CN103788598A - Anti-yellowing anti-separation flame-retardant enhanced PBT composition and use thereof - Google Patents
Anti-yellowing anti-separation flame-retardant enhanced PBT composition and use thereof Download PDFInfo
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Abstract
The invention discloses an anti-yellowing anti-separation flame-retardant enhanced PBT (Poly Butylece Terephthalate) composition and a use thereof. The anti-yellowing anti-separation flame-retardant enhanced PBT composition is composed of, by weight percentage, 50.0-60.0% of PBT, 10.0-15.0% of flame retardant, 15-35% of enhancer, 3-10% of flame retardant synergist, 0.5-1.5% of antioxidant, 0.5-1.5% of light stabilizer, 3-8% of flexibilizer, 0.2-1.0% of coupling agent, 0.2-1.2% of processing agent. The invention also provides a use of the anti-yellowing anti-separation flame-retardant enhanced PBT composition special for a relay. The flame-retardant enhanced PBT composition is special for a relay, and has excellent dimension stability in addition to excellent mechanical and physical properties.
Description
Technical field
The present invention relates to polymeric composition field, relate in particular to anti-flame-retardant reinforced PBT composition and the purposes separated out of a kind of anti-yellowing change.
Background technology
PBT virgin resin has stable flame-retarding characteristic and good physical strength through adding after fire retardant and toughener and other auxiliary agents carry out physically modified, also have that antifatigue is heat-resisting, abrasion abrasion is low, electric insulating quality good simultaneously, chemically-resistant solvent, can rapid crystallization moulding etc. characteristic.Thereby resistance so strengthens PBT at platypelloid type electronic transformer, rectangle electronic transformer, rail type electronic rectifier, surge protector, intelligent breaker, electric motor protecting rly., vertical coil rack, horizontal coil rack, computer is organized junctor soon, PLC intubate lamp socket, the complete small-bore energy-saving lampholder of spiral shell, pluggable energy-saving lampholder, spiral energy-saving lamp socket, bayonet socket energy-saving lampholder, semi-spiral heavy caliber energy-saving lampholder, calandria energy-saving lampholder, ring-type energy-saving lampholder, electric ballast shell, fence type connecting terminal, SUK connection terminal, PCB connection terminal, plug-in type connection terminal, network sockets etc. are electric, lighting industry is widely used.
Being applied to people aspect lighting at fire-retardant enhancing modified PBT in recent years has higher requirement, these technical requirementss have two aspects: the one, and the each money white based on making of flame-retardant reinforced PBT or light energy-saving lampholder are subject to for a long time the double influence of light and heat and produce the phenomenon of xanthochromia in the various climatopes that use, this xanthochromia makes the weather resistance of goods become bad, physical strength to decline and affect work-ing life, make on the other hand the apparent outmoded aesthetic property that has influence on the one hand.The 2nd, problem is separated out in the agent of flame-retardant reinforced PBT surface flame-retardant, and fire retardant is separated out and not only made goods flame retardant effect decline, but also makes the goods electrical property settling that especially phase ratio creepage tracking index CTI reduces, separates out simultaneously also can cause mould corrosion.Anti-yellowing change is anti-for this reason separates out flame-retardant reinforced PBT and becomes the upgraded product of common flame-retardant reinforced PBT.
Summary of the invention
The object of the present invention is to provide a kind of existing superior mechanical physicals to have again the low warpage resistance of good dimensional stabilizing so to strengthen PBT rly. PP Pipe Compound.
For achieving the above object, the invention provides the anti-flame-retardant reinforced PBT composition of separating out of a kind of anti-yellowing change, its composition forms by the composition of following weight percent:
Described PBT resin can be one or more of product within the scope of limiting viscosity (IV) 0.65 ± 0.015～1.10 ± 0.15dl/g; Preferably one or more of product within the scope of limiting viscosity (IV) 0.65 ± 0.015～0.90 ± 0.15dl/g; Further one or more of product within the scope of limiting viscosity (IV) 0.75 ± 0.015～0.85 ± 0.015dl/g preferably.
Described fire retardant can be brominated Polystyrene, brominated epoxy resin, polydibromstyrol, polyacrylic acid pentabromo-benzyl ester, phenoxy group tetrabromobisphenol A carbonic ester oligopolymer, three (tribromophenoxy) cyanurate, 1, one or more in two (tetrabromo phthalimide) ethane of 2-; Preferably brominated Polystyrene, brominated epoxy resin, polyacrylic acid pentabromo-benzyl ester, 1, one or more in two (tetrabromo phthalimide) ethane of 2-; Further preferably brominated Polystyrene, 1, one or more in two (tetrabromo phthalimide) ethane of 2-.
It is that 7～24 μ m, length-to-diameter ratio are that 4:1～8:1, length are that chopped strand, the alkali-free plying Non-twisting glass fibre diameter of 100～300 object powders, alkali free glass fibre diameter 8～16 μ m, length 2.5～6.5 ± 1.0mm is one or more in 8～18 μ m, the linear density rove that is 1200～2800 that described toughener can be alkali-free milled glass fiber diameter; Preferably the chopped strand of alkali free glass fibre diameter 10～15 μ m, length 2.5～6.5 ± 1.0mm, alkali-free plying Non-twisting glass fibre diameter is one or more in 8～18 μ m, the linear density rove that is 1200～2800; Preferably alkali-free plying Non-twisting glass fibre diameter is one or more in 8～15 μ m, the linear density rove that is 1200～2800.
Described fire retarding synergist can be one or more in nano zine oxide, nano aluminium oxide, 4A molecular sieve, barium metaborate, ammonium metaborate, antimonous oxide, antimony peroxide, sodium pyroantimoniate, potassium pyroantimoniate, sodium antimoniate, zinc borate, zinc; Preferably one or more in antimonous oxide, antimony peroxide, sodium pyroantimoniate, zinc borate, zinc; Further preferably one or more in antimonous oxide, sodium pyroantimoniate, zinc borate.
Described oxidation inhibitor is β (3, 5-di-tert-butyl-hydroxy phenyl) propionic acid pentaerythritol ester, β (3, 5-di-t-butyl 4-hydroxy phenyl) propionic acid octadecyl alcohol ester, N, N ＇-bis-[3-(3, 5-di-tert-butyl-hydroxy phenyl) propionyl]-1, 6-hexanediamine, N, N ＇-bis-[3-(3, 5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine, two stearyl alcohol pentaerythritol diphosphites, two (3, 5-di-tert-butyl-phenyl) pentaerythritol diphosphites, tricresyl phosphite (2, 4-di-tert-butyl-phenyl) ester, thio-2 acid 2 stearyl ester, Tyox B, one or more of β-dodecyl propane thioic acid pentaerythritol ester, preferably β (3,5-di-tert-butyl-hydroxy phenyl) propionic acid pentaerythritol ester, β (3,5-di-t-butyl 4-hydroxy phenyl) propionic acid octadecyl alcohol ester, two stearyl alcohol pentaerythritol diphosphites, two (3,5-di-tert-butyl-phenyl) one or more in pentaerythritol diphosphites, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester, thio-2 acid 2 stearyl ester, Tyox B, further preferably β (3,5-di-tert-butyl-hydroxy phenyl) propionic acid pentaerythritol ester, two (3,5-di-tert-butyl-phenyl) one or more in pentaerythritol diphosphites, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester, thio-2 acid 2 stearyl ester.
Described photostabilizer is 2'-(the 2'-hydroxyl-3'-tertiary butyl-5'-aminomethyl phenyl) the chloro-benzotriazole of-5-, 2-(2'-hydroxyl-3', 5'-di-tert-butyl-phenyl) the chloro-benzotriazole of-5-, 2-(2'-hydroxyl-3', 5'-di-tert-pentyl-phenyl) benzotriazole, 2-(the tertiary octyl phenyl of 2'-hydroxyl-5'-) benzotriazole, 2-(2'-hydroxyl-3'-isobutyl--5'-tert-butyl-phenyl) benzotriazole, two (2, 2, 6, 6-tetramethyl--4-piperidines) sebate, poly-succinic (4-hydroxyl-2, 2, 6, 6-tetramethyl--1-piperidines ethanol) ester, 4-anisole methylene radical dimethyl malonate, 2, 2'-(1, 4-phenylenedimethylidyne) two propanedioic acid tetra-ethyl esters, 2-(2H-benzotriazole-2-yl)-4, 6-bis-(1-methyl isophthalic acid-phenylethyl) phenol, 2-(4, 6-two (2, 4-3,5-dimethylphenyl)-1, 3, 5-triazine-2-yl)-5-octyloxy phenol, 2-(4, 6-phenylbenzene-1, 3, 5-triazine-2-yl)-5-hexyl oxygen base-phenol, poly-[[6-[(1, 1, 3, 3-tetramethyl butyl) amino]-1, 3, 5-triazine-2, 4-two [(2, 2, 6, 6-tetramethyl--4-piperidyl) imino-]-1, 6-oneself two support [(2, 2, 6, 6-tetramethyl--4-piperidyl) imino-]] in one or more, preferably 2'-(the 2'-hydroxyl-3'-tertiary butyl-5'-aminomethyl phenyl)-5-chlorobenzotriazole, 2-(the tertiary octyl phenyl of 2'-hydroxyl-5'-) benzotriazole, 2-(2'-hydroxyl-3', 5'-di-tert-pentyl-phenyl) benzotriazole, two (2, 2, 6, 6-tetramethyl--4-piperidines) sebate, 2, 2'-(1, 4-phenylenedimethylidyne) two propanedioic acid tetra-ethyl esters, 2-(2H-benzotriazole-2-yl)-4, 6-bis-(1-methyl isophthalic acid-phenylethyl) phenol, 2-(4, 6-two (2, 4-3,5-dimethylphenyl)-1, 3, 5-triazine-2-yl)-5-octyloxy phenol, poly-[[6-[(1, 1, 3, 3-tetramethyl butyl) amino]-1, 3, 5-triazine-2, 4-two [(2, 2, 6, 6-tetramethyl--4-piperidyl) imino-]-1, 6-oneself two support [(2, 2, 6, 6-tetramethyl--4-piperidyl) imino-]] in one or more, further preferably 2'-(the 2'-hydroxyl-3'-tertiary butyl-5'-aminomethyl phenyl) the chloro-benzotriazole of-5-, 2-(the tertiary octyl phenyl of 2'-hydroxyl-5'-) benzotriazole, two (2, 2, 6, 6-tetramethyl--4-piperidines) sebate, 2-(4, 6-two (2, 4-3,5-dimethylphenyl)-1, 3, 5-triazine-2-yl)-5-octyloxy phenol, poly-[[6-[(1, 1, 3, 3-tetramethyl butyl) amino]-1, 3, 5-triazine-2, 4-two [(2, 2, 6, 6-tetramethyl--4-piperidyl) imino-]-1, 6-oneself two support [(2, 2, 6, 6-tetramethyl--4-piperidyl) imino-]] in one or more.
Described toughner can be ethylene-methyl methacrylate glycidyl ester copolymer (EGMA), ethylene-methyl acrylate-glyceryl methacrylate multipolymer (EMAG), vinyl cyanide-ethylene-propylene-butadiene-styrene copolymer (AES), methyl methacrylate-glycidyl methacrylate-ethyl acrylate copolymer (MGE), Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer (PTW), ethylene-propylene acid butyl ester-copolymer-maleic anhydride (EMH), methyl acrylate-butadiene-styrene copolymer (MBS), ethylene-methyl acrylate copolymer (EMA), one or more in ethylene-octene copolymer grafted maleic anhydride (POE-G-MAH), preferably one or more in ethylene-methyl acrylate-glyceryl methacrylate multipolymer (EMAG), Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer (PTW), ethylene-propylene acid butyl ester-copolymer-maleic anhydride (EMH), further preferably one or more in ethylene-methyl acrylate-glyceryl methacrylate multipolymer (EMAG), Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer (PTW).
Described coupling agent is γ-glycidyl ether oxygen base propyl trimethoxy silicane, γ-glycidyl ether oxygen base propyl group methyl dimethoxysilane, γ-aminopropyl triethoxysilane, γ-aminopropyltrimethoxysilane, 3-[(2,3)-epoxy the third oxygen] one or more in propyl group methyl dimethoxysilane, γ-(methacryloxypropyl) propyl trimethoxy silicane, gamma-mercaptopropyltriethoxysilane, γ-mercaptopropyl trimethoxysilane; Preferably one or more in γ-glycidyl ether oxygen base propyl trimethoxy silicane, γ-glycidyl ether oxygen base propyl group methyl dimethoxysilane, γ-aminopropyl triethoxysilane, γ-aminopropyltrimethoxysilane; Further preferably one or more in γ-glycidyl ether oxygen base propyl trimethoxy silicane, 3-aminopropyl triethoxysilane;
Optional, described processing aid is commercially available common dispersed lubricant, as N, N '-ethylene bis stearamide, N, the two amine hydroxybenzenes of N '-ethylene, N, the two laurylamides of N '-ethylene, amide waxe, esterified wax, montanin wax, Fischer-Tropsch wax, oxidized polyethlene wax, Zinic stearas, calcium stearate etc.
The anti-purposes of flame-retardant reinforced PBT composition for rly. PP Pipe Compound of separating out of described anti-yellowing change.
Fire retardant and synergistic flame retardant have been all fire retardations, and toughener and toughner are to strengthen product performance, and oxidation inhibitor and photostabilizer are anti-oxidation and anti-yellowing changes, anti-separating out; Coupling agent is that glass and resin can better be merged; Processing aid is lubricant.
Object of the present invention will be made the anti-flame-retardant reinforced PBT composition of separating out of a kind of anti-yellowing change exactly, the technical problem of easily separating out to solve the easy xanthochromia of common flame-retardant reinforced PBT, make the existing good flame retardant properties of PBT and mechanical property, meet the anti-characteristic service requirements of separating out of long-acting anti-yellowing change simultaneously.
It is base resin that the present invention adopts PBT, using toughener and fire retardant and fire retarding synergist as fire-retardant enhancing system, with oxidation inhibitor and photostabilizer constitution system, and add toughner, coupling agent, processing aid, with the anti-flame-retardant reinforced PBT of separating out of the anti-yellowing change of preparation of blending extrusion technique.
A kind of anti-yellowing change of the present invention is the anti-preparation method who separates out flame-retardant reinforced PBT composition have the following steps:
(1). PBT is dried to 3～4 hours at 130～140 ℃, and toughener is dried 2～3 hours at 110～120 ℃.
(2). take by weight percentage each material, the each material except toughener is placed in to homogenizer and adds coupling agent in 800～900 revs/min of lower high-speed stirring 8～10 minutes, until all blowings after spoon of mixing of materials.
(3) material is placed in twin screw extruder loading hopper, twin screw extruder temperature turns round under 290～310 revs/min of states at 215～265 ℃, rotating speed, toughener from the second charging opening lead into, the tape of extruding is through circulating water air-dry pelletizing.
Embodiment
Describe embodiments of the invention below in detail, the example of described embodiment is intended to for explaining the present invention, and can not be interpreted as limitation of the present invention.Unreceipted concrete technology or condition person in embodiment, according to the described technology of the document in this area or condition or carry out according to product description.The unreceipted person of production firm of agents useful for same or instrument, being can be by the conventional products of commercial acquisition.
In the following example, anti-yellowing change is anti-separate out in flame-retardant reinforced PBT composition each material respectively from:
It is the product of limiting viscosity in TH6000 series (IV) 0.75 ± 0.015～0.85 ± 0.015dl/g that PBT resin adopts the production of TUNHE CHEMICAL company, product type.
Fire retardant employing WEIDONG CHEMICAL company or HEYE SPECIAL company produce, product type is 1 of RDT-5 or HD-OI, two (tetrabromo phthalimide) ethane of 2-.
It is the alkali free glass fibre assembled roving of WBO EW723 (Fibre diameter 14 μ m, linear density 2000TEX) that toughener adopts the production of WEIBO company, product type.
Antimonous oxide or the Mu Liti industry company that fire retarding synergist employing flash star Ti Ye company produces, product type is TULONG-0 level type produces, product type is 3A level antimonous oxide.
Oxidation inhibitor adopts the β (3 that Li Anlong company produces, product type is THANOX1010,5-di-tert-butyl-hydroxy phenyl) propionic acid pentaerythritol ester, that scene company produces, product type is YFK626 two (3,5-di-tert-butyl-phenyl) pentaerythritol diphosphites, three rich companies produce, product type is the thio-2 acid 2 stearyl ester of SONOX PS802.
Photostabilizer adopts 2-(the tertiary octyl phenyl of the 2'-hydroxyl-5'-) benzotriazole that Milan company produces, product type is UV-5411, the production of angel Synesis Company, product type are two (2 of Sanol LS-770,2,6,6-tetramethyl--4-piperidines) sebate, the poly-[[6-[(1 that Milan company produces, product type is UV-944,1,3,3-tetramethyl butyl) amino]-1,3,5-triazine-2,4-two [(2,2,6,6-tetramethyl--4-piperidyl) imino-]-1,6-oneself two support [(2,2,6,6-tetramethyl--4-piperidyl) imino-]].
Toughner adopts ethylene-acrylate-glycidyl methacrylate terpolymer that DuPont company produces, product type is PTW.
Coupling agent adopts γ-glycidyl ether oxygen propyl trimethoxy silicane that Shuguang company produces, product type is SG-Si187 or γ-glycidyl ether oxygen propyl trimethoxy silicane that Chengong company produces, product type is CG-560.
Dispersed lubricant adopts can match the two hydroxyl stearylamides of WAX2000 ethylene that successful company produces.
Comparative example is commercially available common flame-retardant reinforced PBT.
ASTM standard testing is mainly pressed in main test of the present invention.Density is tested by ASTM D792 requirement.Tensile strength and elongation at break are tested by ASTM D638 requirement.Flexural strength and modulus are tested by ASTM D790 requirement.Notch shock performance is tested by ASTM D256 requirement.Heat-drawn wire by ASTM D648 requirement test, state is 1.82MPa load.Content of glass fiber is tested by ASTM D2584 requirement.Flame retardant properties is tested by UL94 (1.6mm) requirement.The anti-method of separating out test of anti-yellowing change is: 20 20W energy-saving lamp boxes (case volume is long 70cm, wide 40cm, high 35cm), be heated to 110 ℃, then in product being entered, and 2cm fixedly shelves clean transparent sheet glass that can topped product above product, after 1000 hours, test xanthiochromatic difference DELTA E and check and on transparent glass sheet, have or not dirt.
Embodiment 1:
PBT resin 53.40%, fire retardant 1, two (tetrabromo phthalimide) ethane 11.35% of 2-, fire retarding synergist antimonous oxide 3.5%, oxidation inhibitor β (3, 5-di-tert-butyl-hydroxy phenyl) propionic acid pentaerythritol ester 0.25%, oxidation inhibitor two (3, 5-di-tert-butyl-phenyl) pentaerythritol diphosphites 0.25%, oxidation inhibitor thio-2 acid 2 stearyl ester 0.30%, photostabilizer 2-(the tertiary octyl phenyl of 2'-hydroxyl-5'-) benzotriazole 0.15%, photostabilizer gathers [[6-[(1, 1, 3, 3-tetramethyl butyl) amino]-1, 3, 5-triazine-2, 4-[(2, 2, 6, 6-tetramethyl--4-piperidyl) imino-]-1, 6-oneself two support [(2, 2, 6, 6-tetramethyl--4-piperidyl) imino-]] 0.20%, toughner ethylene-acrylate-glycidyl methacrylate terpolymer 4.80%, coupling agent γ-glycidyl ether oxygen propyl trimethoxy silicane 0.30%, dispersed lubricant 0.50%, alkali-free plying Non-twisting glass fibre rove 25%.
Embodiment 2
PBT resin 53.40%, fire retardant 1, two (tetrabromo phthalimide) ethane 11.35% of 2-, fire retarding synergist antimonous oxide 3.5%, oxidation inhibitor β (3, 5-di-tert-butyl-hydroxy phenyl) propionic acid pentaerythritol ester 0.20%, oxidation inhibitor two (3, 5-di-tert-butyl-phenyl) pentaerythritol diphosphites 0.20%, oxidation inhibitor thio-2 acid 2 stearyl ester 0.35%, photostabilizer 2-(the tertiary octyl phenyl of 2'-hydroxyl-5'-) benzotriazole 0.20%, photostabilizer gathers [[6-[(1, 1, 3, 3-tetramethyl butyl) amino]-1, 3, 5-triazine-2, 4-[(2, 2, 6, 6-tetramethyl--4-piperidyl) imino-]-1, 6-oneself two support [(2, 2, 6, 6-tetramethyl--4-piperidyl) imino-]] 0.20%, toughner ethylene-acrylate-glycidyl methacrylate terpolymer 4.80%, coupling agent γ-glycidyl ether oxygen propyl trimethoxy silicane 0.30%, dispersed lubricant 0.50%, alkali-free plying Non-twisting glass fibre rove 25%.
Embodiment 3
PBT resin 53.50%, fire retardant 1, two (tetrabromo phthalimide) ethane 11.25% of 2-, fire retarding synergist antimonous oxide 3.4%, oxidation inhibitor β (3, 5-di-tert-butyl-hydroxy phenyl) propionic acid pentaerythritol ester 0.15%, oxidation inhibitor two (3, 5-di-tert-butyl-phenyl) pentaerythritol diphosphites 0.30%, oxidation inhibitor thio-2 acid 2 stearyl ester 0.35%, photostabilizer 2-(the tertiary octyl phenyl of 2'-hydroxyl-5'-) benzotriazole 0.2%, photostabilizer gathers [[6-[(1, 1, 3, 3-tetramethyl butyl) amino]-1, 3, 5-triazine-2, 4-[(2, 2, 6, 6-tetramethyl--4-piperidyl) imino-]-1, 6-oneself two support [(2, 2, 6, 6-tetramethyl--4-piperidyl) imino-]] 0.25%, toughner ethylene-acrylate-glycidyl methacrylate terpolymer 4.8%, coupling agent γ-glycidyl ether oxygen propyl trimethoxy silicane 0.30%, dispersed lubricant 0.50%, alkali-free plying Non-twisting glass fibre rove 25%.
Embodiment 4
PBT resin 53.50%, fire retardant 1, two (tetrabromo phthalimide) ethane 11.25% of 2-, fire retarding synergist antimonous oxide 3.4%, oxidation inhibitor β (3, 5-di-tert-butyl-hydroxy phenyl) propionic acid pentaerythritol ester 0.20%, oxidation inhibitor two (3, 5-di-tert-butyl-phenyl) pentaerythritol diphosphites 0.30%, oxidation inhibitor thio-2 acid 2 stearyl ester 0.30%, photostabilizer 2-(the tertiary octyl phenyl of 2'-hydroxyl-5'-) benzotriazole 0.15%, photostabilizer gathers [[6-[(1, 1, 3, 3-tetramethyl butyl) amino]-1, 3, 5-triazine-2, 4-[(2, 2, 6, 6-tetramethyl--4-piperidyl) imino-]-1, 6-oneself two support [(2, 2, 6, 6-tetramethyl--4-piperidyl) imino-]] 0.30%, toughner ethylene-acrylate-glycidyl methacrylate terpolymer 4.8%, coupling agent γ-glycidyl ether oxygen propyl trimethoxy silicane 0.30%, dispersed lubricant 0.50%, alkali-free plying Non-twisting glass fibre rove 25%.
Embodiment 5
PBT resin 48.59%, fire retardant 1, two (tetrabromo phthalimide) ethane 11.10% of 2-, fire retarding synergist antimonous oxide 3.3%, oxidation inhibitor β (3, 5-di-tert-butyl-hydroxy phenyl) propionic acid pentaerythritol ester 0.18%, oxidation inhibitor two (3, 5-di-tert-butyl-phenyl) pentaerythritol diphosphites 0.18%, oxidation inhibitor thio-2 acid 2 stearyl ester 0.25%, photostabilizer 2-(the tertiary octyl phenyl of 2'-hydroxyl-5'-) benzotriazole 0.15%, photostabilizer gathers [[6-[(1, 1, 3, 3-tetramethyl butyl) amino]-1, 3, 5-triazine-2, 4-[(2, 2, 6, 6-tetramethyl--4-piperidyl) imino-]-1, 6-oneself two support [(2, 2, 6, 6-tetramethyl--4-piperidyl) imino-]] 0.25%, toughner ethylene-acrylate-glycidyl methacrylate terpolymer 5.0%, coupling agent γ-glycidyl ether oxygen propyl trimethoxy silicane 0.45%, dispersed lubricant 0.55%, alkali-free plying Non-twisting glass fibre rove 30%.
Embodiment 6
PBT resin 48.51%, fire retardant 1, two (tetrabromo phthalimide) ethane 11.10% of 2-, fire retarding synergist antimonous oxide 3.3%, oxidation inhibitor β (3, 5-di-tert-butyl-hydroxy phenyl) propionic acid pentaerythritol ester 0.18%, oxidation inhibitor two (3, 5-di-tert-butyl-phenyl) pentaerythritol diphosphites 0.36%, oxidation inhibitor thio-2 acid 2 stearyl ester 0.25%, photostabilizer 2-(the tertiary octyl phenyl of 2'-hydroxyl-5'-) benzotriazole 0.15%, photostabilizer gathers [[6-[(1, 1, 3, 3-tetramethyl butyl) amino]-1, 3, 5-triazine-2, 4-[(2, 2, 6, 6-tetramethyl--4-piperidyl) imino-]-1, 6-oneself two support [(2, 2, 6, 6-tetramethyl--4-piperidyl) imino-]] 0.15%, toughner ethylene-acrylate-glycidyl methacrylate terpolymer 5.0%, coupling agent γ-glycidyl ether oxygen propyl trimethoxy silicane 0.45%, dispersed lubricant 0.55%, alkali-free plying Non-twisting glass fibre rove 30%.
Comparative example is commercially available common flame-retardant reinforced PBT, and comparative example 1 is for the commercially available common flame-retardant reinforced PBT containing glass fibre 25%, comparative example 2 are for containing the commercially available common flame-retardant reinforced PBT of glass fibre 30%.
The measured data of embodiment 1～embodiment 6 and comparative example 1～comparative example 2 are in table 1.
Table 1. embodiment 1～embodiment 6 and comparative example 1～comparative example 2 performances
From the data measured of table 1, the anti-anti-property separated out of the existing good anti-yellowing change of flame-retardant reinforced PBT of separating out of anti-yellowing change that adopts the present invention to prepare has again satisfactory flame retardant resistance, also possesses certain physical strength simultaneously.
Although illustrated and described embodiments of the invention above, be understandable that, above-described embodiment is exemplary, can not be interpreted as limitation of the present invention, those of ordinary skill in the art can change above-described embodiment within the scope of the invention in the situation that not departing from principle of the present invention and aim, modification, replacement and modification.
Claims (10)
1. the anti-flame-retardant reinforced PBT composition of separating out of anti-yellowing change, its composition forms by the composition of following weight percent:
2. described in claim 1, anti-yellowing change is anti-separates out flame-retardant reinforced PBT composition, it is characterized in that, described PBT resin can be one or more of product within the scope of limiting viscosity (IV) 0.65 ± 0.015～1.10 ± 0.15dl/g; Be preferably one or more of product within the scope of limiting viscosity (IV) 0.65 ± 0.015～0.90 ± 0.15dl/g; More preferably one or more of product within the scope of limiting viscosity (IV) 0.75 ± 0.015～0.85 ± 0.015dl/g.
3. the anti-flame-retardant reinforced PBT composition of separating out of anti-yellowing change described in claim 1, it is characterized in that, described fire retardant can be brominated Polystyrene, brominated epoxy resin, polydibromstyrol, polyacrylic acid pentabromo-benzyl ester, phenoxy group tetrabromobisphenol A carbonic ester oligopolymer, three (tribromophenoxy) cyanurate, 1, one or more in two (tetrabromo phthalimide) ethane of 2-; Be preferably brominated Polystyrene, brominated epoxy resin, polyacrylic acid pentabromo-benzyl ester, 1, one or more in two (tetrabromo phthalimide) ethane of 2-; More preferably brominated Polystyrene, 1, one or more in two (tetrabromo phthalimide) ethane of 2-.
4. the anti-flame-retardant reinforced PBT composition of separating out of anti-yellowing change described in claim 1, it is characterized in that, it is that 7～24 μ m, length-to-diameter ratio are that 4:1～8:1, length are 100～300 object powders that described toughener can be alkali-free milled glass fiber diameter, the chopped strand of alkali free glass fibre diameter 8～16 μ m, length 2.5～6.5 ± 1.0mm, alkali-free plying Non-twisting glass fibre diameter is one or more in 8～18 μ m, the linear density rove that is 1200～2800; Be preferably the chopped strand of alkali free glass fibre diameter 10～15 μ m, length 2.5～6.5 ± 1.0mm, alkali-free plying Non-twisting glass fibre diameter is one or more in 8～18 μ m, the linear density rove that is 1200～2800; One or more in the rove that to be preferably alkali-free plying Non-twisting glass fibre diameter and to be 8～15 μ m, linear density be 1200～2800.
5. the anti-flame-retardant reinforced PBT composition of separating out of anti-yellowing change described in claim 1, it is characterized in that, described fire retarding synergist can be one or more in nano zine oxide, nano aluminium oxide, 4A molecular sieve, barium metaborate, ammonium metaborate, antimonous oxide, antimony peroxide, sodium pyroantimoniate, potassium pyroantimoniate, sodium antimoniate, zinc borate, zinc; Be preferably one or more in antimonous oxide, antimony peroxide, sodium pyroantimoniate, zinc borate, zinc; More preferably one or more in antimonous oxide, sodium pyroantimoniate, zinc borate.
6. the anti-flame-retardant reinforced PBT composition of separating out of anti-yellowing change described in claim 1, it is characterized in that, described oxidation inhibitor is β (3, 5-di-tert-butyl-hydroxy phenyl) propionic acid pentaerythritol ester, β (3, 5-di-t-butyl 4-hydroxy phenyl) propionic acid octadecyl alcohol ester, N, N ＇-bis-[3-(3, 5-di-tert-butyl-hydroxy phenyl) propionyl]-1, 6-hexanediamine, N, N ＇-bis-[3-(3, 5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine, two stearyl alcohol pentaerythritol diphosphites, two (3, 5-di-tert-butyl-phenyl) pentaerythritol diphosphites, tricresyl phosphite (2, 4-di-tert-butyl-phenyl) ester, thio-2 acid 2 stearyl ester, Tyox B, one or more of β-dodecyl propane thioic acid pentaerythritol ester, be preferably β (3,5-di-tert-butyl-hydroxy phenyl) propionic acid pentaerythritol ester, β (3,5-di-t-butyl 4-hydroxy phenyl) propionic acid octadecyl alcohol ester, two stearyl alcohol pentaerythritol diphosphites, two (3,5-di-tert-butyl-phenyl) one or more in pentaerythritol diphosphites, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester, thio-2 acid 2 stearyl ester, Tyox B, more preferably β (3,5-di-tert-butyl-hydroxy phenyl) propionic acid pentaerythritol ester, two (3,5-di-tert-butyl-phenyl) one or more in pentaerythritol diphosphites, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester, thio-2 acid 2 stearyl ester.
7. the anti-flame-retardant reinforced PBT composition of separating out of anti-yellowing change described in claim 1, it is characterized in that, described photostabilizer is 2'-(the 2'-hydroxyl-3'-tertiary butyl-5'-aminomethyl phenyl) the chloro-benzotriazole of-5-, 2-(2'-hydroxyl-3', 5'-di-tert-butyl-phenyl) the chloro-benzotriazole of-5-, 2-(2'-hydroxyl-3', 5'-di-tert-pentyl-phenyl) benzotriazole, 2-(the tertiary octyl phenyl of 2'-hydroxyl-5'-) benzotriazole, 2-(2'-hydroxyl-3'-isobutyl--5'-tert-butyl-phenyl) benzotriazole, two (2, 2, 6, 6-tetramethyl--4-piperidines) sebate, poly-succinic (4-hydroxyl-2, 2, 6, 6-tetramethyl--1-piperidines ethanol) ester, 4-anisole methylene radical dimethyl malonate, 2, 2'-(1, 4-phenylenedimethylidyne) two propanedioic acid tetra-ethyl esters, 2-(2H-benzotriazole-2-yl)-4, 6-bis-(1-methyl isophthalic acid-phenylethyl) phenol, 2-(4, 6-two (2, 4-3,5-dimethylphenyl)-1, 3, 5-triazine-2-yl)-5-octyloxy phenol, 2-(4, 6-phenylbenzene-1, 3, 5-triazine-2-yl)-5-hexyl oxygen base-phenol, poly-[[6-[(1, 1, 3, 3-tetramethyl butyl) amino]-1, 3, 5-triazine-2, 4-two [(2, 2, 6, 6-tetramethyl--4-piperidyl) imino-]-1, 6-oneself two support [(2, 2, 6, 6-tetramethyl--4-piperidyl) imino-]] in one or more, be preferably 2'-(the 2'-hydroxyl-3'-tertiary butyl-5'-aminomethyl phenyl)-5-chlorobenzotriazole, 2-(the tertiary octyl phenyl of 2'-hydroxyl-5'-) benzotriazole, 2-(2'-hydroxyl-3', 5'-di-tert-pentyl-phenyl) benzotriazole, two (2, 2, 6, 6-tetramethyl--4-piperidines) sebate, 2, 2'-(1, 4-phenylenedimethylidyne) two propanedioic acid tetra-ethyl esters, 2-(2H-benzotriazole-2-yl)-4, 6-bis-(1-methyl isophthalic acid-phenylethyl) phenol, 2-(4, 6-two (2, 4-3,5-dimethylphenyl)-1, 3, 5-triazine-2-yl)-5-octyloxy phenol, poly-[[6-[(1, 1, 3, 3-tetramethyl butyl) amino]-1, 3, 5-triazine-2, 4-two [(2, 2, 6, 6-tetramethyl--4-piperidyl) imino-]-1, 6-oneself two support [(2, 2, 6, 6-tetramethyl--4-piperidyl) imino-]] in one or more, more preferably 2'-(the 2'-hydroxyl-3'-tertiary butyl-5'-aminomethyl phenyl) the chloro-benzotriazole of-5-, 2-(the tertiary octyl phenyl of 2'-hydroxyl-5'-) benzotriazole, two (2, 2, 6, 6-tetramethyl--4-piperidines) sebate, 2-(4, 6-two (2, 4-3,5-dimethylphenyl)-1, 3, 5-triazine-2-yl)-5-octyloxy phenol, poly-[[6-[(1, 1, 3, 3-tetramethyl butyl) amino]-1, 3, 5-triazine-2, 4-two [(2, 2, 6, 6-tetramethyl--4-piperidyl) imino-]-1, 6-oneself two support [(2, 2, 6, 6-tetramethyl--4-piperidyl) imino-]] in one or more.
8. the anti-flame-retardant reinforced PBT composition of separating out of anti-yellowing change described in claim 1, it is characterized in that, described toughner can be ethylene-methyl methacrylate glycidyl ester copolymer (EGMA), ethylene-methyl acrylate-glyceryl methacrylate multipolymer (EMAG), vinyl cyanide-ethylene-propylene-butadiene-styrene copolymer (AES), methyl methacrylate-glycidyl methacrylate-ethyl acrylate copolymer (MGE), Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer (PTW), ethylene-propylene acid butyl ester-copolymer-maleic anhydride (EMH), methyl acrylate-butadiene-styrene copolymer (MBS), ethylene-methyl acrylate copolymer (EMA), one or more in ethylene-octene copolymer grafted maleic anhydride (POE-G-MAH), be preferably one or more in ethylene-methyl acrylate-glyceryl methacrylate multipolymer (EMAG), Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer (PTW), ethylene-propylene acid butyl ester-copolymer-maleic anhydride (EMH), more preferably one or more in ethylene-methyl acrylate-glyceryl methacrylate multipolymer (EMAG), Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer (PTW).
9. the anti-flame-retardant reinforced PBT composition of separating out of anti-yellowing change described in claim 1, it is characterized in that, described coupling agent is γ-glycidyl ether oxygen base propyl trimethoxy silicane, γ-glycidyl ether oxygen base propyl group methyl dimethoxysilane, γ-aminopropyl triethoxysilane, γ-aminopropyltrimethoxysilane, 3-[(2,3)-epoxy the third oxygen] one or more in propyl group methyl dimethoxysilane, γ-(methacryloxypropyl) propyl trimethoxy silicane, gamma-mercaptopropyltriethoxysilane, γ-mercaptopropyl trimethoxysilane; Be preferably one or more in γ-glycidyl ether oxygen base propyl trimethoxy silicane, γ-glycidyl ether oxygen base propyl group methyl dimethoxysilane, γ-aminopropyl triethoxysilane, γ-aminopropyltrimethoxysilane; More preferably one or more in γ-glycidyl ether oxygen base propyl trimethoxy silicane, 3-aminopropyl triethoxysilane;
Optional, described processing aid is commercially available common dispersed lubricant, as N, N '-ethylene bis stearamide, N, the two amine hydroxybenzenes of N '-ethylene, N, the two laurylamides of N '-ethylene, amide waxe, esterified wax, montanin wax, Fischer-Tropsch wax, oxidized polyethlene wax, Zinic stearas, calcium stearate etc.
10. the anti-purposes of flame-retardant reinforced PBT composition for rly. PP Pipe Compound of separating out of the arbitrary described anti-yellowing change of claim 1-9.
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| CN105315493A (en) * | 2015-04-23 | 2016-02-10 | 广西华锑科技有限公司 | Low-smoke environment-friendly type antimony system compound flame retardant and preparation method thereof |
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| CN105086381A (en) * | 2015-07-31 | 2015-11-25 | 深圳市兴盛迪新材料有限公司 | Polybutylene terephthalate composite and preparation method thereof |
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| CN106566197A (en) * | 2016-10-21 | 2017-04-19 | 邹小凤 | Alumina thermal conductive composite material and preparation method thereof |
| CN108424624A (en) * | 2018-04-16 | 2018-08-21 | 南京真宸科技有限公司 | A kind of HI high impact enhancing polyethylene naphthalate composite material |
| CN108504054A (en) * | 2018-04-16 | 2018-09-07 | 南京真宸科技有限公司 | A kind of fiberglass reinforced polyethylene naphthalate composite material |
| CN109438933A (en) * | 2018-11-09 | 2019-03-08 | 四川长虹电器股份有限公司 | Modified enhancing flame-retardant PBT material and preparation method thereof |
| CN110305454A (en) * | 2019-08-15 | 2019-10-08 | 深圳市兴盛迪新材料有限公司 | A kind of PBT composite and its application |
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| CN110698821B (en) * | 2019-10-31 | 2021-08-27 | 东莞市东翔塑胶有限公司 | Multi-oxygen-containing functional polyester resin, and preparation method and application thereof |
| CN112778710A (en) * | 2020-12-25 | 2021-05-11 | 金发科技股份有限公司 | high-PTI (polybutylene terephthalate) and high-toughness PBT (polybutylene terephthalate) composition as well as preparation method and application thereof |
| CN114350022A (en) * | 2021-12-03 | 2022-04-15 | 国家能源集团宁夏煤业有限责任公司 | Anti-yellowing antioxidant and application thereof, anti-yellowing polyolefin composition and application thereof, anti-yellowing polyolefin and preparation method and application thereof |
| CN114350022B (en) * | 2021-12-03 | 2023-12-22 | 国家能源集团宁夏煤业有限责任公司 | Anti-yellowing antioxidant and application thereof, anti-yellowing polyolefin composition and application thereof, anti-yellowing polyolefin and preparation method and application thereof |
| CN115926390A (en) * | 2022-12-09 | 2023-04-07 | 安庆会通新材料有限公司 | Flame-retardant low-warpage glass fiber reinforced PBT (polybutylene terephthalate) composite material and preparation method thereof |
| CN115926390B (en) * | 2022-12-09 | 2024-03-29 | 安庆会通新材料有限公司 | Flame-retardant low-warpage glass fiber reinforced PBT composite material and preparation method thereof |
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