trimethylphenyl phosphate, tris(2,4,6-trimethylphenyl) phosphate, tris(2,4) -di-tert-butylphenyl)ester, tris(2,6-di-tert-butylphenyl)phosphate, resorcinol bis(diphenyl phosphate), hydroquinone bis(diphenyl phosphate) ), bisphenol A-bis (diphenyl phosphate), resorcinol bis (2,6-di-tert-butylphenyl phosphate), hydroquinone bis (2,6-dimethylphenyl) One or more of phosphates.
  • auxiliary agents may be appropriately added as needed, and the other auxiliary agents are selected from the group consisting of heat stabilizers, antioxidants, and anti-drip agents.
  • heat stabilizers one or more of a falling agent, a light stabilizer, a plasticizer, a filler, and a coloring agent.
  • Suitable heat stabilizers include organic phosphites such as triphenyl phosphite, tris-(2,6-dimethylphenyl) phosphite, tri-decylphenyl phosphite, dimethylphenylphosphine. Acid ester, trimethyl phosphate, and the like.
  • Suitable antioxidants include organic phosphites, alkylated monohydric or polyhydric phenols, alkylation products of polyphenols and dienes, butylated reaction products of p-cresol or dicyclopentadiene, alkane Alkalized hydroquinones, hydroxylated thiodiphenyl ethers, alkylene-bisphenols, benzyl compounds, polyol esters, and the like.
  • Suitable anti-drip agents are preferably fluorinated polyolefins, which are well known (see for example EP-A 640 655). Commercially available products such as those from DuPont 30N.
  • Suitable light stabilizers include one or more combinations of benzotriazoles, benzophenones.
  • a suitable plasticizer is a phthalate.
  • Suitable fillers include titanium dioxide, talc, mica and barium sulfate.
  • Suitable colorants include various pigments, dyes.
  • the preparation method of the above polycarbonate composition comprises the following steps:
  • the aspect ratio of the inner large island structure rubber phase and the inner smallest long-path small island structure of the butadiene copolymer structure is in the range of 1.01-80, and the type of island structure accounts for more than 90% of butadiene copolymerization.
  • All ingredients may be added to the processing system first, or some additives may be premixed with one or more of the major components.
  • the flame retardant composition can be dry blended to form a mixture in a device such as a Henschel mixer or a Waring blender prior to feeding to the extruder, wherein the mixture is molten Blended.
  • a portion of the polycarbonate composition can be premixed with a flame retardant to form a dry premix. The dry premix is then melt blended with the remaining polycarbonate composition in an extruder.
  • some of the flame retardant composition may be fed first at the mouth of the extruder while the remainder of the flame retardant composition is fed downstream through the port of the mouth.
  • Blending of the flame retardant composition includes using a combination of shear, tensile, compressive, ultrasonic, electromagnetic, thermal, or at least one of the above-described forces or forms of energy, and is performed in a processing facility , by single screw, multi-screw, meshing co-rotating or counter-rotating screw, non-intermeshing co-rotating or counter-rotating screw, reciprocating screw, screw with pin, barrel with pin, roller, ram
  • Blending involving the above forces can be carried out in machines such as single or multi-screw extruders, Buss kneaders, Henschel mixers, spiral mixers, Ross mixers, internal mixers (Banbury), roll mills, molding The machine (such as an injection molding machine, a vacuum molding machine, a blow molding machine) or the like, or a combination comprising at least one of the above machines.
  • machines such as single or multi-screw extruders, Buss kneaders, Henschel mixers, spiral mixers, Ross mixers, internal mixers (Banbury), roll mills, molding The machine (such as an injection molding machine, a vacuum molding machine, a blow molding machine) or the like, or a combination comprising at least one of the above machines.
  • the flame retardant composition can be introduced into the melt blending unit as a masterbatch.
  • a portion of the polycarbonate composition can be pre-blended with a phosphate flame retardant to form a masterbatch, and then the masterbatch is blended with the remaining ingredients to form a flame retardant composition.
  • the masterbatch can be introduced into a blending device downstream of the location where the remaining components of the flame retardant composition are introduced.
  • the polycarbonate compositions of the present invention are useful in the preparation of molded articles such as durable articles, electrical and electronic components, automotive parts, and the like.
  • the composition can be converted into articles using common thermoplastic processes such as film and sheet extrusion, injection molding, gas assisted injection molding, extrusion molding, compression molding, and blow molding.
  • the polycarbonate composition of the present invention can be used for outdoor and indoor applications, such as mobile phones, since it can significantly improve the impact strength of the polycarbonate composition without affecting its flame retardancy, fluidity, and heat resistance.
  • the invention has the following beneficial effects:
  • the present invention overcomes the conventional rubber-modified graft copolymer by using a composition obtained by blending a butadiene copolymer containing a rubber phase of a large island structure and a rubber phase of a small island structure with a polycarbonate. Will reduce the shortcomings of flame retardant properties.
  • the present invention selects a total of butadiene containing a rubber phase of a large island structure and a rubber phase of a small island structure Polymer, the rubber phase can induce silver streaks well and terminate the silver streak, thereby further improving the toughness and impact strength of the polycarbonate composition, thereby not affecting its flame retardancy, fluidity, heat resistance
  • the impact strength of the polycarbonate composition is markedly improved, and it is particularly suitable for applications where the use environment is relatively high.
  • Figure 1 is a schematic view showing the long-diameter structure of a large island structure and its internal small island structure in the butadiene copolymer component of the present invention.
  • 1 indicates the long diameter of the large island structure
  • 2 is the long diameter of the small island structure
  • 3 is the long diameter of the small island structure with the smallest long diameter.
  • the test method for the aspect ratio of the large island structure rubber phase and the smallest long-path small island structure in the butadiene copolymer component is dyed by the dyeing agent ruthenium tetroxide (RuO 4 ) or osmium tetroxide (OsO 4 ).
  • RuO 4 ruthenium tetroxide
  • OsO 4 osmium tetroxide
  • the transmission electron micrograph the small island structure existing in the large island structure is presented.
  • the TEM image is imported into Photoshop or Nano measurer image processing software, and the software is tested by comparing the scale scale in the transmission electron microscope image.
  • the long diameter of the specific large island rubber phase and the smallest long diameter small island long diameter are obtained. Dividing the measured long diameter of the large island structure by the longest diameter of the small island structure is the ratio of the specific long diameter of the rubber phase of the large island structure to the specific long diameter of the smallest long diameter small island structure in the interior.
  • the fixed aspect ratio range of the size of the island structure ratio test method refers to the transmission of the butadiene copolymer treated by the above method, and the transmission electron micrographs of a plurality of different regions are randomly photographed.
  • the length-to-diameter ratio of each size of the island structure in the transmission electron microscope is measured one by one, and the length-to-diameter ratio of the island structure with 500 specific sizes is obtained by random measurement, and the aspect ratio is 1.01-80.
  • the number of island structures divided by 500 is the ratio of the size of the island structure to the fixed aspect ratio range.
  • the flammability test was carried out in accordance with the procedures of Underwriters Laboratories Bulletin 94 entitled "Tests for Flammability of Plastic Materials, UL94.”. Several grades can be applied based on the rate of combustion, the time of extinction, the ability to resist dripping, and whether the drip is burning.
  • the sample used for the test was a rod having a size of 125 mm length x 13 mm width x no more than 13 mm thickness. The rod thickness is 1.5 mm. According to this procedure, based on the test results obtained for the five samples, Materials can be classified as UL 94HB (horizontal combustion), V0, V1, V2, 5VA, and/or 5VB; however, only the compositions herein are tested and classified as V0, V1, and V2,
  • V0 In a sample placed such that its long axis is 180 degrees with respect to the flame, after the ignition flame is removed, the period of combustion and/or smoldering does not exceed ten (10) seconds, and the sample placed vertically does not produce a lead. Dropping of burning particles of the defatted cotton. Flame out time is the fifth bar flame out time of five bars, each lit twice, wherein the first (t 1) and the second (t 2) is less than or equal to the ignition and flame out time of 50 seconds The maximum flame out time (t 1 +t 2 ).
  • V1 In a sample placed such that its long axis is 180 degrees with respect to the flame, after the ignition flame is removed, the period of combustion and/or smoldering does not exceed thirty (30) seconds, and the vertically placed sample is not produced. Drip the burning particles of the defatted cotton.
  • Flame out time is the fifth bar flame out time of five bars, each lit twice, wherein the first (t 1) and the second (t 2) is less than or equal to the ignition and flame out time of 250 seconds The maximum flame out time (t 1 +t 2 ).
  • V2 In a sample placed such that its long axis is 180 degrees with respect to the flame, the average period of combustion and/or smoldering after removal of the igniting flame does not exceed thirty (30) seconds, but the vertically placed sample is produced. The dripping of the burning particles of the igniting cotton. Flame out time is the fifth bar flame out time of five bars, each lit twice, wherein the first (t 1) and the second (t 2) is less than or equal to the ignition and flame out time of 250 seconds The maximum flame out time (t 1 +t 2 ).
  • Melt flow rate (MFR) method The plastic pellets are melted into a plastic fluid under a certain time (10 minutes), a certain temperature and pressure (different materials standards), and then passed through a 2.1 mm diameter round tube. The number of grams that flowed out. The larger the value, the better the processing fluidity of the plastic material, and vice versa; the test standard used herein is ASTM D1238, unit: g/10 min.
  • the test conditions were as follows: melt flow rate (MFR) at 230 ° C under a load of 2.16 kg.
  • HDT heat deflection temperature
  • Component a-1 PC 1300-10 (LG, Korea);
  • Component a-2 PC 1225 (Japanese Teijin);
  • butadiene copolymer used in the present invention is not limited to:
  • Component b-1 ABS1 emulsion method 757 (Taiwan Chi Mei);
  • Component b-2 ABS2 Ontology Method 8391 (Shanghai Gaoqiao);
  • Component b-3 MBS EM500 (LG, Korea);
  • Component c BDP, bisphenol A-bis(diphenyl phosphate) (Idico);
  • Component d-1 AO1076: ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid n-octadecyl alcohol ester CAS NO.: [2082-79-3]) as an antioxidant ;
  • Component d-2 PTFE (polytetrafluoroethylene) as an anti-drip agent.
  • the aspect ratio of the internal large island structure rubber phase and the internal small island structure of the butadiene copolymer structure is in the range of 1.01-80, and the island structure of the type accounts for more than 90% of the butadiene copolymer;
  • the formula is prepared by weighing polycarbonate, butadiene copolymer, flame retardant and other auxiliary agents in proportion, and then blending, extruding, cooling by water, granulation to obtain columnar particles by high-mixer or mixer. Polycarbonate composition; flame retardancy, melt flow rate MFR, heat deflection temperature and notched Izod impact strength of the polycarbonate composition were tested. The data is shown in Table 1.
  • the present invention exhibits a large island structure rubber phase by the polybutadiene copolymer structure in the butadiene copolymer component of the polycarbonate composition formulation.
  • the impact strength of the polycarbonate composition is markedly improved without affecting the flame retardancy, fluidity, and heat resistance, and is particularly suitable for applications where the use environment is relatively high.

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Abstract

本发明公开了一种聚碳酸酯组合物，按重量份计，包括以下组成： a、30.4份-80.2份的聚碳酸酯； b、8.4份-49.6份的丁二烯共聚物； c、5.4份-25.2份的阻燃剂； d、0-9.6份的其它助剂；其中，a、b、c、d四种组分的重量份之和为100份。本发明通过在聚碳酸酯组合物配方内选用丁二烯共聚物组分，该组分中聚丁二烯共聚物结构呈现大海岛结构橡胶相，在该大海岛结构橡胶相内部进一步还存在着1至50个小海岛结构，其中90％及90％以上大海岛结构橡胶相与其内部最小长径小海岛结构的长径比值为1.01-80时，能够在不影响其阻燃性、流动性、耐热性的情况下明显提高聚碳酸酯组合物的冲击强度，且特别适用于使用环境要求比较高的场合。

Description

一种聚碳酸酯组合物及其制备方法 技术领域
本发明涉及工程塑料技术领域，特别涉及一种聚碳酸酯组合物及其制备方法。
背景技术
聚碳酸酯PC具有较高耐冲击性及耐热性等特性，为改善其加工性能及对缺口冲击敏感的缺点，通常可加入橡胶类改性聚合物，如ABS、MBS等，特别是以PC和ABS为主要原料的PC/ABS合金是一种重要的工程塑料，一方面能提高ABS的耐热性和拉伸强度，另一方面能降低PC熔体粘度，改善加工性能，减少制品内应力和冲击强度对制品厚度的敏感性。
由于电子、电器、建筑、办公设备对材料阻燃性的高要求，希望改善材料的阻燃性以减少火灾相关的危险，必须对聚碳酸酯组合物进行阻燃处理。众所周知，芳族磷酸酯化合物的加入能够满足材料阻燃性的高要求，但是它的加入通常会使混合物的缺口冲击强度下降，因此，在很多应用方面又对材料的耐冲击性提出更高的要求。
专利US20130079443A1公开了一种改善PC/ABS树脂合金的方法，采用了马来酸酐接枝乙丙橡胶提高了混合物的冲击强度，但是增韧剂的使用会影响材料的强度并且提高了材料成本，另外橡胶的加入通常还会对阻燃性带来负面的影响。
到目前为止，关于在聚碳酸酯组合物内的丁二烯共聚物组分中聚丁二烯共聚物结构呈现大海岛结构橡胶相，在该大海岛结构橡胶相内部进一步还存在着1至50个小海岛结构，其中90％及90％以上大海岛结构橡胶相与其内部最小长径小海岛结构的长径比值为1.01-80对所述聚碳酸酯组合物的冲击强度的影响未见报道。
本发明人经过大量实验惊讶地发现，在聚碳酸酯组合物配方内选用丁二烯共聚物组分，该组分中聚丁二烯共聚物结构呈现大海岛结构橡胶相，在该大海岛结构橡胶相内部进一步还存在着1至50个小海岛结构，其中90％及90％以上大海 岛结构橡胶相与其内部最小长径小海岛结构的长径比值为1.01-80时，该橡胶相能够很好地引发银纹并终止银纹，继而更好地提高聚碳酸酯组合物的韧性和冲击强度，从而能够在不影响其阻燃性、流动性、耐热性的情况下明显提高聚碳酸酯组合物的冲击强度，且特别适用于使用环境要求比较高的场合。
发明内容
为了克服现有技术的缺点与不足，本发明的首要目的在于提供一种在不影响其阻燃性、流动性和耐热性的情况下明显提高其冲击强度的聚碳酸酯组合物。
本发明的另一目的的提供上述聚碳酸酯组合物的制备方法。
本发明是通过以下技术方案实现的：
一种聚碳酸酯组合物，按重量份计，包括以下组成
a、30.4份-80.2份的聚碳酸酯；
b、8.4份-49.6份的丁二烯共聚物；
c、5.4份-25.2份的阻燃剂；
d、0-9.6份的其它助剂；
其中，a、b、c、d四种组分的重量份之和为100份。
优选地，一种聚碳酸酯组合物，按重量份计，包括以下组成：
a、32份-75份的聚碳酸酯；
b、9份-35份的丁二烯共聚物；
c、6份-25份的阻燃剂；
d、0-9.6份的其它助剂；其中，a、b、c、d四种组分的重量份之和为100份，
丁二烯共聚物组分中聚丁二烯共聚物结构呈现大海岛结构橡胶相，在该大海岛结构橡胶相内部进一步还存在着1至50个小海岛结构，其中90％及90％以上大小海岛结构中大海岛结构橡胶相与其内部最小长径小海岛结构的长径比值为1.01-80。
更优选地，一种聚碳酸酯组合物，按重量份计，包括以下组成：
a、42份-70份的聚碳酸酯；
b、9份-30份的丁二烯共聚物；
c、6份-18份的阻燃剂；
d、0-9.6份的其它助剂；其中，a、b、c、d四种组分的重量份之和为100份，
丁二烯共聚物组分中聚丁二烯共聚物结构呈现大海岛结构橡胶相，在该大海岛结构橡胶相内部进一步还存在着1至50个小海岛结构，其中90％及90％以上大海岛结构橡胶相与其内部最小长径小海岛结构的长径比值为1.01-80。
优选地，所述大海岛结构橡胶相与其内部最小长径小海岛结构的长径比值为1.01-80的海岛结构，在所有海岛结构中占比为92％以上，更优选为94％以上。
大海岛结构橡胶相，指丁二烯共聚物组分中聚丁二烯结构(即橡胶相)通过染色剂四氧化钌(RuO4)或四氧化锇(OsO4)染色，在透射电镜图中呈现大海岛结构，长径范围为50nm-2000nm，其为橡胶相被染色剂染色，显现出如图1所示的大海岛结构。
小海岛结构橡胶相，指丁二烯共聚物组分中聚丁二烯结构(即橡胶相)通过染色剂四氧化钌(RuO4)或四氧化锇(OsO4)染色，在透射电镜图中呈现大海岛结构内存在的1至50个小海岛结构，长径范围为10nm-1500nm，其为在大海岛结构(即橡胶相)内存在着不可被染色剂染色的非橡胶相，可为聚碳酸酯相或与聚丁二烯橡胶接枝的其他共聚物，显现出如图1所示的小海岛结构。
丁二烯共聚物组分中大海岛结构橡胶相与其内部最小长径小海岛结构的长径比值的测试方法，是指通过染色剂四氧化钌(RuO4)或四氧化锇(OsO4)染色，在透射电镜图中呈现大海岛结构内存在的小海岛结构，将所拍得透射电镜图导入Photoshop或Nano measurer图片处理软件中，通过比对透射电镜图中的比例标尺，在上述软件中测试得到具体的大海岛橡胶相长径与其内的最小长径小海岛长径。将测量得到的大海岛结构长径除以最小长径小海岛结构长径即为大海岛结构橡胶相的具体长径与其内部最小长径小海岛结构的具体长径的比值。
长径比值为1.01-80的大小海岛结构占比测试方法，是指用透射电镜拍摄上述方法处理过的丁二烯共聚物，随机拍摄得到多张不同区域的透射电镜图。利用上述量取大小海岛结构长径比的方法逐一测量得到透射电镜图中每一个大小海岛结构的长径比值，随机测量得到500个具体大小海岛结构长径比值，将长径比在1.01-80的大小海岛结构个数除以500即为固定长径比范围的大小海岛结构占比。
其中，该大海岛结构橡胶相长径为50nm-2000nm。
所述丁二烯共聚物选自本体法、乳液法、本体-悬浮聚合法制备的聚丁二烯 共聚物的一种或几种。
所述丁二烯共聚物，按重量份计，选自包含如下b.1在b.2上的接枝共聚物：
b.1、5份-95份的b.1.1和b.1.2的混合物：
b.1.1、50份-95份的苯乙烯、苯乙烯衍生物如α-甲基苯乙烯、对苯甲基苯乙烯，二乙烯基苯乙烯，甲基丙烯酸C1-C8-烷基酯、丙烯酸C1-C8-烷基酯、二甲基硅氧烷、苯基硅氧烷、多烷基硅氧烷的一种或几种；
b.1.2、5份-50份的丙烯腈、甲基丙烯腈、甲基丙烯酸C1-C8-烷基酯、丙烯酸C1-C8-烷基酯的一种或几种；
b.2、5份-95份的聚丁二烯、苯乙烯-丁二烯无规共聚物及嵌段共聚物、丙烯腈-丁二烯无规共聚物及嵌段共聚物、聚丁二烯和聚异戊二烯共聚物、乙烯和a-烯烃共聚物、乙烯和a-不饱和羧酸酯共聚物、乙烯-丙烯-非共轭二烯三元共聚物中一种或几种。
优选地，所述丁二烯共聚物选自苯乙烯-丁二烯-苯乙烯嵌段共聚物SBS、丙烯腈-丁二烯-苯乙烯接枝共聚物ABS、甲基丙烯酸甲酯-丙烯腈-丁二烯苯乙烯共聚物MABS、甲基丙烯酸甲酯-丁二烯-苯乙烯接枝共聚物MBS中的一种或几种；更优选为丙烯腈-丁二烯-苯乙烯接枝共聚物ABS；其中，MBS的粒径优选0.1um-0.5um，本体聚合法ABS粒径优选0.1um-2um，乳液聚合法ABS粒径优选0.05um-0.2um。
在本发明中优选使用的丙烯腈-丁二烯-苯乙烯共聚物(ABS树脂)是通过将丁二烯橡胶组分与丙烯腈和苯乙烯接枝聚合获得的热塑性接枝共聚物和丙烯腈-苯乙烯共聚物的混合物。
其中，所述聚碳酸酯选自通过界面聚合法、熔融酯交换法、吡啶法、环状碳酸酯化合物的开环聚合法和预聚物的固相酯交换法制备的聚碳酸酯的一种或几种。下面将详细说明其特别优选的方法。
首先将说明通过界面聚合法来生产聚碳酸酯树脂的方法：在界面聚合法中，首先，使二羟基化合物和碳酸酯前体(优选光气)在惰性有机溶剂和碱水溶液的存在下反应同时通常维持pH为9以上，然后在聚合催化剂的存在下进行界面聚合从而获得聚碳酸酯树脂。分子量调节剂(链终止剂)以及防止二羟基化合物的氧化的抗氧化剂也可以按需要存在于反应体系中。
上面已经列出了二羟基化合物和碳酸酯前体。光气作为碳酸酯前体的使用是 特别优选的，并且其中使用光气的这种方法特别称为光气法。
惰性有机溶剂的实例包括氯代烃，例如二氯甲烷、1,2-二氯乙烷、氯仿、单氯苯和二氯苯；和芳香族烃，例如苯、甲苯和二甲苯。可以使用一种有机溶剂，或者可以以期望的组合和比例一起使用其两种以上。
碱水溶液中包含的碱化合物的实例包括碱金属化合物，例如氢氧化钠、氢氧化钾、氢氧化锂和碳酸氢钠；以及碱土金属化合物。氢氧化钠和氢氧化钾是优选的。可以使用一种碱化合物，或者可以以期望的组合和比例一起使用其两种以上。
虽然碱水溶液中的碱化合物的浓度这里不受限制，但通常使用5wt％-10wt％以控制在反应期间的碱水溶液的pH为10-12。此外，例如，当光气鼓泡时，双酚化合物与碱化合物的摩尔比通常设定为1：1.9以上，和优选为1：2.0以上，但是1：3.2以下，和优选为1：2.5以下，从而控制水相的pH为10-12，优选为10-11。
聚合催化剂的实例包括脂肪族叔胺，例如三甲胺、三乙胺、三丁胺、三丙胺和三己胺等；脂环族叔胺，例如N,N'-二甲基环己胺和N,N'-二乙基环己胺等；芳香族叔胺，例如N,N'-二甲基苯胺和N,N'-二乙基苯胺等；季铵盐，例如三甲基苄基氯化铵、四甲基氯化铵和三乙基苄基氯化铵等；吡啶；鸟嘌呤；和胍盐等。可以使用一种聚合催化剂，或者可以以期望的组合和比例一起使用其两种以上。
分子量调节剂的实例包括具有一价酚式羟基的芳香族酚；脂肪族醇，例如甲醇和丁醇等；硫醇；和邻苯二甲酰亚胺类；等等，并且这些之中，芳香族酚是优选的。此类芳香族酚的具体实例包括烷基取代的酚如间甲基苯酚、对甲基苯酚、间丙基苯酚、对丙基苯酚、对叔丁基苯酚和对-长链烷基取代的苯酚等；含乙烯基的酚如异丙烯基苯酚；含环氧基的酚；和含羧基的酚，例如邻羟基苯甲酸和2-甲基-6-羟基苯基乙酸等。可以使用一种分子量调节剂，或者可以以期望的组合和比例一起使用其两种以上。
分子量调节剂的用量通常相对于每100摩尔二羟基化合物为0.5摩尔以上，且优选1摩尔以上，但通常为50摩尔以下，和优选为30摩尔以下。设定分子量调节剂的量至该范围可以改进聚碳酸酯树脂组合物的热稳定性和耐水解性。
反应基质、反应介质、催化剂和添加剂等可以在反应期间以任意期望的顺序混合在一起，只要可以获得期望的聚碳酸酯树脂即可，并且可以按需要建立适合的顺序。例如，当光气用作碳酸酯前体时，分子量调节剂可以在二羟基化合物与 光气的反应(光气化)时和在聚合反应开始时之间在任意期望的时机添加。
反应温度通常设定为0-40℃，和反应时间通常在几分钟(例如，10分钟)至几小时(例如，6小时)的范围内。
接下来，将说明通过熔融酯交换法的聚碳酸酯树脂的制造方法：在熔融酯交换法中，例如，酯交换反应在碳酸二酯和二羟基化合物之间进行。
同时，碳酸二酯的实例包括碳酸二烷基酯化合物，例如碳酸二甲酯、碳酸二乙酯和碳酸二叔丁酯；碳酸二苯酯；和取代的碳酸二苯酯，例如碳酸二甲苯酯等。这些之中，碳酸二苯酯和取代的碳酸二苯酯是优选的，并且特别地，碳酸二苯酯甚至是更优选的。可以使用一种的碳酸二酯，或者可以以期望的组合和比例一起使用其两种以上。
可以使用期望的比例的二羟基化合物与碳酸二酯，条件是可以获得目标聚碳酸酯树脂，但是使用相对于每1摩尔二羟基化合物为1摩尔当量以上的碳酸二酯是优选的，并且使用1.01以上摩尔当量的甚至是更优选的。然而，上限通常为1.30以下摩尔当量。末端羟基的量可以通过设定两种化合物的比例在此类范围内而调节至优选的范围。
聚碳酸酯树脂中的末端羟基的量倾向于极大影响热稳定性、耐水解性和色调等。因此，末端羟基的量可以通过任意公知的期望的方法根据需要来调节。在酯交换反应中，其中调节末端羟基的量的聚碳酸酯树脂通常可以通过在反应期间调节在碳酸二酯和芳香族二羟基化合物之间的混合比，和压力减小的程度等来获得。此外，所得聚碳酸酯树脂的分子量通常也可以通过该过程来调节。
在其中末端羟基的量通过调节二碳酸酯和二羟基化合物的混合比来调节的情况中使用上述混合比。
可以提到其中在反应期间单独地添加链终止剂的方法作为更积极的调节方法。在该过程期间的链终止剂的实例包括例如，单价酚、单价羧酸和碳酸二酯等。可以使用一种链终止剂，或者可以以期望的组合和比例一起使用其两种以上。
当通过熔融酯交换法生产聚碳酸酯树脂时，通常使用酯交换催化剂。可以使用任意期望的酯交换催化剂。这些之中，例如，碱金属化合物和/或碱土金属化合物的使用是优选的。此外，作为辅助化合物，例如，可以使用碱性化合物如碱性硼化合物、碱性磷化合物、碱性铵化合物和碱性胺化合物等。可以使用一种酯交换催化剂，或者可以以期望的组合和比例一起使用其两种以上。
熔融酯交换法中的反应温度通常为100℃-320℃。此外，反应通常在2mmHg以下的减压下进行。详细过程应该为其中熔融缩聚反应在上述条件下进行同时除去副产物如芳香族羟基化合物等的过程。
熔融缩聚反应可以通过分批法或连续法来进行。当进行分批法时，反应基质、反应介质、催化剂和添加剂等可以任意期望的顺序混合在一起，只要可以获得目标芳香族聚碳酸酯树脂即可，并且可以按需要建立适合的顺序。然而，这些之中，考虑到例如聚碳酸酯和聚碳酸酯树脂组合物的稳定性，通过连续过程进行熔融缩聚是优选的。
催化剂失活剂可以在熔融酯交换法中根据需要来使用。任意期望的中和酯交换催化剂的化合物可以用作催化剂失活剂。实例包括含硫有机化合物及其衍生物等。可以使用一种催化剂失活剂，或者可以以期望的组合和比例一起使用其两种以上。
催化剂失活剂的用量应当通常相对于酯交换催化剂中包含的碱金属或碱土金属为0.5重量当量以上和优选1重量当量以上，但是应通常为10重量当量以下，和优选5重量当量以下。另外，其浓度应当通常相对于芳香族聚碳酸酯树脂为1ppm以上，但通常为100ppm以下，和优选为20ppm以下。
其中，所述聚碳酸酯选自芳香族聚碳酸酯、脂肪族聚碳酸酯、芳香族-脂肪族聚碳酸酯、支化聚碳酸酯中的一种或几种；优选为芳香族聚碳酸酯。
优选地，所述芳香族聚碳酸酯为粘均分子量13000-40000的芳香族聚碳酸酯，更优选为粘均分子量16000-28000的芳香族聚碳酸酯，进一步优选为粘均分子量17000-24000的芳香族聚碳酸酯。当粘均分子量在上述范围内，机械强度良好并且能保持优异的成型性。
其中，粘均分子量是通过使用二氯甲烷作为溶剂在测试温度为25℃的溶液粘度计算出来的。聚碳酸酯树脂中的末端羟基的浓度是任意的，并且可以按需要选择和确定，但是通常为1,000ppm以下，优选为800ppm以下，和更优选为600ppm以下。浓度的下限，特别是在通过熔融酯交换法生产的聚碳酸酯树脂的情况下，通常为10ppm以上，优选为30ppm以上，和更优选为40ppm以上。可以防止分子量的降低，由此可以更加改进聚碳酸酯树脂组合物的机械特性。末端羟基浓度的单位这里表示为基于末端羟基的质量相对于聚碳酸酯树脂的质量的ppm。通过四氯化碳/乙酸过程的比色分析用作测量方法(参见 Macromol.Chem.,88,215,1965)。
其中，所述聚碳酸酯树脂的分子量是任意的，并且可以适当地选择和确定，但是由液体粘度计算的粘均分子量[Mv]通常为为13000-40000，优选为16000-28000，更优选为17000-24000。通过设定粘均分子量在上述范围的下限以上，可以更加提高本发明的聚碳酸酯树脂组合物的机械强度，并且当组合物用于要求高机械强度的应用时这甚至是更期望的。同时，通过设定粘均分子量在上述范围的上限以下，本发明的聚碳酸酯树脂组合物的流动性的降低可以得到控制或改进，这提高成型性且促进薄壁成型法。两种以上具有不同粘均分子量的聚碳酸酯树脂可以混合和使用在一起，并且在此情况下粘均分子量在上述优选范围之外的聚碳酸酯树脂也可以包括在混合物中。
术语粘均分子量[Mv]是指由其中通过用乌氏粘度计在20℃下使用氯甲烷作为溶剂的测量确定特性粘度[η](单位：dl/g)的Schnell粘度方程即η＝1.23×10-4Mv0.83计算得到的值。此外，特性粘度[η]为在各种浓度[C](g/dl)的溶液中测量比粘度[ηsp]之后通过下述方程计算得到的值。
Figure PCTCN2016085077-appb-000001
聚碳酸酯树脂中的末端羟基的浓度是任意的，并且可以按需要选择和确定，但是通常为1,000ppm以下，优选为800ppm以下，和更优选为600ppm以下。因此，甚至可以更加改进本发明的聚碳酸酯树脂组合物的滞留热稳定性(residual thermal stability)和色调。浓度的下限，特别是在通过熔融酯交换法生产的聚碳酸酯树脂的情况下，通常为10ppm以上，优选为30ppm以上，和更优选为40ppm以上。可以防止分子量的降低，由此可以更加改进聚碳酸酯树脂组合物的机械特性。
末端羟基浓度的单位这里表示为基于末端羟基的质量相对于聚碳酸酯树脂的质量的ppm。通过四氯化碳/乙酸过程的比色分析用作测量方法(参见Macromol.Chem.,88,215,1965)。
聚碳酸酯树脂可以用作单独的聚碳酸酯树脂(其中术语"单独的聚碳酸酯树脂"不限定为仅包括一种聚碳酸酯树脂的模式，例如，包括包含多种具有不同单体配方和分子量的聚碳酸酯树脂的模式)，或者其可以以聚碳酸酯树脂和不同的热塑性树脂的合金(混合物)来组合和使用。另外，聚碳酸酯树脂可以构成具有 聚碳酸酯树脂作为其主体组分的共聚物，如为了进一步提高阻燃性和耐冲击性的目的的包括包含硅氧烷结构的低聚物或聚合物的共聚物；为了进一步提高热氧化稳定性和阻燃性的目的的包括包含磷原子的单体、低聚物或聚合物的共聚物；为了提高热氧化稳定性的目的的包括包含二羟基蒽醌结构的单体、低聚物或聚合物；为了改进光学性质的目的的包括如由聚苯乙烯表示的包含烯烃系结构的低聚物或聚合物的共聚物；和为了提高耐化学品性的目的的包括聚酯树脂低聚物或聚合物的共聚物；等等。
为了提高成型制品的外观和改进流动性的目的，聚碳酸酯树脂也可以包含聚碳酸酯低聚物。该聚碳酸酯低聚物的粘均分子量[Mv]通常为1,500以上，和优选为2,000以上，但通常为9,500以下，和优选为9,000以下。另外，优选地，所包含的聚碳酸酯低聚物的含量设定为聚碳酸酯树脂(包含聚碳酸酯低聚物)的30wt％以下。
另外，聚碳酸酯树脂可以为由用过的制造产品再生的而不是由未用过的原料制成的那种的聚碳酸酯树脂(所谓的再生材料聚碳酸酯树脂)。用过的制造产品的实例包括光学记录介质如光盘等；导光板；透明汽车部件如汽车窗玻璃、汽车大灯玻璃和挡风玻璃等；容器如水瓶等；眼镜镜片；和建筑材料如隔音板、玻璃窗、波纹板；等等。此外，还可以使用由残次品、熔渣和流道(runner)等获得的粉碎品或熔融的粒料。
然而，应当注意到，再生的聚碳酸酯树脂优选为本发明的聚碳酸酯树脂组合物中包含的聚碳酸酯树脂的80wt％以下，和更优选为50wt％以下。再生的聚碳酸酯树脂将很可能由于热或老化而经历劣化，并且如果此类聚碳酸酯树脂以比上述范围大的量使用，可能不利地影响色调和机械特性。
其中，所述阻燃剂选自卤系阻燃剂或无卤阻燃剂，优选无卤阻燃剂；所述卤系阻燃剂选自溴化聚苯乙烯、溴化聚苯醚、溴化双酚A型环氧树脂、溴化苯乙烯-马来酸酐共聚物、溴化环氧树脂、溴化苯氧基树脂、十溴二苯醚、十溴代联苯、溴化聚碳酸酯、全溴三环十五烷或溴化芳香族交联聚合物的一种或几种，优选为溴化聚苯乙烯；所述无卤阻燃剂选自含氮阻燃剂、含磷阻燃剂或含氮和磷的阻燃剂中的一种或几种，优选为含磷阻燃剂。
优选地，所述含磷阻燃剂选自单体和低聚的磷酸酯和膦酸酯、膦酸酯胺和膦腈，其中也可以使用选自这些组的一组或多组的多种化合物的混合物；优选为磷 酸三苯基酯、磷酸三甲苯基酯、磷酸甲苯基二苯基酯、磷酸三二甲苯基酯、磷酸三(2,4,6-三甲基苯基)酯、磷酸三(2,4-二叔丁基苯基)酯、磷酸三(2,6-二叔丁基苯基)酯、间苯二酚双(磷酸二苯基酯)、对苯二酚双(磷酸二苯基酯)、双酚A-双(磷酸二苯基酯)、间苯二酚双(2,6-二叔丁基苯基磷酸酯)、对苯二酚双(2,6-二甲基苯基磷酸酯)的一种或几种。
进一步地，在上述聚碳酸酯树脂与丁二烯共聚物、阻燃剂混合时，还包括可以根据需要适当添加其它助剂，所述其它助剂选自热稳定剂、抗氧剂、抗滴落剂、光稳定剂、增塑剂、填料、着色剂的一种或几种。
合适的热稳定剂包括有机亚磷酸酯，如亚磷酸三苯酯，亚磷酸三-(2,6-二甲基苯基)酯，亚磷酸三-壬基苯基酯，二甲基苯膦酸酯，磷酸三甲酯等。
合适的抗氧剂包括有机亚磷酸酯，烷基化的一元酚或者多元酚，多元酚和二烯的烷基化反应产物，对甲酚或者二环戊二烯的丁基化反应产物，烷基化的氢醌类，羟基化的硫代二苯基醚类，亚烷基-双酚，苄基化合物，多元醇酯类等。
合适的抗滴落剂优选氟化聚烯烃，氟化聚烯烃是公知的(参见例如EP-A 640 655)。商业上惯用的产品例如是得自DuPont公司的
Figure PCTCN2016085077-appb-000002
30N。
合适的光稳定剂包括苯并三唑类，二苯甲酮类的一种或者多种组合。
合适的增塑剂为邻苯二甲酸酯。
合适的填料包括钛白粉、滑石粉、云母和硫酸钡等。
合适的着色剂包括各种颜料，染料。
上述聚碳酸酯组合物的制备方法，包括如下步骤：
1)选取丁二烯共聚物结构的内部大海岛结构橡胶相与其内部最小长径小海岛结构的长径比值在1.01-80区间，且该类型大小海岛结构占比90％以上的丁二烯共聚物；
2)将聚碳酸酯、丁二烯共聚物、阻燃剂、其它助剂按照比例称量后，通过高混机或者混合机完成共混，挤出，过水冷却，造粒得到柱状颗粒的聚碳酸酯组合物。
可以首先将所有成分添加至加工系统，或某些添加剂可以与一种或多种主要组分预混合。
在一种实施方式中，可以干式共混阻燃剂组合物以在进料至挤出机之前在装置如亨舍尔混合机或韦林氏搅切器中形成混合物，其中，混合物是熔融共混的。 在另一个实施方式中，部分聚碳酸酯组合物可以与阻燃剂预混合以形成干燥预混物。然后，将干燥预混物与剩余的聚碳酸酯组合物在挤出机中熔融共混。在一种实施方式中，一些阻燃剂组合物可以首先在挤出机的口部进料，同时阻燃剂组合物的剩余部分通过口部的端口下游进料。
阻燃剂组合物的共混包括使用剪切力、拉伸力、压缩力、超声波能、电磁能、热能、或包含上述力或形式的能量的至少一种的组合，并且在加工设备中进行，其中，通过单螺杆、多螺杆、啮合同向旋转或异向旋转螺杆、非啮合同向旋转或异向旋转螺杆、往复式螺杆、具有销的螺杆、具有销的桶、辊筒、撞锤、螺旋转子，或包含上述中的至少一种的组合施加上述力。
涉及上述力的共混可以在机器如单螺杆或多螺杆挤出机、Buss捏合机、亨舍尔混合机、螺旋混合机、Ross混合机、密炼机(Banbury)、辊磨机、模制机(如注射模制机、真空模制机、吹塑模制机)等，或包含上述机器中的至少一种的组合中进行。
可以将阻燃剂组合物以母料形式引入至熔融共混装置中。例如，部分聚碳酸酯组合物可以与磷酸酯阻燃剂预共混以形成母料，然后，将母料与剩余的成分共混以形成阻燃剂组合物。在这种工艺中，可以将母料引入至在引入阻燃剂组合物的剩余成分的位置下游的共混装置中。
本发明的聚碳酸酯组合物可用于制备模制品，例如耐用制品、电气和电子部件、汽车零件等。利用常见热塑工艺如膜和片材挤出、注射模制、气体辅助注射模制、挤出模制、压缩模制以及吹塑模制，可以将组合物转化成制品。
本发明的聚碳酸酯组合物由于能够在不影响其阻燃性、流动性、耐热性的情况下明显提高聚碳酸酯组合物的冲击强度，可用于户外以及室内的应用领域，例如手机、MP3播放器、计算机、笔记本电脑、照相机、录像机、平板电脑、手持受话器、厨房电器或者电气壳体的一部分等，或者在户外使用的汽车部件，建筑领域的外壳或者盖子，以及电器用具外壳和边框。
本发明与现有技术相比，具有如下有益效果：
1)本发明通过用选取含有大海岛结构橡胶相和小海岛结构橡胶相的丁二烯共聚物，与聚碳酸酯共混得到的组合物，克服了现有橡胶改性的接枝共聚物通常会降低阻燃性能的缺点。
2)本发明通过选取含有大海岛结构橡胶相和小海岛结构橡胶相的丁二烯共 聚物，该橡胶相能够很好地引发银纹并终止银纹，继而更好地提高聚碳酸酯组合物的韧性和冲击强度，从而能够在不影响其阻燃性、流动性、耐热性的情况下明显提高聚碳酸酯组合物的冲击强度，且特别适用于使用环境要求比较高的场合。
附图说明
图1为本发明的丁二烯共聚物组分中大海岛结构与其内部小海岛结构长径的示意图。
图中1表示为大海岛结构的长径，2为小海岛结构的长径，3为最小长径的小海岛结构长径。
具体实施方式
下面通过具体实施方式来进一步说明本发明，以下实施例为本发明较佳的实施方式，但本发明的实施方式并不受下述实施例的限制。
各性能的测试标准或方法：
丁二烯共聚物组分中大海岛结构橡胶相与其内部最小长径小海岛结构的长径比值的测试方法，是指通过染色剂四氧化钌(RuO4)或四氧化锇(OsO4)染色，在透射电镜图中呈现大海岛结构内存在的小海岛结构，将所拍得透射电镜图导入Photoshop或Nano measurer图片处理软件中，通过比对透射电镜图中的比例标尺，在上述软件中测试得到具体的大海岛橡胶相长径与其内的最小长径小海岛长径。将测量得到的大海岛结构长径除以最小长径小海岛结构长径即为大海岛结构橡胶相的具体长径与其内部最小长径小海岛结构的具体长径的比值。
固定长径比范围的大小海岛结构占比测试方法，是指用透射电镜拍摄上述方法处理过的丁二烯共聚物，随机拍摄得到多张不同区域的透射电镜图。利用上述量取大小海岛结构长径比的方法逐一测量得到透射电镜图中每一个大小海岛结构的长径比值，随机测量得到500个具体大小海岛结构长径比值，将长径比在1.01-80的大小海岛结构个数除以500即为固定长径比范围的大小海岛结构占比。
UL-94阻燃的测定方法：
按照题为“塑料材料的可燃性测试，UL94。(Tests for Flammability of Plastic Materials,UL94.)”的保险商实验室公告94的程序进行可燃性测试。基于燃烧速率、熄灭时间、抵抗滴落的能力、以及落滴(drip)是否正燃烧，可以应用若干等级。用于测试的样品是具有125mm长度×13mm宽度×不大于13mm厚度的尺寸的棒。棒厚度是1.5mm。根据该规程，基于针对五个样品获得的测试结果， 可以将材料分类为UL 94HB(水平燃烧)、V0、V1、V2、5VA和/或5VB；然而，仅将本文中的组合物测试并分类为V0、V1和V2，
以下描述了针对其中的每一个的标准。
V0：在放置使得其长轴相对于火焰是180度的试样中，在除去点燃火焰以后，燃烧和/或熏烧的时期不超过十(10)秒，并且垂直放置的试样没有产生引燃脱脂棉的燃烧颗粒的滴落。第五个棒的消焰时间是五个棒的消焰时间，每个点燃两次，其中，第一(t1)和第二(t2)点燃的消焰时间的和小于或等于50秒的最大消焰时间(t1+t2)。
V1：在放置使得其长轴相对于火焰是180度的试样中，在除去点燃火焰以后，燃烧和/或熏烧的时期不超过三十(30)秒，并且垂直放置的试样没有产生引燃脱脂棉的燃烧颗粒的滴落。第五个棒的消焰时间是五个棒的消焰时间，每个点燃两次，其中，第一(t1)和第二(t2)点燃的消焰时间的和小于或等于250秒的最大消焰时间(t1+t2)。
V2：在放置使得其长轴相对于火焰是180度的试样中，在除去点燃火焰以后，燃烧和/或熏烧的平均时期不超过三十(30)秒，但是垂直放置的试样产生引燃棉的燃烧颗粒的滴落。第五个棒的消焰时间是五个棒的消焰时间，每个点燃两次，其中，第一(t1)和第二(t2)点燃的消焰时间的和小于或等于250秒的最大消焰时间(t1+t2)。
熔体流动速率(MFR)的测定方法：让塑料粒在一定时间(10分钟)内、一定温度及压力(各种材料标准不同)下，融化成塑料流体，然后通过一直径为2.1mm圆管所流出的克数。其值越大，表示该塑胶材料的加工流动性越佳，反之则越差；本文中采用测试标准是ASTM D1238，单位：g/10min。采用测试条件为：在230℃、2.16kg载荷下的熔体流动速率(MFR)。
热挠曲温度(HDT)的测定方法：在升高的温度同时支撑负载下，材料进行持续短时间的能力的相对测量。测试测量温度对刚度的影响：给予标准测试试样定义的表面应力，并且温度以匀速上升。根据ASTM D648，在1.82MPa负载下，用3.2mm和/或6.4mm厚度的棒平放测定HDT，以℃记录结果。
悬臂梁冲击强度的测定方法：在23℃和0℃下，使用3.2mm厚的模制缺口悬臂梁冲击棒测定缺口悬臂梁冲击强度。根据ASTM D256测定缺口悬臂梁冲击 强度，以焦耳/米记录结果。在室温(23℃)下进行测试。
本发明中使用的聚碳酸酯：
组分a-1：PC 1300-10(韩国LG)；
组分a-2：PC 1225(日本帝人)；
本发明中使用的丁二烯共聚物：
组分b-1：ABS1 乳液法 757(台湾奇美)；
组分b-2：ABS2 本体法 8391(上海高桥)；
组分b-3：MBS EM500(韩国LG)；
本发明中使用的阻燃剂：
组分c：BDP，双酚A-双(磷酸二苯基酯)(艾迪科)；
本发明中使用的其它助剂：
组分d-1：AO1076：β-(3,5-二叔丁基-4-羟基苯基)丙酸正十八碳醇酯CAS NO.：〔2082-79-3〕)作为抗氧剂；
组分d-2：PTFE(聚四氟乙烯)作为抗滴落剂。
实施例1-12及对比例1-6：聚碳酸酯组合物的制备
选取丁二烯共聚物结构的内部大海岛结构橡胶相与其内部小海岛结构的长径比值在1.01-80区间，且该类型大小海岛结构占比90％以上的丁二烯共聚物；按表1的配方将聚碳酸酯、丁二烯共聚物、阻燃剂、其它助剂按照比例称量后，通过高混机或者混合机完成共混，挤出，过水冷却，造粒得到柱状颗粒的聚碳酸酯组合物；对聚碳酸酯组合物的阻燃性、熔体流动速率MFR、热挠曲温度和缺口悬臂梁冲击强度进行测试，数据见表1。
表1实施例1-12及对比例1-6的具体配比(重量份)及其测试性能结果
Figure PCTCN2016085077-appb-000003
Figure PCTCN2016085077-appb-000004
续表1
Figure PCTCN2016085077-appb-000005
Figure PCTCN2016085077-appb-000006
从表1的实施例和对比例的比较可以看出，本发明通过在聚碳酸酯组合物配方内的丁二烯共聚物组分中聚丁二烯共聚物结构呈现大海岛结构橡胶相，在该大海岛结构橡胶相内部进一步还存在着1至50个小海岛结构，其中90％及90％以上大海岛结构橡胶相与其内部最小长径小海岛结构的长径比值为1.01-80时，能够在不影响其阻燃性、流动性、耐热性的情况下明显提高聚碳酸酯组合物的冲击强度，且特别适用于使用环境要求比较高的场合。

Claims (14)

  1. 一种聚碳酸酯组合物，按重量份计，包括以下组成：
    a、30.4份-80.2份的聚碳酸酯；
    b、8.4份-49.6份的丁二烯共聚物；
    c、5.4份-25.2份的阻燃剂；
    d、0-9.6份的其它助剂；其中，a、b、c、d四种组分的重量份之和为100份。
  2. 一种如权利要求1所述的聚碳酸酯组合物，按重量份计，包括以下组成：
    a、32份-75份的聚碳酸酯；
    b、9份-35份的丁二烯共聚物；
    c、6份-25份的阻燃剂；
    d、0-9.6份的其它助剂；
    其中，a、b、c、d四种组分的重量份之和为100份，
    丁二烯共聚物组分中聚丁二烯共聚物结构呈现大海岛结构橡胶相，在该大海岛结构橡胶相内部进一步还存在着1至50个小海岛结构，其中90％及90％以上大海岛结构橡胶相与其内部最小长径小海岛结构的长径比值为1.01-80。
  3. 一种如权利要求1所述的聚碳酸酯组合物，按重量份计，包括以下组成：
    a、42份-70份的聚碳酸酯；
    b、9份-30份的丁二烯共聚物；
    c、6份-18份的阻燃剂；
    d、0-9.6份的其它助剂；
    其中，a、b、c、d四种组分的重量份之和为100份，
    丁二烯共聚物组分中聚丁二烯共聚物结构呈现大海岛结构橡胶相，在该大海岛结构橡胶相内部进一步还存在着1至50个小海岛结构，其中90％及90％以上大海岛结构橡胶相与其内部最小长径小海岛结构的长径比值为1.01-80。
  4. 根据权利要求2或3所述的聚碳酸酯组合物，其特征在于，所述大海岛结构橡胶相与其内部最小长径小海岛结构的长径比值为1.01-80的海岛结构，在所有海岛结构中占比为92％以上，优选为94％以上。
  5. 根据权利要求2-4任一项所述的聚碳酸酯组合物，其特征在于，该大海岛 结构橡胶相长径为50nm-2000nm。
  6. 根据权利要求1-3任一项所述的聚碳酸酯组合物，其特征在于，所述丁二烯共聚物选自本体聚合法、乳液聚合法、本体-悬浮聚合法制备的丁二烯共聚物的一种或几种。
  7. 根据权利要求1-3任一项所述的聚碳酸酯组合物，其特征在于，所述丁二烯共聚物，按重量份计，选自包含如下b.1在b.2上的接枝共聚物：
    b.1、5份-95份的b.1.1和b.1.2的混合物：
    b.1.1、50份-95份的苯乙烯、苯乙烯衍生物如α-甲基苯乙烯、对苯甲基苯乙烯，二乙烯基苯乙烯，甲基丙烯酸C1-C8-烷基酯、丙烯酸C1-C8-烷基酯、二甲基硅氧烷、苯基硅氧烷、多烷基硅氧烷的一种或几种；
    b.1.2、5份-50份的丙烯腈、甲基丙烯腈、甲基丙烯酸C1-C8-烷基酯、丙烯酸C1-C8-烷基酯的一种或几种；
    b.2、5份-95份的聚丁二烯、苯乙烯-丁二烯无规共聚物及嵌段共聚物、丙烯腈-丁二烯无规共聚物及嵌段共聚物、聚丁二烯和聚异戊二烯共聚物、乙烯和a-烯烃共聚物、乙烯和a-不饱和羧酸酯共聚物、乙烯-丙烯-非共轭二烯三元共聚物中一种或几种。
  8. 根据权利要求7所述的聚碳酸酯组合物，其特征在于，所述丁二烯共聚物选自苯乙烯-丁二烯-苯乙烯嵌段共聚物SBS、丙烯腈-丁二烯-苯乙烯接枝共聚物ABS、甲基丙烯酸甲酯-丙烯腈-丁二烯苯乙烯共聚物MABS、甲基丙烯酸甲酯-丁二烯-苯乙烯接枝共聚物MBS中的一种或几种；优选为丙烯腈-丁二烯-苯乙烯接枝共聚物ABS；其中，MBS的粒径优选0.1um-0.5um，本体聚合法ABS粒径优选0.1um-2um，乳液聚合法ABS粒径优选0.05um-0.2um。
  9. 根据权利要求1-3任一项所述的聚碳酸酯组合物，其特征在于，所述聚碳酸酯选自通过界面聚合法、熔融酯交换法、吡啶法、环状碳酸酯化合物的开环聚合法和预聚物的固相酯交换法制备的聚碳酸酯的一种或几种。
  10. 根据权利要求1-3任一项所述的聚碳酸酯组合物，其特征在于，所述聚碳酸酯选自芳香族聚碳酸酯、脂肪族聚碳酸酯、芳香族-脂肪族聚碳酸酯、支化聚碳酸酯中的一种或几种；优选为芳香族聚碳酸酯；所述芳香族聚碳酸酯选自粘均分子量13000-40000的芳香族聚碳酸酯，优选为粘均分子量16000-28000的芳 香族聚碳酸酯，更优选为粘均分子量17000-24000的芳香族聚碳酸酯。
  11. 根据权利要求1-3任一项所述的聚碳酸酯组合物，其特征在于，所述阻燃剂选自卤系阻燃剂或无卤阻燃剂，优选无卤阻燃剂；所述卤系阻燃剂选自溴化聚苯乙烯、溴化聚苯醚、溴化双酚A型环氧树脂、溴化苯乙烯-马来酸酐共聚物、溴化环氧树脂、溴化苯氧基树脂、十溴二苯醚、十溴代联苯、溴化聚碳酸酯、全溴三环十五烷或溴化芳香族交联聚合物的一种或几种，优选为溴化聚苯乙烯；所述无卤阻燃剂选自含氮阻燃剂、含磷阻燃剂或含氮和磷的阻燃剂中的一种或几种，优选为含磷阻燃剂。
  12. 根据权利要求11所述的聚碳酸酯组合物，其特征在于，所述含磷阻燃剂选自磷酸三苯基酯、磷酸三甲苯基酯、磷酸甲苯基二苯基酯、磷酸三二甲苯基酯、磷酸三(2,4,6-三甲基苯基)酯、磷酸三(2,4-二叔丁基苯基)酯、磷酸三(2,6-二叔丁基苯基)酯、间苯二酚双(磷酸二苯基酯)、对苯二酚双(磷酸二苯基酯)、双酚A-双(磷酸二苯基酯)、间苯二酚双(2,6-二叔丁基苯基磷酸酯)、对苯二酚双(2,6-二甲基苯基磷酸酯)的一种或几种。
  13. 根据权利要求1-3任一项所述的聚碳酸酯组合物，其特征在于，所述组分d的其它助剂选自热稳定剂、抗氧剂、抗滴落剂、光稳定剂、增塑剂、填料、着色剂的一种或几种。
  14. 一种如权利要求1-13任一项所述的聚碳酸酯组合物的制备方法，其特征在于，包括如下步骤：
    1)选取丁二烯共聚物结构的内部大海岛结构橡胶相与其内部最小长径小海岛结构的长径比值在1.01-80区间，且该类型大小海岛结构占比90％以上的丁二烯共聚物；
    2)将聚碳酸酯、丁二烯共聚物、阻燃剂、其它助剂按照比例称量后，通过高混机或者混合机完成共混，挤出，过水冷却，造粒得到柱状颗粒的聚碳酸酯组合物。
PCT/CN2016/085077 2015-06-08 2016-06-07 一种聚碳酸酯组合物及其制备方法 Ceased WO2016197906A1 (zh)

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