CN103724953A - Special low-warpage flame-retardant reinforced PBT (polybutylene terephthalate) material for relay and application of material - Google Patents
Special low-warpage flame-retardant reinforced PBT (polybutylene terephthalate) material for relay and application of material Download PDFInfo
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- CN103724953A CN103724953A CN201410019072.0A CN201410019072A CN103724953A CN 103724953 A CN103724953 A CN 103724953A CN 201410019072 A CN201410019072 A CN 201410019072A CN 103724953 A CN103724953 A CN 103724953A
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Abstract
The invention discloses a special low-warpage flame-retardant reinforced PBT (polybutylene terephthalate) material for a relay and an application of the material. The special low-warpage flame-retardant reinforced PBT material comprises the following components by weight percent: 40 to 55 percent of PBT resin, 10 to 15 percent of flame-retardant agent, 2 to 7 percent of flame-retardant synergist, 20 to 35 percent of reinforcing agent, 2 to 9 percent of anti-warping resin, 1 to 5 percent of anti-warpage filler, 2 to 5 percent of plasticizer, 0.1 to 0.5 percent of coupling agent, 0.2 to 0.8 percent of antioxidant and 0.2 to 0.8 percent of processing aid. According to the material disclosed by the invention, the warping performance of each side and the four-side warping performance of the material are greatly improved, and other mechanical properties such as tensile strength, bending strength, notch impacting stretch, thermal deformation temperature, flame retardant property and the like can be maintained at a normal level and are not reduced. After being molded and assembled, the material can be applied to different relays such as a telecom relay, a power relay and a guide relay.
Description
Technical field
The present invention relates to field of polymer technology compositions field, relate in particular to a kind of low warpage flame-retardant reinforced PBT rly. PP Pipe Compound.
Background technology
PBT is the saturated linear polyester of a kind of important hemicrystalline in thermoplastic polyester series, PBT has that the high and resistance to fatigue of excellent mechanical performances intensity and chemical proofing, while weather resistance are good in conjunction with making for the regularity of its flexible fatty alcohol and rigidity phenyl ring, low wear-resistant, the electric insulating quality of frictional coefficient and arc resistance good, be easy to the advantages such as machine-shaping.But PBT also has, and notch sensitivity is large, heat-drawn wire is low, do not possess anti-flaming function and the shortcoming such as easily burning, molding shrinkage be large.In PBT application, need targetedly for this reason to its carry out physically modified with the requirement that meets market, especially electric industry material requirements physical strength and flame-retarding characteristic are possessed, specifically to meet thin-walled component and also require the requirement of the low warpage of low contraction as all kinds of relay products.
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 flame-retardant reinforced PBT of good dimensional stabilizing rly. PP Pipe Compound.
For achieving the above object, the invention provides a kind of low warpage flame-retardant reinforced PBT rly. PP Pipe Compound, it is characterized in that, form by the weight percent of following each component and form, include:
Described PBT resin is one or more in 15～95g/10min, limiting viscosity 0.65 ± 0.015～1.10 ± dl/g under 250 ℃ of melting index, 2.16Kg condition; Preferably under 250 ℃ of melting index, 2.16Kg condition 45～85g/10min, limiting viscosity (IV) 0.65 ± 0.015～0.90 ± dl/g one or more; Be more preferably one or more in 55～80g/10min, limiting viscosity 0.75 ± 0.015～0.90 ± 0.015dl/g under 250 ℃ of melting index, 2.16Kg condition.
Described fire retardant is one or more in TDE, brominated Polystyrene, brominated epoxy resin, poly-dibromobenzene aether, polyacrylic acid pentabromo-benzyl ester, phenoxy group tetrabromobisphenol A carbonic ester oligopolymer, three (tribromophenoxy) cyanurate, the two tetrabromo phthalimides of ethylene; One or more in the two tetrabromo phthalimides of brominated Polystyrene, brominated epoxy resin, phenoxy group tetrabromobisphenol A carbonic ester oligopolymer, three (tribromophenoxy) cyanurate, ethylene preferably; One or more in brominated Polystyrene, brominated epoxy resin, three (tribromophenoxy) cyanurate more preferably.
Described fire retarding synergist can be one or more in antimonous oxide, antimony peroxide, sodium pyroantimoniate, zinc borate, zinc, zinc hydroxyl stannate, sodium wolframate, Sodium orthomolybdate; One or both in antimonous oxide, antimony peroxide, sodium pyroantimoniate, zinc borate, zinc preferably; One or more in antimonous oxide, sodium pyroantimoniate, zinc borate more preferably.
Described toughener can be one or more in the chopped strand that alkali-free plying Non-twisting glass fibre diameter is 8～18 μ m, the linear density rove that is 1000～2800, alkali free glass fibre diameter 8～16 μ m, length 2.5～6.5 ± 1.0mm; One or more in the chopped strand of alkali free glass fibre diameter 10～15 μ m, length 2.5～6.5 ± 1.0mm preferably; One or more in the chopped strand of alkali free glass fibre diameter 11～13 μ m, length 3.0～4.5 ± 1.0mm more preferably.
Described anti-warpage resin can be one or more in styrene-acrylonitrile-copolymer-maleic anhydride SMA, acrylonitrile acryloid styrene ASA, acrylonitrile-butadiene-styrene copolymer ABS, acrylonitrile ethylene styrene copolymer AES, acrylonitritrile-styrene resin AS, acrylonitrile-chlorianted polyethylene-styrene terpolymer ACS; One or more in styrene-acrylonitrile-copolymer-maleic anhydride SMA, acrylonitrile acryloid styrene ASA, acrylonitritrile-styrene resin AS, acrylonitrile-chlorianted polyethylene-styrene terpolymer ACS preferably; One or more in styrene-acrylonitrile-copolymer-maleic anhydride SMA, acrylonitrile acryloid styrene ASA more preferably.
Described anti-warpage filler is one or more in kaolin, diatomite, barite, wollastonite, calcite, grey gypsum, white mica, talcum powder; One or more in barite, wollastonite, calcite, grey gypsum, white mica preferably; One or more in barite, wollastonite, grey gypsum more preferably.
Described toughner can be one or more in ethylene-propylene acid butyl ester-copolymer-maleic anhydride EMH, Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer PTW, methyl acrylate-butadiene-styrene copolymer MBS, ethylene/methyl acrylate copolymer EMA, ethylene-octene copolymer grafted maleic anhydride POE-G-MAH; One or more in ethylene-propylene acid butyl ester-copolymer-maleic anhydride EMH, Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer PTW preferably; One or more in ethylene-propylene acid butyl ester-copolymer-maleic anhydride, Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer more preferably.
Described coupling agent is 3-aminopropyl triethoxysilane, γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-(methacryloxypropyl) propyl trimethoxy silicane, gamma-mercaptopropyltriethoxysilane, γ-mercaptopropyl trimethoxysilane, 3-[(2,3)-epoxy the third oxygen] one or more in propyl group methyl dimethoxysilane; One or more in 3-aminopropyl triethoxysilane, γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-(methacryloxypropyl) propyl trimethoxy silicane, gamma-mercaptopropyltriethoxysilane preferably; One or more in 3-aminopropyl triethoxysilane, γ-glycidyl ether oxygen propyl trimethoxy silicane more preferably;
Optional, described oxidation inhibitor is four (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, β-(4-hydroxy phenyl-3,5-di-t-butyl) the positive octadecanol ester of propionic acid, 2, [3-(3 for 2'-thiobis, 5-di-tert-butyl-hydroxy phenyl) ethyl propionate], N, [3-(3 for N ＇-bis-, 5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester, 2,2-oxalyl amido-bis-(ethyl-3-(3,5-di-tert-butyl-hydroxy phenyl)) one or more in propionic ester; Four (β-(3 preferably, 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, β-(4-hydroxy phenyl-3,5-di-t-butyl) the positive octadecanol ester of propionic acid, 2, [3-(3 for 2'-thiobis, 5-di-tert-butyl-hydroxy phenyl) ethyl propionate], one or more in tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester; One or more in the positive octadecanol ester of β-(4-hydroxy phenyl-3,5-di-t-butyl) propionic acid, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester more preferably;
Optional, other described auxiliary agent is at least one in commercially available common dispersion agent, lubricant.
After described low warpage flame-retardant reinforced PBT rly. PP Pipe Compound moulding assembling, can be used for letter electrical relay, power relay, guiding rly., high frequency relay, intermediate relay, light coupling relay, the time relay, counting relay, leakage relay, over current relay, pulse relay, sun power rly., high electric current and magnetic latching relay etc.
The invention reside in and adopting PBT is base resin, using glass fibre and fire retardant and fire retarding synergist as fire-retardant enhancing system, with anti-contraction warpage resin and filler, form anti-contraction warpage system, at other, about auxiliary agent makes existing superior mechanical physicals under as the cooperation of toughner, coupling agent, oxidation inhibitor and processing aid, have again the low warpage flame-retardant reinforced PBT of good dimensional stabilizing rly. PP Pipe Compound.
PBT resin model of the present invention can be melting index (MI) 15～95g/10min (250 ℃, 2.16Kg), limiting viscosity (IV) 0.65 ± 0.015～1.10 ± dl/g, is more preferably melting index (MI) 45～85g/10min (250 ℃, 2.16Kg), limiting viscosity (IV) 0.65 ± 0.015～0.90 ± dl/g more than one or more than one.One or more in melting index (MI) 55～80g/10min (250 ℃, 2.16Kg), limiting viscosity (IV) 0.75 ± 0.015～0.90 ± 0.015dl/g preferably.
Fire retardant of the present invention can be one or more in TDE, brominated Polystyrene, brominated epoxy resin, poly-dibromobenzene aether, polyacrylic acid pentabromo-benzyl ester, phenoxy group tetrabromobisphenol A carbonic ester oligopolymer, three (tribromophenoxy) cyanurate, the two tetrabromo phthalimides of ethylene.One or more in the two tetrabromo phthalimides of brominated Polystyrene, brominated epoxy resin, phenoxy group tetrabromobisphenol A carbonic ester oligopolymer, three (tribromophenoxy) cyanurate, ethylene even more preferably.One or more in brominated Polystyrene, brominated epoxy resin, three (tribromophenoxy) cyanurate preferably.
Fire retarding synergist of the present invention can be one or more in antimonous oxide, antimony peroxide, sodium pyroantimoniate, zinc borate, zinc, zinc hydroxyl stannate, sodium wolframate, Sodium orthomolybdate.One or more in antimonous oxide, antimony peroxide, sodium pyroantimoniate, zinc borate, zinc even more preferably.One or more in antimonous oxide, sodium pyroantimoniate, zinc borate preferably.
Toughener of the present invention can be one or more in the chopped strand that alkali-free plying Non-twisting glass fibre diameter is 8～18 μ m, the linear density rove that is 1000～2800, alkali free glass fibre diameter 8～16 μ m, length 2.5～6.5 ± 1.0mm.One or more in the chopped strand of alkali free glass fibre diameter 10～15 μ m, length 2.5～6.5 ± 1.0mm even more preferably.One or more in the chopped strand of alkali free glass fibre diameter 11～13 μ m, length 3.0～4.5 ± 1.0mm preferably.
Anti-warpage resin of the present invention can be one or more in styrene/acrylonitrile/copolymer-maleic anhydride (SMA), vinyl cyanide/acrylate/styrol copolymer (ASA), acrylonitrile/butadiene/styrene multipolymer (ABS), vinyl cyanide/ethylene/styrene multipolymer (AES), vinyl cyanide/styrol copolymer (AS), vinyl cyanide/chlorinatedpolyethylene/styrol copolymer (ACS).
One or more in styrene/acrylonitrile/copolymer-maleic anhydride (SMA), vinyl cyanide/acrylate/styrol copolymer (ASA), vinyl cyanide/styrol copolymer (AS), vinyl cyanide/chlorinatedpolyethylene/styrol copolymer (ACS) even more preferably.One or more in styrene/acrylonitrile/copolymer-maleic anhydride (SMA), vinyl cyanide/acrylate/styrol copolymer (ASA) preferably.
Anti-warpage filler of the present invention is one or more in kaolin, diatomite, barite, wollastonite, calcite, grey gypsum, white mica, talcum powder.One or more in barite, wollastonite, calcite, grey gypsum, white mica even more preferably.One or more in barite, wollastonite, grey gypsum preferably.
Toughner of the present invention can be ethylene-propylene acid butyl ester-copolymer-maleic anhydride (EMH), Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer (PTW), methyl acrylate-butadiene-styrene copolymer (MBS), ethylene/methyl acrylate copolymer (EMA), ethylene-octene copolymer grafted maleic anhydride (POE-G-MAH).One or more in ethylene-propylene acid butyl ester-copolymer-maleic anhydride, Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer even more preferably.Be preferably one or more in ethylene-propylene acid butyl ester-copolymer-maleic anhydride, Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer.
Coupling agent of the present invention is 3-aminopropyl triethoxysilane, γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-(methacryloxypropyl) propyl trimethoxy silicane, gamma-mercaptopropyltriethoxysilane, γ-mercaptopropyl trimethoxysilane, 3-[(2,3)-epoxy the third oxygen] one or more in propyl group methyl dimethoxysilane.One or more in 3-aminopropyl triethoxysilane, γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-(methacryloxypropyl) propyl trimethoxy silicane, gamma-mercaptopropyltriethoxysilane even more preferably.One or more in 3-aminopropyl triethoxysilane, γ-glycidyl ether oxygen propyl trimethoxy silicane preferably.
Oxidation inhibitor of the present invention is four (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, β-(4-hydroxy phenyl-3,5-di-t-butyl) the positive octadecanol ester of propionic acid, 2, [3-(3 for 2'-thiobis, 5-di-tert-butyl-hydroxy phenyl) ethyl propionate], N, [3-(3 for N ＇-bis-, 5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester, 2,2-oxalyl amido-bis-(ethyl-3-(3,5-di-tert-butyl-hydroxy phenyl)) one or more in propionic ester.Four (β-(3 even more preferably, 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, β-(4-hydroxy phenyl-3,5-di-t-butyl) the positive octadecanol ester of propionic acid, 2, [3-(3 for 2'-thiobis, 5-di-tert-butyl-hydroxy phenyl) ethyl propionate], one or more in tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester.One or more in the positive octadecanol ester of β-(4-hydroxy phenyl-3,5-di-t-butyl) propionic acid, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester preferably.
Other auxiliary agent of the present invention is the processing aids such as commercially available common dispersion agent, lubricant.
The preparation method of low warpage flame-retardant reinforced PBT rly. PP Pipe Compound of the present invention has the following steps:
(1). PBT is placed in to 130～140 ℃ of dry 2～4h, and anti-warpage resin is placed in 80～85 ℃ of dry 2～3h, and anti-warpage filler is placed in 95～110 ℃ of dry 3～4h.The present invention produces after first drying material again, and the mechanical property of product improves 30% left and right than the product that does not dry material direct production.
(2). the material taking by weight percentage except alkali free glass fibre chopped strand is placed in material agitator, in 5～10 minutes blowings after the equal spoon of mixing of materials of 750～850 revs/min of lower high-speed stirring.
(3). twin screw extruder temperature turns round under 300～400 revs/min of states at 220～260 ℃, rotating speed, alkali free glass fibre chopped strand is added by side direction spout, mix all materials of spoon and introduced by twin screw extruder elevating hopper, extrude tape by cooling air-drying pelletizing.
In above method, excess Temperature or rotating speed are too slow, all can cause product easily oxidation in mixing process, and temperature is too low or rotating speed is too fast, is unfavorable for the mutual dispersion of each component, all can affect the performance of product.
In method for testing performance of the present invention:
Density, mechanical property, thermal characteristics adopt ASTM standard, wherein density by ASTM D792 requirement test, tensile strength by ASTM D638 requirement test, flexural strength and modulus by ASTM D790 requirement test, notch shock performance by ASTM D256 requirement test, heat-drawn wire tests (state is 1.82MPa load) by ASTM D648 requirement.
Flame retardant properties adopts UL94 standard (state is 1.6mm)
It is qualified that warpage performance adopts described in JJG62-2007 clearance gauge to check the logical method of stopping in products formed measured size and horizontal plane gap to judge whether.
After low warpage flame-retardant reinforced PBT rly. PP Pipe Compound moulding assembling of the present invention, can be used for letter electrical relay, power relay, guiding rly., high frequency relay, intermediate relay, light coupling relay, the time relay, counting relay, leakage relay, over current relay, pulse relay, sun power rly., high electric current and magnetic latching relay etc.
Embodiments of the invention 7 results show, by adding in right amount anti-warpage resin and anti-warpage filler (embodiment 1-6 fill a prescription products obtained therefrom), every limit warpage performance of product and four limit warpage performances all improve greatly, while is for other mechanical property, as tensile strength, flexural strength, notched Izod impact strength etc., and heat-drawn wire and flame retardant resistance, can remain on normal level and not decline.
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.
Embodiment main agents used
PBT resin adopts commercially available melting index (MI) 55～80g/10min (250 ℃, 2.16Kg) limiting viscosity (IV) 0.85 ± 0.015dl/g, the Wei Sanfang of manufacturer lane group or Xingchen Synthetic Matrials Co., Ltd., Nantong.
It is the brominated Polystyrene (BPS) of GREATBAY XZ-6700 and the brominated epoxy resin (BEO) that model is BEO-1 that fire retardant adopts model, and manufacturer is respectively Shandong Xiongdi Science & Technology Co., Ltd. and Shandong Chemical Co., Ltd. of Futong.
Fire retarding synergist adopts the antimonous oxide that model is Sb2O3-99.90, and manufacturer is Anhua Hua Yuti industry company limited.
It is the alkali free glass fibre chopped strand of 534W (Fibre diameter 13 μ m, length 4.5mm) that toughener adopts model, and manufacturer is Jushi Group Co., Ltd..
Anti-warpage resin adopts styrene/acrylonitrile/copolymer-maleic anhydride (SMA) that model is SMA3000, vinyl cyanide/acrylate/styrol copolymer (ASA) that model is XC-200, and manufacturer is respectively Cray Willie chemical company He Jinhu petroleum chemistry company.
Anti-warpage filler adopts the acicular wollastonite that model is 2000M, and manufacturer is Jiangxi Ao Te fine powder company limited.
Toughner adopts the Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer that model is PTW, and manufacturer is E.I.Du Pont Company.
Coupling agent adopts γ-glycidyl ether oxygen propyl trimethoxy silicane that model is SG-Si187, and manufacturer is Nanjing dawn Chemical Co., Ltd..
Oxidation inhibitor adopts four (β-(3 that model is AT10,5-di-tert-butyl-hydroxy phenyl) tricresyl phosphite (2 that propionic acid) pentaerythritol ester and model are AT168,4-di-tert-butyl-phenyl) ester, manufacturer is Jinhai-Yabao Chemical Co., Ltd., Ningbo.
Processing aid is the N of Shanghai hundred gorgeous auxiliary agents, N '--ethylene bis stearic acid amide (EBS).
Embodiment 1: the preparation of low warpage flame-retardant reinforced PBT rly. PP Pipe Compound
PBT is placed in to 130～140 ℃ of dry 2～4h, and anti-warpage resin is placed in 80～85 ℃ of dry 2～3h, and anti-warpage filler is placed in 95～110 ℃ of dry 3～4h.
PBT resin 42.55%, flame retardant brominated polystyrene 12.25%, fire retarding synergist antimonous oxide 3.2%, alkali free glass fibre chopped strand 30%, anti-warpage Resin A SA3.5%, anti-warpage resin SMA2.5%, anti-warpage filler acicular wollastonite 1.5%, toughner 3.5%, oxidation inhibitor 0.3% weight part, coupling agent 0.2%, processing aid 0.5%.Preparation method is that the material taking by weight percentage except alkali free glass fibre chopped strand is placed in homogenizer, in 7 minutes blowings after the equal spoon of mixing of materials of 800 revs/min of lower high-speed stirring.The material after mixed spoon is placed in twin screw extruder loading hopper, twin screw extruder temperature turns round under 350 revs/min of states at 225～255 ℃, rotating speed again, and alkali free glass fibre chopped strand is added by side direction spout, extrudes tape through cooling air-drying pelletizing.
Embodiment 2: the preparation of low warpage flame-retardant reinforced PBT rly. PP Pipe Compound
PBT is placed in to 130～140 ℃ of dry 2～4h, and anti-warpage resin is placed in 80～85 ℃ of dry 2～3h, and anti-warpage filler is placed in 95～110 ℃ of dry 3～4h.
PBT resin 41.55, flame retardant brominated polystyrene 12.25%, fire retarding synergist antimonous oxide 3.2%, alkali free glass fibre chopped strand 30%, anti-warpage Resin A SA4.0%, anti-warpage resin SMA2.5%, anti-warpage filler acicular wollastonite 2.0%, toughner 3.5%, oxidation inhibitor 0.3%, coupling agent 0.2%, processing aid 0.5%.Preparation method is that the material taking by weight percentage except alkali free glass fibre chopped strand is placed in homogenizer, in 7 minutes blowings after the equal spoon of mixing of materials of 800 revs/min of lower high-speed stirring.The material after mixed spoon is placed in twin screw extruder loading hopper, twin screw extruder temperature turns round under 350 revs/min of states at 225～255 ℃, rotating speed again, and alkali free glass fibre chopped strand is added by side direction spout, extrudes tape through cooling air-drying pelletizing.
Embodiment 3: the preparation of low warpage flame-retardant reinforced PBT rly. PP Pipe Compound
PBT is placed in to 130～140 ℃ of dry 2～4h, and anti-warpage resin is placed in 80～85 ℃ of dry 2～3h, and anti-warpage filler is placed in 95～110 ℃ of dry 3～4h.
PBT resin 41.05, flame retardant brominated polystyrene 12.25%, fire retarding synergist antimonous oxide 3.2%, alkali free glass fibre chopped strand 30%, anti-warpage Resin A SA5.0%, anti-warpage resin SMA2.5%, anti-warpage filler acicular wollastonite 1.5%, toughner 3.5%, oxidation inhibitor 0.3%, coupling agent 0.2%, processing aid 0.5%.Preparation method is that the material taking by weight percentage except alkali free glass fibre chopped strand is placed in homogenizer, in 7 minutes blowings after the equal spoon of mixing of materials of 800 revs/min of lower high-speed stirring.The material after mixed spoon is placed in twin screw extruder loading hopper, twin screw extruder temperature turns round under 350 revs/min of states at 225～255 ℃, rotating speed again, and alkali free glass fibre chopped strand is added by side direction spout, extrudes tape through cooling air-drying pelletizing.
Embodiment 4: the preparation of low warpage flame-retardant reinforced PBT rly. PP Pipe Compound
PBT is placed in to 130～140 ℃ of dry 2～4h, and anti-warpage resin is placed in 80～85 ℃ of dry 2～3h, and anti-warpage filler is placed in 95～110 ℃ of dry 3～4h.
PBT resin 41.95%, flame retardant brominated epoxy resin 12.75%, fire retarding synergist antimonous oxide 3.3%, alkali free glass fibre chopped strand 30%, anti-warpage Resin A SA3.5%, anti-warpage resin SMA2.5%, anti-warpage filler acicular wollastonite 1.5%, toughner 3.5%, oxidation inhibitor 0.3% weight part, coupling agent 0.2%, processing aid 0.5%.Preparation method is that the material taking by weight percentage except alkali free glass fibre chopped strand is placed in homogenizer, in 7 minutes blowings after the equal spoon of mixing of materials of 800 revs/min of lower high-speed stirring.The material after mixed spoon is placed in twin screw extruder loading hopper, twin screw extruder temperature turns round under 350 revs/min of states at 225～255 ℃, rotating speed again, and alkali free glass fibre chopped strand is added by side direction spout, extrudes tape through cooling air-drying pelletizing.
Embodiment 5: the preparation of low warpage flame-retardant reinforced PBT rly. PP Pipe Compound
PBT is placed in to 130～140 ℃ of dry 2～4h, and anti-warpage resin is placed in 80～85 ℃ of dry 2～3h, and anti-warpage filler is placed in 95～110 ℃ of dry 3～4h.
PBT resin 40.95%, flame retardant brominated epoxy resin 12.75%, fire retarding synergist antimonous oxide 3.3%, alkali free glass fibre chopped strand 30%, anti-warpage Resin A SA4.0%, anti-warpage resin SMA2.5%, anti-warpage filler acicular wollastonite 2.0%, toughner 3.5%, oxidation inhibitor 0.3% weight part, coupling agent 0.2%, processing aid 0.5%.Preparation method is that the material taking by weight percentage except alkali free glass fibre chopped strand is placed in homogenizer, in 7 minutes blowings after the equal spoon of mixing of materials of 800 revs/min of lower high-speed stirring.The material after mixed spoon is placed in twin screw extruder loading hopper, twin screw extruder temperature turns round under 350 revs/min of states at 225～255 ℃, rotating speed again, and alkali free glass fibre chopped strand is added by side direction spout, extrudes tape through cooling air-drying pelletizing.
Embodiment 6: the preparation of low warpage flame-retardant reinforced PBT rly. PP Pipe Compound
PBT is placed in to 130～140 ℃ of dry 2～4h, and anti-warpage resin is placed in 80～85 ℃ of dry 2～3h, and anti-warpage filler is placed in 95～110 ℃ of dry 3～4h.
PBT resin 41.45%, flame retardant brominated epoxy resin 12.75%, fire retarding synergist antimonous oxide 3.3%, alkali free glass fibre chopped strand 30%, anti-warpage Resin A SA5.0%, anti-warpage resin SMA2.0%, anti-warpage filler acicular wollastonite 1.0%, toughner 3.5%, oxidation inhibitor 0.3% weight part, coupling agent 0.2%, processing aid 0.5%.Preparation method is that the material taking by weight percentage except alkali free glass fibre chopped strand is placed in homogenizer, in 7 minutes blowings after the equal spoon of mixing of materials of 800 revs/min of lower high-speed stirring.The material after mixed spoon is placed in twin screw extruder loading hopper, twin screw extruder temperature turns round under 350 revs/min of states at 225～255 ℃, rotating speed again, and alkali free glass fibre chopped strand is added by side direction spout, extrudes tape through cooling air-drying pelletizing.
Embodiment 7: compliance test result test
Comparative example 1
PBT resin 50.05%, flame retardant brominated polystyrene 12.25%, fire retarding synergist antimonous oxide 3.2%, alkali free glass fibre chopped strand 30%, toughner 3.5%, oxidation inhibitor 0.3% weight part, coupling agent 0.2%, processing aid 0.5%.Preparation method is that the material taking by weight percentage except alkali free glass fibre chopped strand is placed in homogenizer, in 7 minutes blowings after the equal spoon of mixing of materials of 800 revs/min of lower high-speed stirring.The material after mixed spoon is placed in twin screw extruder loading hopper, twin screw extruder temperature turns round under 350 revs/min of states at 225～255 ℃, rotating speed again, and alkali free glass fibre chopped strand is added by side direction spout, extrudes tape through cooling air-drying pelletizing.
Comparative example 2
PBT resin 49.45%, flame retardant brominated epoxy resin 12.75%, fire retarding synergist antimonous oxide 3.3%, alkali free glass fibre chopped strand 30%, toughner 3.5%, oxidation inhibitor 0.3% weight part, coupling agent 0.2%, processing aid 0.5%.Preparation method is that the material taking by weight percentage except alkali free glass fibre chopped strand is placed in homogenizer, in 7 minutes blowings after the equal spoon of mixing of materials of 800 revs/min of lower high-speed stirring.The material after mixed spoon is placed in twin screw extruder loading hopper, twin screw extruder temperature turns round under 350 revs/min of states at 225～255 ℃, rotating speed again, and alkali free glass fibre chopped strand is added by side direction spout, extrudes tape through cooling air-drying pelletizing.
In method for testing performance of the present invention:
Density, mechanical property, thermal characteristics adopt ASTM standard, wherein density by ASTM D792 requirement test, tensile strength by ASTM D638 requirement test, flexural strength and modulus in flexure by ASTM D790 requirement test, notched Izod impact strength performance by ASTM D256 requirement test, heat-drawn wire tests (state is 1.82MPa load) by ASTM D648 requirement.
Flame retardant properties adopts UL94 standard (state is 1.6mm).
It is qualified that warpage performance (every limit warpage performance and surrounding warpage performance) adopts described in JJG62-2007 clearance gauge to check the logical method of stopping in products formed measured size and horizontal plane gap to judge whether.
Test has detected embodiment 1-6 and contrast, the results are shown in Table 1
As can be seen from Table 1, by adding in right amount anti-warpage resin and anti-warpage filler, every limit warpage performance of product and four limit warpage performances all improve greatly, while is for other mechanical property, as tensile strength, flexural strength, notched Izod impact strength etc., and heat-drawn wire and flame retardant resistance, can remain on normal level and not decline.
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. a low warpage flame-retardant reinforced PBT rly. PP Pipe Compound, is characterized in that, forms by the weight percent of following each component and forms, and includes:
。
2. low warpage flame-retardant reinforced PBT rly. PP Pipe Compound according to claim 1, it is characterized in that, described PBT resin is one or more in 15～95g/10min, limiting viscosity 0.65 ± 0.015～1.10 ± dl/g under 250 ℃ of melting index, 2.16Kg condition; Preferably under 250 ℃ of melting index, 2.16Kg condition 45～85g/10min, limiting viscosity (IV) 0.65 ± 0.015～0.90 ± dl/g one or more; Be more preferably one or more in 55～80g/10min, limiting viscosity 0.75 ± 0.015～0.90 ± 0.015dl/g under 250 ℃ of melting index, 2.16Kg condition.
3. low warpage flame-retardant reinforced PBT rly. PP Pipe Compound according to claim 1, it is characterized in that, described fire retardant is one or more in TDE, brominated Polystyrene, brominated epoxy resin, poly-dibromobenzene aether, polyacrylic acid pentabromo-benzyl ester, phenoxy group tetrabromobisphenol A carbonic ester oligopolymer, three (tribromophenoxy) cyanurate, the two tetrabromo phthalimides of ethylene; One or more in the two tetrabromo phthalimides of brominated Polystyrene, brominated epoxy resin, phenoxy group tetrabromobisphenol A carbonic ester oligopolymer, three (tribromophenoxy) cyanurate, ethylene preferably; One or more in brominated Polystyrene, brominated epoxy resin, three (tribromophenoxy) cyanurate more preferably.
4. low warpage flame-retardant reinforced PBT rly. PP Pipe Compound according to claim 1, it is characterized in that, described fire retarding synergist can be one or more in antimonous oxide, antimony peroxide, sodium pyroantimoniate, zinc borate, zinc, zinc hydroxyl stannate, sodium wolframate, Sodium orthomolybdate; One or both in antimonous oxide, antimony peroxide, sodium pyroantimoniate, zinc borate, zinc preferably; One or more in antimonous oxide, sodium pyroantimoniate, zinc borate more preferably.
5. low warpage flame-retardant reinforced PBT rly. PP Pipe Compound according to claim 1, it is characterized in that, described toughener can be one or more in the chopped strand that alkali-free plying Non-twisting glass fibre diameter is 8～18 μ m, the linear density rove that is 1000～2800, alkali free glass fibre diameter 8～16 μ m, length 2.5～6.5 ± 1.0mm; One or more in the chopped strand of alkali free glass fibre diameter 10～15 μ m, length 2.5～6.5 ± 1.0mm preferably; One or more in the chopped strand of alkali free glass fibre diameter 11～13 μ m, length 3.0～4.5 ± 1.0mm more preferably.
6. low warpage flame-retardant reinforced PBT rly. PP Pipe Compound according to claim 1, it is characterized in that, described anti-warpage resin can be one or more in styrene-acrylonitrile-copolymer-maleic anhydride SMA, acrylonitrile acryloid styrene ASA, acrylonitrile-butadiene-styrene copolymer ABS, acrylonitrile ethylene styrene copolymer AES, acrylonitritrile-styrene resin AS, acrylonitrile-chlorianted polyethylene-styrene terpolymer ACS; Preferably styrene-acrylonitrile-copolymer-maleic anhydride SMA, acrylonitrile acryloid styrene ASA, acrylonitritrile-styrene resin AS,
One or more in acrylonitrile-chlorianted polyethylene-styrene terpolymer ACS; One or more in styrene-acrylonitrile-copolymer-maleic anhydride SMA, acrylonitrile acryloid styrene ASA more preferably.
7. low warpage flame-retardant reinforced PBT rly. PP Pipe Compound according to claim 1, it is characterized in that, described anti-warpage filler is one or more in kaolin, diatomite, barite, wollastonite, calcite, grey gypsum, white mica, talcum powder; One or more in barite, wollastonite, calcite, grey gypsum, white mica preferably;
One or more in barite, wollastonite, grey gypsum more preferably.
8. low warpage flame-retardant reinforced PBT rly. PP Pipe Compound according to claim 1, it is characterized in that, described toughner can be one or more in ethylene-propylene acid butyl ester-copolymer-maleic anhydride EMH, Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer PTW, methyl acrylate-butadiene-styrene copolymer MBS, ethylene/methyl acrylate copolymer EMA, ethylene-octene copolymer grafted maleic anhydride POE-G-MAH; One or more in ethylene-propylene acid butyl ester-copolymer-maleic anhydride EMH, Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer PTW preferably; One or more in ethylene-propylene acid butyl ester-copolymer-maleic anhydride, Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer more preferably.
9. low warpage flame-retardant reinforced PBT rly. PP Pipe Compound according to claim 1, it is characterized in that, described coupling agent is 3-aminopropyl triethoxysilane, γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-(methacryloxypropyl) propyl trimethoxy silicane, gamma-mercaptopropyltriethoxysilane, γ-mercaptopropyl trimethoxysilane, 3-[(2,3)-epoxy the third oxygen] one or more in propyl group methyl dimethoxysilane; One or more in 3-aminopropyl triethoxysilane, γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-(methacryloxypropyl) propyl trimethoxy silicane, gamma-mercaptopropyltriethoxysilane preferably; One or more in 3-aminopropyl triethoxysilane, γ-glycidyl ether oxygen propyl trimethoxy silicane more preferably;
Optional, described oxidation inhibitor is four (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, β-(4-hydroxy phenyl-3,5-di-t-butyl) the positive octadecanol ester of propionic acid, 2, [3-(3 for 2'-thiobis, 5-di-tert-butyl-hydroxy phenyl) ethyl propionate], N, [3-(3 for N ＇-bis-, 5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester, 2,2-oxalyl amido-bis-(ethyl-3-(3,5-di-tert-butyl-hydroxy phenyl)) one or more in propionic ester; Four (β-(3 preferably, 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, β-(4-hydroxy phenyl-3,5-di-t-butyl) the positive octadecanol ester of propionic acid, 2, [3-(3 for 2'-thiobis, 5-di-tert-butyl-hydroxy phenyl) ethyl propionate], one or more in tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester; One or more in the positive octadecanol ester of β-(4-hydroxy phenyl-3,5-di-t-butyl) propionic acid, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester more preferably;
Optional, other described auxiliary agent is at least one in commercially available common dispersion agent, lubricant.
10. after the arbitrary described low warpage flame-retardant reinforced PBT rly. PP Pipe Compound moulding assembling of claim 1-9, can be used for letter electrical relay, power relay, guiding rly., high frequency relay, intermediate relay, light coupling relay, the time relay, counting relay, leakage relay, over current relay, pulse relay, sun power rly., high electric current and magnetic latching relay etc.
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| CN110128799A (en) * | 2019-05-31 | 2019-08-16 | 珠海格力新材料有限公司 | A kind of PBT composite and preparation method |
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