CN102888086A - Flame-retardant composition having improved melt liquidity - Google Patents
Flame-retardant composition having improved melt liquidity Download PDFInfo
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Abstract
The invention discloses a flame-retardant composition. The composition comprises polycarbonate, polypropylene terephthalate, an impact modifier, an organophosphorus ester flame retardant, a melt flow modifier and other optional additives. Good balance among the flame retardance, liquidity and mechanical property is realized by controlling the using amount of the melt modifier. The flame-retardant composition and a molding article prepared from the flame-retardant composition disclosed by the invention are suitable to be taken as electric/electronic device components, automobile components, machine components and the like.
Description
Technical field
The present invention relates to the polymeric composition technical field, especially relate to a kind of the have flame-retardant composition that improves fluidity of molten and good mechanical properties, the preparation method of this flame-retardant composition and application thereof.
Background technology
Comprise polycarbonate (PC), polyester and Elastic reactance impact modifier for example the thermoplastic compounds of acrylonitrile-butadiene-styrene copolymer (ABS) or methyl acrylate-butadiene-styrene copolymer (MBS) be known.In thermoplastic compounds (having another name called the PC/ polyester alloy, PC/polyester alloy), add impact modifier not only to cause improved shock resistance, and cause improved overall mechanical properties.Rear a kind of effect ascribes non-crystalline PC to and the crystallinity polyester mediates and has better consistency by impact modifier.
The PC/ polyester alloy, for the production of film, fiber, extrusion sheet, laminated multi-layer product and moulded product, is particularly useful for instrument housing, car body plate and other part member for automobile, Electrical and Electronic application.Good physical strength, anti-rush intensity and flame retardant resistance and be easy to processing be some key features of PC/ polyester alloy, this impels it for above-mentioned application.
In recent years, especially, for the PC/ polyester alloy is used as to electric or electronic part material, requirement is fire safety, and therefore described material often is required to have high fire resistance to pass through UL-94(American insurance people laboratory standard) the V-0 grade.Therefore developed various fire retardants, and it has been studied, to give the thermoplastic compounds high fire resistance.For environment and healthy consideration, the industry is preferably used halogen-free flame retardants.In many different types of halogen-free flame retardantss, organophosphate enjoys favor recently.
For example, CN101104731A discloses a kind of flame-retardant composition, and it comprises 50-85% PC, 5-30% PET, 2-15 % core-shell graft copolymer, 5-15 % phosphonium flame retardants, and other optional member.Described phosphonium flame retardant is selected from trimethyl phosphite 99, triethyl phosphate, triphenylphosphate and/or Resorcinol two (diphenyl phosphate) (RDP).Described composition has good flame retardant resistance, and UL94 V-0(batten thickness is 1.6 millimeters).Do not mention in the disclosure document and can add using flow ability modifying agent as additive described composition.
Yet, when thermoplastic compounds during with relative high density preparation, may cause fluidity of molten significantly to descend with various additives such as impact modifier and fire retardant etc.Especially, have for processing that the parts of Fine design are not enough with regard to the mobility of finding conventional flame retardants PC/ polyester alloy with the complexity of small flow cross section.
CN101050302A discloses a kind of flame retardant resistance PC/polytrimethylene terephthalate (PTT) alloy, it comprises 50-60 % by weight PC and 20-30 % by weight PTT, flame-retardant compound with 5-7 % by weight aromatics organophosphates and 2-4 % by weight polyphenylmethyl base silicone, expanding material mixture with 4-6 % by weight MBS and 3-5 % by weight phenylethylene-maleic anhydrides (SMAH), and other additive.The polyphenylmethyl base silicone of this flame-retardant compound it is said the consumption (optimum proportion of aromatics organophosphate and polyphenylmethyl base silicone is 6: 3) that can reduce the aromatics organophosphate, still meet the requirement (batten thickness is 0.8 millimeter) of UL-94 V-0 simultaneously, also can improve the fluidity of molten (melt flow index is 18 g/10 min) of described alloy, make it be equivalent to similar imported product.
The invention provides a kind of flame retardant resistance PC/PTT composition, its following character is very excellent: flame retardant resistance, physical strength and mouldability, the present composition disclosed herein is not sacrifice its mechanical property by the polyvalent alcohol of blend significant quantity to realize high workability as melt flow properties-correcting agent.
Summary of the invention
The present invention relates to a kind of flame-retardant composition, said composition comprises:
(a) aromatic polycarbonate of about 50-75 % by weight,
(b) polytrimethylene terephthalate of about 8-20 % by weight,
(c) impact modifier of about 3-15 % by weight
(d) the organophosphorus ester flame-proof agent of about 10-20 % by weight, and
(e) the melt flow properties-correcting agent of about 0.01-0.5 % by weight,
Wherein said percentage ratio is based on the gross weight of flame-retardant composition.
In one embodiment, in flame-retardant composition of the present invention, described aromatic polycarbonate is the polycarbonate of dihydroxyphenyl propane base.
In one embodiment, in flame-retardant composition of the present invention, the melt mass flow rate of described aromatic polycarbonate is about 5-20 gram/10 minute.
In one embodiment, in flame-retardant composition of the present invention, the limiting viscosity of described polytrimethylene terephthalate is about 0.8 to 1.2.
In one embodiment, in flame-retardant composition of the present invention, described impact modifier is the core-shell type multipolymer, the shell that it comprises polymethylmethacrylate.
In one embodiment, in flame-retardant composition of the present invention, described impact modifier is the core-shell type multipolymer, the shell that it comprises polymethylmethacrylate, and this shell is grafted on rubbery kernel.
In one embodiment, in flame-retardant composition of the present invention, the second-order transition temperature of the rubbery kernel of described impact modifier is about-80 ℃ to-20 ℃.
In one embodiment, in flame-retardant composition of the present invention, the rubbery kernel of described impact modifier is divinyl rubber or silicon rubber.
In one embodiment, in flame-retardant composition of the present invention, described organophosphate is the compound of formula 1:
Wherein
R
1be phenyl, it is optionally by three C at the most
1-C
4alkyl replaces; With
R
2q1, Q2 or Q3:
In one embodiment, in flame-retardant composition of the present invention, described organophosphate is selected from Resorcinol two (diphenyl phosphate), Resorcinol two (2,6-dimethylbenzene phosphoric acid ester), dihydroxyphenyl propane two (diphenyl phosphate) and quinhydrones two (diphenyl phosphate).
In one embodiment, in flame-retardant composition of the present invention, described melt flow properties-correcting agent is polyvalent alcohol, be selected from 2，2-dimethyl-1，3-propanediol, glycerine, 1,1,1-tri-(methylol) ethane, 1,1,1-tri-(methylol) propane, tetramethylolmethane, Xylitol, Sorbitol Powder, Dipentaerythritol and tripentaerythritol.
In one embodiment, in flame-retardant composition of the present invention, described melt flow properties-correcting agent is 1,1,1-tri-(methylol) ethane, tetramethylolmethane, Xylitol or Sorbitol Powder.In one embodiment, in flame-retardant composition of the present invention, described melt flow properties-correcting agent tetramethylolmethane, Dipentaerythritol or tripentaerythritol.
In one embodiment, flame-retardant composition of the present invention also comprises and is selected from least one following additive: anti-dripping agent, antioxidant, stable radiation agent, thermo-stabilizer, UV light stabilizing agent, ultraviolet absorbers, hydrolysis-resisting agent, the tinting material that comprises dyestuff and pigment, reinforced filling, processing aid, lubricant, releasing agent, static inhibitor and combination thereof.
In one embodiment, in flame-retardant composition of the present invention, described at least one additive is selected from: anti-dripping agent, antioxidant, thermo-stabilizer, hydrolysis-resisting agent, releasing agent and combination thereof.
The invention still further relates to a kind of moulded parts that comprises described flame-retardant composition or made by described flame-retardant composition.The invention still further relates to described moulded parts as electrical/electronic device component, trolley part, the purposes of mechanical part etc.
By reading right require, following description and embodiment, people can more understand other various features of the present invention, emphasis and advantage.
Embodiment
Unless otherwise indicated, the mode that mentioned all publications, patent application, patent and other reference of this paper all quoted with integral body is incorporated herein, as it is set forth in full.
Unless otherwise defined, all technology that this paper is used and scientific terminology have common the understood identical meanings of one skilled in the art of the present invention.In the situation that inconsistent, with the definition in this specification sheets, be as the criterion.
Unless otherwise indicated, all percentage ratio, umber, ratio etc. are all by weight.
In this article, term " by ... make " be equal to " comprising ".Term used herein " comprises ", " comprising ", " having ", " having ", " containing " or its any other variant are intended to contain comprising of non-exclusionism.For example, the composition that comprises a series of key elements, technique, method, goods or equipment might not be only limited to those key elements, but can also comprise key element that these compositions, technique, method, goods or equipment clearly do not enumerate or other intrinsic key elements.
Conjunction " by ... form " do not comprise any key element of clearly not enumerating, step or composition.If there is in the claims, this conjunction will make claim be limited to described material and not comprise the material of not describing, but still comprise and those described materials relevant impurity usually.When conjunction " by ... form " appear at the characteristic of claim, but not immediately during preamble, the key element that it only limits to set forth in characteristic; Other key elements are not required to get rid of in integral body by Accessory Right.
Conjunction " substantially by ... form " for also comprising combination, method or the equipment of other material, step, feature, component or key element outside literal the above those materials, step, feature, component or the key element of definite division, prerequisite is essential characteristic and the novel feature that these other materials, step, feature, component or key element substantially do not affect invention required for protection.Conjunction " substantially by ... form " in " comprising " and " by ... form " between a rank.
Conjunction " comprise " intention comprise conjunction " substantially by ... form " and " by ... composition " embodiment of containing.Similarly, conjunction " substantially by ... form " intention comprise conjunction " by ... form " embodiment that contains.
When with scope, preferable range or a series of upper limit preferred value and lower limit preferred value, providing quantity, concentration or other numerical value or parameter, should understand it and specifically disclose the formed all scopes of any logarithmic value by any range limit value or preferred value and any scope lower value or preferred value, and no matter whether these scopes are disclosed respectively.For example, when describing the scope of " 1 to 5 ", described scope should be interpreted as comprising the scopes such as " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to 5 ", " 1 to 3 and 5 ".Except as otherwise noted, at this paper, describe the numerical range part, described scope intention comprises all integers and the mark in scope end value and scope.
When term " about " is used for describing the end value of numerical value or scope, disclosed content is understood to include occurrence or related end value.
In addition, unless clearly meaned contrary, "or" refers to the "or" of pardon but not exclusive "or".For example, below arbitrary condition all applicable elements A "or" B:A be that true (or existence) and B are false (or not existing), A is that false (or not existing) and B are true (or existence), and A and B are true (or existence).
In addition, the word before key element of the present invention or component " " and " a kind of " intention mean that appearance (the occurring) number of times for this key element or component does not have restricted.Therefore, " one " or " a kind of " be understood to include a kind of or at least one, unless clearly meaned that quantity is odd number, otherwise the described key element of singulative or component also comprise plural situation.
In specification sheets of the present invention and/or claims, term " homopolymer " refers to the product derived from a kind of polyreaction of monomer; " multipolymer " refers to the product derived from the polyreaction of two or more monomers.Described multipolymer comprises copolymer, terpolymer or multiple copolymer.Unless clearly meaned term " polymer " " comprise homopolymer and multipolymer, it also writes (being total to) polymkeric substance.
When describing some polymkeric substance, should understand applicant sometimes by the monomer for preparing polymkeric substance and use or prepare the amount of monomer that polymkeric substance uses and describe this polymkeric substance.Although this description may not comprise the concrete name of this final polymkeric substance, or may not comprise the term of method-restriction-product, but the polymkeric substance that is interpreted as meaning comprising those monomers (being the copolymerization units of those monomers) or amount of monomer for the statement of monomer and amount thereof, with and corresponding polymkeric substance and composition.
Embodiment of the present invention, be included in the embodiment of following any other of embodiment of the present invention described in the summary of the invention part and this paper, all can at random be combined, and in embodiment, the description of variable is not only applicable to described flame-retardant composition, also be applicable to the moulded parts made by it.
Below describe the present invention.At first the component (a)-(e) that forms flame-retardant composition of the present invention is described.
(a) aromatic polycarbonate
The component of flame-retardant composition of the present invention (a) aromatic polycarbonate is by diphenol and carbonate precursor, by solution method or scorification, makes; For example by diphenol and phosgene reaction, make, or carry out transesterification reaction by diphenol and dipheryl carbonate base ester and make.
The present invention can use various diphenol, for example: 2, two (4-hydroxy phenyl) propane (being dihydroxyphenyl propane) of 2-, two (4-hydroxy phenyl) methane, 1, two (4-hydroxy phenyl) ethane, 2 of 1-, two (4-hydroxyl-3 of 2-, the 5-3,5-dimethylphenyl) propane, 4,4' dihydroxy diphenyl, two (4-hydroxy phenyl) naphthenic hydrocarbon, bis oxide (4-hydroxy phenyl), sulfuration two (4-hydroxy phenyl), two (4-hydroxy phenyl) sulfones, two (4-hydroxy phenyl) sulfoxide, two (4-hydroxy phenyl) ether, two (4-hydroxy phenyl) ketone etc.Other diphenol, also can be for the present invention such as quinhydrones, Resorcinol, pyrocatechol etc.Diphenol of the present invention may be used singly or in combin.
Comprise carbonyl carboxylic acid halides, carbonyl ester, haloformate for carbonate precursor of the present invention, comprise specifically phosgene, dihalo formic acid hexichol phenolic ester, dipheryl carbonate base ester, methylcarbonate, diethyl carbonate etc.
By add the cladodification agent in polymerization process, can make the polycarbonate of cladodification.These cladodification agent are that people are well-known, can comprise the polyfunctional group organic compound that contains at least three functional groups, and described functional group can be hydroxyl, carboxyl, acid anhydride, halo formyl radical and their mixture.Concrete example comprises trimellitic acid, trimellitic acid 1,2-anhydride, inclined to one side benzene three acyl chlorides, 1; 1; 1-tri-(4-hydroxyl) diphenylphosphino ethane, isatin bis-phenol, triphenol TC (1; 3; 5-tri-((p-hydroxybenzene)-sec.-propyl) benzene), triphenol PA (4 (4 (1; two (the p-hydroxybenzene)-ethyls of 1-) a, a-dimethyl benzyl) phenol), 4-chloroformyl Tetra hydro Phthalic anhydride, trimesic acid and benzophenone tetracarboxylic acid.The amount that the cladodification agent can add is approximately the 0.05-2.0 % by weight.United States Patent (USP) the 3rd, 635, No. 895; 4,001,184; With 4,204, cladodification agent and the technique of the polycarbonate of preparation cladodification has been described in No. 047.
Various polycarbonate resin can be mixed, the mixed polycarbonate resin made is for the present invention.For example, polycarbonate can be the polycarbonate of cladodification or the polycarbonate of non-cladodification, their multipolymer, and their mixture.In another embodiment, described polycarbonate resin is the mixture of two or more polycarbonate resins.
The wherein noticeable aromatic polycarbonate that is based on dihydroxyphenyl propane, i.e. dihydroxyphenyl propane base aromatic polycarbonate.In another embodiment, described aromatic polycarbonate is according to ISO1133, and the melt mass flow rate recorded under the load of 300 ℃ and 1.2 kilograms is about 5-20 gram/10 minute, preferably is about 8-12 gram/10 minute.
Suitable polycarbonate can be selected from existing goods, for example, purchased from the MAKROLON of Bayer AG (Bayer)
tM, purchased from the LEXAN of SABIC innovation Plastics Company (SABIC Innovative Plastics)
?, purchased from the PANLITE of Te Jin company (Teijin)
?, purchased from the XANTAR of DSM
?, purchased from the IUPILON of Mitsubishi (Mitsubishi)
?, and purchased from the CALIBER of the Dow Chemical Company (Dow)
?.More than enumerate is exemplary but not exhaustive.
The consumption of aromatic polycarbonate (a) in flame-retardant composition of the present invention is about the 50-75 % by weight of flame-retardant composition gross weight, preferably is about the 55-65 % by weight.
(b) polytrimethylene terephthalate
Polytrimethylene terephthalate (PTT) as the component (b) of flame-retardant composition of the present invention is a kind of polyester.Polyester polymers is well known to the skilled person, can comprise by esterification or transesterification reaction and be derived from alcohol and any polycondensation product that comprises the dicarboxylic acid of its ester.
Polytrimethylene terephthalate (PTT) can be by the polycondensation preparation of 1,3-PD and terephthalic acid.Perhaps, polytrimethylene terephthalate can also be by 1,3-PD and dimethyl terephthalate (DMT) preparation.The 1,3-PD that is used for preparing PTT, preferably by biochemical method, obtains (" biological process obtains " 1,3-PD) by renewable resources.
Because polyester and preparation method thereof is well known to the skilled person, in order to compose a piece of writing for purpose of brevity, no longer it is conducted further description herein.
The molecular weight of polymkeric substance can be measured with its limiting viscosity (Intrinsic Viscosity, IV), can measure according to the method for ASTM D4603-96.For example, use Y-900 type Viscotek to force the stream viscometer, with the concentration of 0.5% (weight/volume), polymer dissolution, in phenol/tetrachloroethane (60/40 % by weight) solution, is tested at 25 ℃.Limiting viscosity usually can increase along with the molecular weight of polymkeric substance and increase, but its numerical value also depends on macromolecular kind, its shape or configuration, and test solvent used.
In one embodiment, in flame-retardant composition of the present invention, the limiting viscosity of described polytrimethylene terephthalate is about 0.8-1.2.
The polytrimethylene terephthalate that can buy on market includes but not limited to the SORONA purchased from E.I.Du Pont Company (DuPont)
?and purchased from the CORTERRA of shell chemical company (Shell Chemicals)
?.
The consumption of polytrimethylene terephthalate (b) in flame-retardant composition of the present invention is about the 8-20 % by weight of flame-retardant composition gross weight, preferably is about the 10-16 % by weight.
(c) impact modifier
The component of flame-retardant composition of the present invention (c) is impact modifier.Described impact modifier can be to be selected from following at least one: olefin copolymer, core-shell graft copolymer and combination thereof.
Can include but not limited to for the example of olefin copolymer of the present invention ethylene/propylene rubber, synthetic polyisoprene, ethylene/octene rubber, ethylene-propylene-diene terpolymer (EPDM) etc., and combination.
Described olefin copolymer can be with at least one active function groups grafting of about 0.1-5 % by weight, to form core-shell graft copolymer, described at least one active function groups is selected from maleic anhydride, glycidyl methacrylate, oxazoline etc., and their combination.Those of ordinary skills can enter the active function groups grafting in described olefin copolymer at an easy rate.
Can be used for exemplary core-shell graft copolymer of the present invention can prepare in the following manner: at least one rubber monomer of polymerization, such as elastoprene monomer, acrylic elastomer monomer, rubber monomer etc. or its combination, to form rubber polymer, and with at least one monomer, the rubbery kernel polymkeric substance made is carried out to grafting, form its shell, for example graftable vinylbenzene, alpha-methyl styrene, halogen-or alkyl (C for example
1-C
8vinylbenzene, vinyl cyanide, methacrylonitrile, the methacrylic acid C of alkyl)-replacement
1-C
8alkyl ester, vinylformic acid C
1-C
8alkyl ester, maleic anhydride, unsaturated compound, for example C
1-C
4the maleimide that alkyl or phenyl core replaces etc., or its combination.The content of rubbery kernel can be about the 30-90 % by weight.
Described methacrylic acid C
1-C
8alkyl ester or vinylformic acid C
1-C
8alkyl ester is methacrylic acid or acrylic acid alkyl ester, by the monohydroxy-alcohol preparation that comprises 1-8 carbon atom.The example of these alkyl esters can include but not limited to methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate etc., and combination.
In one embodiment, in flame-retardant composition of the present invention, described impact modifier is the core-shell type multipolymer, the shell that it comprises polymethylmethacrylate.In one embodiment, in flame-retardant composition of the present invention, described impact modifier is the core-shell type multipolymer, the shell that it comprises polymethylmethacrylate, and this shell is grafted on rubbery kernel.
The example of dience rubber can include but not limited to butadiene hydrocarbon rubber, acrylic rubber, ethylene/propylene rubber, styrene/butadiene rubbers, acrylonitrile/butadiene rubber, synthetic polyisoprene, ethylene-propylene-diene terpolymer (EPDM) etc., and its its combination.
Described acrylic elastomer can be by the monomer preparation that comprises acrylate, such as but not limited to methyl acrylate, ethyl propenoate, vinylformic acid n-propyl, n-butyl acrylate, ethyl acrylate, N-Hexyl methacrylate, methacrylic acid-2-ethylhexyl etc., and combination.The example that is applicable to the solidifying agent for preparing described multipolymer can include but not limited to Ethylene glycol dimethacrylate, dimethyl allene acid propylene glycol ester, dimethacrylate 1,3-butanediol ester, dimethacrylate 1,4-butanediol ester, allyl methacrylate(AMA), triallyl cyanurate etc., and combination.
Can be prepared by cyclosiloxane by silicon rubber.The example of cyclosiloxane can include but not limited to hexamethyl cyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentaandoxane, ten diformazan basic ring six siloxanes, trimethyl triphenyl cyclotrisiloxane, tetramethyl tetraphenyl cyclotetrasiloxane, octaphenylcyclotetrasiloxane etc., and their combination.Silicon rubber can be used solidifying agent, by least one above-mentioned siloxanyl monomers preparation.The example of suitable solidifying agent can include but not limited to trimethoxymethylsila,e, triethoxyphenylsilan, tetramethoxy-silicane, tetraethoxysilane etc., and combination.
In one embodiment, in flame-retardant composition of the present invention, the rubbery kernel of described impact modifier is divinyl rubber or silicon rubber.
At United States Patent (USP) the 3rd, 864, No. 428 and the 4th, the preparation of core-shell polymer has been described and as the application of impact modifier in 264, No. 487.
Suitable impact modifier can be the mixture that comprises core-shell impact modifier, and described core-shell impact modifier is used alkyl acrylate, vinylbenzene and divinyl, by letex polymerization, prepares.This comprises core-shell polymers such as MBS (MBS) and methyl methacrylate-butyl acrylate.Particularly preferred graftomer is purchased from (the Rohm & of Rhom and Hass; Haas) commodity are called PARALOID
?core-shell polymer, comprise for example PARALOID
?eXL3691 and PARALOID
?eXL3330, EXL3300 and EXL2300, and purchased from the Clearstrength of Arkema (Arkema)
?e920.
Described impact modifier can have various granularities.Preferred size range is the 50-800 nanometer, but also can adopt larger particle, or small-particle and oarse-grained mixture.
Preferred impact modifier comprises rubbery kernel, the Tg of described rubbery kernel (second-order transition temperature) is between-80 ℃ to-20 ℃, preferably be about-60 ℃ to approximately-30 ℃, it comprises polyalkyl acrylate or polyolefine, and it is grafted with polymethylmethacrylate or styrene-acrylonitrile copolymer.
In one embodiment, in flame-retardant composition of the present invention, the second-order transition temperature of the rubbery kernel of described impact modifier is about-80 ℃ to-20 ℃.
The consumption of impact modifier (c) is about the 3-15 % by weight of flame-retardant composition gross weight, preferably is about the 5-10 % by weight.
When the content of impact modifier is less than about 3 % by weight, this can cause in flame-retardant composition impact-resistant modified effect not remarkable.On the other hand, when the content of impact modifier is approximately higher than 15 % by weight, can cause physical strength (such as tensile strength, the modulus in flexure etc.) variation of flame-retardant composition.
(d) organophosphate
Adding the component (d) of flame-retardant composition of the present invention is organophosphate.Described organophosphate for flame-retardant composition of the present invention is the compound of formula 1:
Wherein
R
1be phenyl, it is optionally by three C at the most
1-C
4alkyl replaces; With
R
2q1, Q2 or Q3:
。
Can be used for organophosphorus ester flame-proof agent of the present invention and include but not limited to phosphoric acid ester, for example Resorcinol two (diphenyl phosphate) (RDP), Resorcinol two (2,6-dimethylbenzene phosphoric acid ester) (RDX), dihydroxyphenyl propane two (diphenyl phosphate) (BDP) and quinhydrones two (diphenyl phosphate) (Doher – 7000).
Commercially available organophosphorus ester flame-proof agent includes but not limited to RDP, BDP, RDX and/or Doher-7000, it can contain chemical industry (Zhejiang Wansheng Chemical Co., Ltd.) purchased from large eight chemistry of Japan (Daihachi Chemical Industry) and Zhejiang ten thousand.
The consumption of organophosphate (d) is about the 10-20 % by weight of flame-retardant composition gross weight, preferably is about the 12-18 % by weight, is more preferably the 13-16 % by weight.When the content of organophosphate is less than 10 % by weight, flame-retardant composition is 1.5 millimeters (1/16 inches) lower requirement that can not meet UL94 V – 0 grade at batten thickness.When the content of organophosphate surpasses 20 % by weight, the mechanical properties of flame-retardant composition can be subject to negative impact.
(e) melt flow properties-correcting agent
The component of flame-retardant composition of the present invention (e) is melt flow properties-correcting agent.Melt flow properties-correcting agent for flame-retardant composition of the present invention is polyvalent alcohol.
Be applicable to melt flow properties-correcting agent of the present invention and include but not limited to polyvalent alcohol, as 2,2-dimethyl-1, ammediol, glycerine, 1,1,1-tri-(methylol) ethane, 1,1,1-tri-(methylol) propane, tetramethylolmethane, Xylitol, Sorbitol Powder, Dipentaerythritol and tripentaerythritol.
In one embodiment, in flame-retardant composition of the present invention, described melt flow properties-correcting agent is polyvalent alcohol, be selected from 2，2-dimethyl-1，3-propanediol, glycerine, 1,1,1-tri-(methylol) ethane, 1,1,1-tri-(methylol) propane, tetramethylolmethane, Xylitol, Sorbitol Powder, Dipentaerythritol and tripentaerythritol.
In one embodiment, in flame-retardant composition of the present invention, described melt flow properties-correcting agent is 1,1,1-tri-(methylol) ethane, tetramethylolmethane, Xylitol or Sorbitol Powder.In one embodiment, in flame-retardant composition of the present invention, described melt flow properties-correcting agent is tetramethylolmethane, Dipentaerythritol and tripentaerythritol.
The consumption of melt flow properties-correcting agent (e) is about the 0.01-0.5 % by weight of flame-retardant composition gross weight, preferably is about the 0.05-0.3 % by weight.When the amount of melt flow properties-correcting agent is about 0.1 % by weight, this flame-retardant composition can be observed mobility and improve when having good mechanical properties.When the amount of melt flow properties-correcting agent surpasses 0.5 % by weight, the mechanical properties of flame-retardant composition can be subject to negative impact.
other additive
Flame-retardant composition of the present invention also can comprise a small amount of polymer arts known optional additives commonly used.The example of additive includes but not limited to anti-dripping agent, antioxidant, stable radiation agent, thermo-stabilizer, UV light stabilizing agent, ultraviolet absorbers, hydrolysis-resisting agent, the tinting material that comprises dyestuff and pigment, reinforced filling, processing aid, lubricant, releasing agent, static inhibitor and combination thereof.
The content of these additives in described flame-retardant composition can be generally the 0.01-15 % by weight, preferred 0.01-10 % by weight, as long as they can not destroy the feature of novelty on the basis of described flame-retardant composition, and cause significant negative impact can not to the performance of flame-retardant composition.
The known anti-dripping agent for example fluoropolymer of chemical modification can be dispersed in thermoplastic compounds, thereby the moulding part made by it improves its flame retardant properties because of given anti-drippage.Fluoropolymer for example PTFE particle can be coated with and guarantee good dispersion in polymeric matrix with acrylic copolymer, styrol copolymer or styrene-acrylonitrile copolymer (SAN).Commercially available anti-dripping agent includes but not limited to Shinepoly
?sN3300 or Shinepoly
?sN3306, it is manufactured by Shangneng Polymer Tech Co., Ltd., Guangzhou (ShinePolymer).The consumption of anti-dripping agent is about 0.1-2 % by weight of flame-retardant composition gross weight.
Reinforced filling is carbon fiber for example, short glass fiber, and long glass fibres, mica, talcum, wollastonite, clay, the fibrillation tetrafluoroethylene is normally well known in the art, and its manufacture method is well-known equally.
Flame-retardant composition of the present invention can form by technology known in the art.Described component and optional additive are generally the form of powder or particle, can be used as mixture and extrude, and/or cut into pill or other suitable shape.Described component can combine in any manner, for example, by dry blending or mix with molten state in forcing machine or other mixing tank.For example, an embodiment comprises the component of melting mixing powder or particle form, and mixture is extruded, and then is ground into pill or other suitable shape.Also comprise component is carried out to dry blending, then, in forcing machine, mixed in molten state.
In fact can make moulded parts by flame-retardant composition of the present invention as above by any extruding process thereof well known by persons skilled in the art or method for hot forming.For example, can adopt extrusion by melting, for example injection moulding, injection moulding altogether, compression moulding, quadric injection mould and profile are extruded.Therefore, described goods can be injection mouldings, compression molding, the profile extrusion moulding etc.The moulded parts that preferably comprises above-mentioned flame-retardant composition or made by above-mentioned flame-retardant composition.
Flame-retardant composition of the present invention can be for the various products of molding, be particularly suitable for trolley part, for example, with the application of manufacturing the Electrical and Electronic related products, housing of TV set, counter body, mobile communication equipment shell and business automation equipment shell.Described flame-retardant composition can also be made the form of film and sheet material.
Embodiment
These embodiment are exemplary, can not form restriction improperly to scope of the present invention.All embodiment and Comparative Examples all are prepared and test with same method.Except as otherwise noted, percentage ratio is by weight.
Component used in embodiment is listed in table 1
Detailed step
A) mix: use super stream mixing tank that the component of each embodiment is mixed, then send into twin screw extruder (Eurolab 16), with the form of pill, make corresponding flame-retardant composition.For the forcing machine that comprises 10 heating zone designs, the Temperature Setting of forcing machine is at 90/180/250/250/250/250/250/250/250/250 ℃.Die head temperature is 250 ℃, and screw speed is 350 rpm, and work output is 4.5 kg/hrs.
B) molding: before molding, by the pill drying of extruding, be less than 40 ppm to moisture content.For the mechanical properties test, on 100 tons of mould machines of Sumitomo, according to the ISO3167 molding, prepare test bars, the screw diameter of mould machine is 32 millimeters, nozzle diameter is 5 millimeters.Barrel temperature is set in 250 ℃, and die temperature is 60 ℃.The basic configuration of described test bars is the dumb-bell shape batten, and long 150 millimeters, centre portions is of a size of wide 10 millimeters * thick 4 millimeters * long 80 millimeters.
Testing method
In 100 tons of mould machines of Sumitomo, use spiral mould to measure eddy flow (spiral flow).Under the fc-specific test FC condition, be determined at length of flow in mould (unit for centimetre).Melt temperature is 250 ℃, and die temperature is 60 ℃, 2 millimeters of eddy flow spacings, supercharging pressure 80 Mpa.Initial 10-15 part is discarded, until reach constant length of flow.What report is the mean value of 5 parts.
Modulus in flexure (0.05%-0.25%) and the flexural stress under 3.5% strain are measured according to ISO178:2001 (E).
The mechanical properties of tensile modulus (0.05%-0.25%) and tensile stress and so on is measured according to ISO 527:1993 (E).
According to title, be " Tests for Flammability of Plasric Materials, UL94 ", the method for Underwriter's Laboratory Bulletin 94, carry out flame retardant test.According to the method, the test-results based on 5 sample gained, be divided into material six grades of 5VA, 5VB, V-0, V-1, V-2 and HB.Obtain the material of V-0 grade, be by a sample, make its major axis with flame, become 180 degree to put, after removing the burning burning things which may cause a fire disaster, the burning of this sample and/or be no more than 10 seconds the mean time of glowing, and the vertical sample of placing does not produce the drippage material that can light absorbent cotton.NVC means that sample can't meet the requirement of the minimum flame retardant rating of UL94.
The each component consumption of embodiment and Comparative Examples, with and assessment result list in table 2,3 and 4.
From the result of table 2, to draw a conclusion, be apparent.
From relatively can find out between embodiment 1 and Comparative Examples 1, (e) melt flow properties-correcting agent (being tetramethylolmethane) by mixing 0.05 % by weight and (a) aromatic polycarbonate of 68.4%, the flame-retardant composition that (d) organophosphate of 9.8% (b) PTT and 5.9% (c) impact modifier and 13.7% (being Doher-7000) obtains demonstrates mobility and significantly improves, be embodied in swirl data (increase approximately 20%), and for example, to mechanical property (tensile modulus, stretching yield stress, modulus in flexure and maximum deflection stress) affect minimum.
From relatively can find out between embodiment 2 and Comparative Examples 2, (e) melt flow properties-correcting agent (being tetramethylolmethane) by mixing 0.08 % by weight and (a) aromatic polycarbonate of 58.8%, the flame-retardant composition that (d) organophosphate of 14.2% (b) PTT and 7.2% (c) impact modifier and 17.6% (being Doher-7000) obtains demonstrates mobility and significantly improves, be embodied in swirl data (increase approximately 30%), and for example, to mechanical property (tensile modulus, stretching yield stress, modulus in flexure and maximum deflection stress) affect minimum.
From relatively can find out between Comparative Examples 3 and Comparative Examples 4, be reduced to 9.3% by the consumption by organophosphate (being PX200) from 14.0%, and replace with 4.7% polyphenyl methyl silicone (according to the optimum proportion of CN101050302A suggestion), cause PC/PTT composition (Comparative Examples 4) can not meet the requirement of the minimum flame retardant rating of UL94.In addition, in the mobility relatively increased between Comparative Examples 4 and embodiment 3,4.7% polyphenylmethyl base silicone does not obviously have 0.1% tetramethylolmethane so effectively to increase mobility (comparison between Comparative Examples 4 and embodiment 3), the latter demonstrates approximately 25% melt flow and improves, this point is to be embodied on its swirl data, still keeps excellent mechanical property and flame retardant resistance simultaneously.
From relatively can find out between the embodiment 4-9 of table 3 and Comparative Examples 5-7, component (a) aromatic polycarbonate by mixing (e) melt flow properties-correcting agent (being tetramethylolmethane) of 0.1% and various weight percents, (b) PTT, (c) impact modifier and (d) flame-retardant composition of the present invention that organophosphate obtains also demonstrate obtained excellent balance between flame retardant resistance, mobility and mechanical property.Please note, although composition has the melt flow properties-correcting agent (0.1 %) of same amount, but the swirl data obtained but increases with the content minimizing of aromatic polycarbonate, and this is because aromatic polycarbonate has poor intrinsic fluidity (intrinsic flowability) than PTT.
Table 3
As shown in table 4, comparative descriptions between Comparative Examples 6 and embodiment 7,10-14, the melt flow properties-correcting agent that the present composition comprises 0.08-0.2 % by weight is tetramethylolmethane (embodiment 7 and embodiment 10), 1 for example, 1,1-trimethylolethane (embodiment 11 and embodiment 12), Xylitol (embodiment 13) or Sorbitol Powder (embodiment 14), all compositions all cause mobility to be improved and have kept excellent mechanical property and flame retardant resistance simultaneously.
Although carry out example and set forth the present invention with typical embodiment, its intention is not to limit the invention to shown details, because may have multiple change and alternative not deviating under purport of the present invention.Thus, those skilled in the art only just may obtain improvement of the present invention disclosed herein and equivalent by normal experiment, and it is within the spirit and scope of the invention limited in appended claim that all these improvement and equivalent all should be considered as.
Claims (15)
1. a flame-retardant composition, it comprises:
(a) aromatic polycarbonate of 50-75 % by weight,
(b) polytrimethylene terephthalate of 8-20 % by weight,
(c) impact modifier of 3-15 % by weight,
(d) the organophosphorus ester flame-proof agent of 10-20 % by weight, and
(d) the melt flow properties-correcting agent of 0.01-0.5 % by weight;
Described percentage ratio is based on the gross weight of flame-retardant composition.
2. flame-retardant composition as claimed in claim 1, wherein said aromatic polycarbonate is dihydroxyphenyl propane base polycarbonate.
3. flame-retardant composition as claimed in claim 1, the melt mass flow rate of wherein said aromatic polycarbonate is 5-20 gram/10 minute.
4. flame-retardant composition as claimed in claim 1, the limiting viscosity of wherein said polytrimethylene terephthalate is 0.8 to 1.2.
5. flame-retardant composition as claimed in claim 1, wherein said impact modifier is the core-shell type multipolymer, this multipolymer is containing the shell of polymethylmethacrylate.
6. flame-retardant composition as claimed in claim 1, wherein said impact modifier is the core-shell type multipolymer, and this multipolymer is containing the shell of polymethylmethacrylate, and this shell is grafted on rubbery kernel.
7. flame-retardant composition as claimed in claim 6, the second-order transition temperature of the rubbery kernel of wherein said impact modifier is-80 ℃ to-20 ℃.
8. flame-retardant composition as claimed in claim 6, the rubbery kernel of wherein said impact modifier is divinyl rubber or silicon rubber.
9. flame-retardant composition as claimed in claim 1, wherein said organophosphorus ester flame-proof agent is the compound of formula 1:
Wherein
R
1be phenyl, it is optionally by three C at the most
1-C
4alkyl replaces; With
R
2q1, Q2 or Q3:
10. flame-retardant composition as claimed in claim 1, wherein said organophosphorus ester flame-proof agent is selected from Resorcinol two (diphenyl phosphate), Resorcinol two (2,6-dimethylbenzene phosphoric acid ester), dihydroxyphenyl propane two (diphenyl phosphate) and quinhydrones two (diphenyl phosphate).
11. flame-retardant composition as claimed in claim 1, wherein said melt flow properties-correcting agent is that polyvalent alcohol is selected from: 2,2-dimethyl-1, ammediol, glycerine, 1,1,1-tri-(methylol) ethane, 1,1,1-tri-(methylol) propane, tetramethylolmethane, Xylitol, Sorbitol Powder, Dipentaerythritol and tripentaerythritol.
12. flame-retardant composition as claimed in claim 11, wherein said melt flow properties-correcting agent is 1,1,1-tri-(methylol) ethane, tetramethylolmethane, Xylitol or Sorbitol Powder.
13. flame-retardant composition as claimed in claim 1, wherein said flame-retardant composition also comprises and is selected from least one following additive: anti-dripping agent, antioxidant, stable radiation agent, thermo-stabilizer, UV light stabilizing agent, ultraviolet absorbers, hydrolysis-resisting agent, the tinting material that comprises dyestuff and pigment, reinforced filling, processing aid, lubricant, releasing agent, static inhibitor and combination thereof.
14. flame-retardant composition as claimed in claim 13, wherein said flame-retardant composition also comprises and is selected from least one following additive: anti-dripping agent, antioxidant, thermo-stabilizer, hydrolysis-resisting agent, releasing agent and combination thereof.
A 15. moulded parts, described moulded parts comprises the described flame-retardant composition of any one in claim 1-14, perhaps in claim 1-14, the described flame-retardant composition of any one is obtained, and it is to be determined as the flame retardant resistance of V-0 grade under 1.5 millimeters at batten thickness that wherein said moulded parts has the UL94 combustion test.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108276751A (en) * | 2017-12-26 | 2018-07-13 | 浙江普利特新材料有限公司 | A kind of high-impact high fire-retardance PC-ABS composite material and preparation methods |
| US10240039B2 (en) | 2014-12-23 | 2019-03-26 | Sabic Global Technologies B.V. | Reinforced polycarbonate compositions |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101171303A (en) * | 2005-05-02 | 2008-04-30 | 通用电气公司 | Thermoplastic polycarbonate compositions with improved optical surface quality, articles made therefrom and method of manufacture |
| CN101175804A (en) * | 2005-08-31 | 2008-05-07 | 通用电气公司 | High flow polyester composition |
| CN101418118A (en) * | 2008-12-05 | 2009-04-29 | 北京化工大学 | Halogen-free flame retardant PC/ABS alloy and preparation method thereof |
| CN101547973A (en) * | 2006-12-01 | 2009-09-30 | 拜尔材料科学有限公司 | Thermoplastic molding composition having improved toughness at low temperatures and surface appearance |
| CN101974216A (en) * | 2010-10-29 | 2011-02-16 | 大河宝利材料科技(苏州)有限公司 | Halogen-free flame-retardant PC/ABS alloy |
-
2011
- 2011-07-22 CN CN2011102063425A patent/CN102888086A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101171303A (en) * | 2005-05-02 | 2008-04-30 | 通用电气公司 | Thermoplastic polycarbonate compositions with improved optical surface quality, articles made therefrom and method of manufacture |
| CN101175804A (en) * | 2005-08-31 | 2008-05-07 | 通用电气公司 | High flow polyester composition |
| CN101547973A (en) * | 2006-12-01 | 2009-09-30 | 拜尔材料科学有限公司 | Thermoplastic molding composition having improved toughness at low temperatures and surface appearance |
| CN101418118A (en) * | 2008-12-05 | 2009-04-29 | 北京化工大学 | Halogen-free flame retardant PC/ABS alloy and preparation method thereof |
| CN101974216A (en) * | 2010-10-29 | 2011-02-16 | 大河宝利材料科技(苏州)有限公司 | Halogen-free flame-retardant PC/ABS alloy |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10240039B2 (en) | 2014-12-23 | 2019-03-26 | Sabic Global Technologies B.V. | Reinforced polycarbonate compositions |
| CN108276751A (en) * | 2017-12-26 | 2018-07-13 | 浙江普利特新材料有限公司 | A kind of high-impact high fire-retardance PC-ABS composite material and preparation methods |
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