CN103724953B - A kind of low warpage flame-retardant reinforced PBT rly. PP Pipe Compound and purposes - Google Patents
A kind of low warpage flame-retardant reinforced PBT rly. PP Pipe Compound and purposes Download PDFInfo
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- CN103724953B CN103724953B CN201410019072.0A CN201410019072A CN103724953B CN 103724953 B CN103724953 B CN 103724953B CN 201410019072 A CN201410019072 A CN 201410019072A CN 103724953 B CN103724953 B CN 103724953B
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Abstract
The invention discloses a kind of low warpage flame-retardant reinforced PBT rly. PP Pipe Compound and purposes.It consists of following weight ratio composition: PBT resin 40 ~ 55%, fire retardant 10 ~ 15%, fire retarding synergist 2 ~ 7%, toughener 20 ~ 35%, that resist warping resin 2 ~ 9%, that resist warping filler 1 ~ 5%, toughner 2 ~ 5%, coupling agent 0.1 ~ 0.5%, oxidation inhibitor 0.2 ~ 0.8%, processing aid 0.2 ~ 0.8%.Every limit warpage performance and the four limit warpage performances of product of the present invention improve greatly, other mechanical properties, and as tensile strength, flexural strength, notched Izod impact strength, heat-drawn wire and flame retardant resistance etc., can remain on normal level and not decline.Various rly. is can be used for, as in the multiple rly. of letter electrical relay, power relay, guiding rly. etc. after shaping assembling.
Description
Technical field
The present invention relates to field of polymer technology compositions field, particularly relate 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, the regularity of its flexible fatty alcohol and rigidity phenyl ring combine make PBT have the high and resistance to fatigue of excellent mechanical performances intensity and chemical proofing, while low wear-resistant, the electric insulating quality of weather resistance good, 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 easily burn, the shortcoming such as molding shrinkage is large.Need in PBT application for this reason targetedly to its carry out physically modified with the requirement meeting market, especially electric industry possesses material requirements physical strength and flame-retarding characteristic, specifically to meet thin-wall part such as all kinds of relay product and also require the requirement of the low warpage of lower shrinkage.
Summary of the invention
A kind of existing superior mechanical physicals is the object of the present invention is to provide to have again superior dimensional to stablize low warpage flame-retardant reinforced PBT 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, the weight percent that composition presses following ingredients is formed, and includes:
Described PBT resin is one or more under melting index 250 DEG C, 2.16Kg condition in 15 ~ 95g/10min, limiting viscosity 0.65 ± 0.015 ~ 1.10 ± dl/g; Preferably under melting index 250 DEG C, 2.16Kg condition 45 ~ 85g/10min, limiting viscosity (IV) 0.65 ± 0.015 ~ 0.90 ± dl/g one or more; Be more preferably under melting index 250 DEG C, 2.16Kg condition in 55 ~ 80g/10min, limiting viscosity 0.75 ± 0.015 ~ 0.90 ± 0.015dl/g one or more.
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 phthalimide of ethylene; One or more preferably in brominated Polystyrene, brominated epoxy resin, phenoxy group tetrabromobisphenol A carbonic ester oligopolymer, three (tribromophenoxy) cyanurate, the two tetrabromo phthalimide of ethylene; One or more more preferably in brominated Polystyrene, brominated epoxy resin, three (tribromophenoxy) cyanurate.
Described fire retarding synergist can be in antimonous oxide, antimony peroxide, sodium pyroantimoniate, zinc borate, zinc, zinc hydroxyl stannate, sodium wolframate, Sodium orthomolybdate one or more; One or both preferably in antimonous oxide, antimony peroxide, sodium pyroantimoniate, zinc borate, zinc; One or more more preferably in antimonous oxide, sodium pyroantimoniate, zinc borate.
Described toughener can be in the chopped strand of alkali-free plying Non-twisting glass fibre diameter is 8 ~ 18 μm, linear density is 1000 ~ 2800 rove, alkali free glass fibre diameter 8 ~ 16 μm, length 2.5 ~ 6.5 ± 1.0mm one or more; One or more in the chopped strand of preferably alkali free glass fibre diameter 10 ~ 15 μm, length 2.5 ~ 6.5 ± 1.0mm; One or more in the chopped strand of more preferably alkali free glass fibre diameter 11 ~ 13 μm, length 3.0 ~ 4.5 ± 1.0mm.
Described that resist warping resin can be 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; One or more in preferably styrene-acrylonitrile-copolymer-maleic anhydride SMA, acrylonitrile acryloid styrene ASA, acrylonitritrile-styrene resin AS, acrylonitrile-chlorianted polyethylene-styrene terpolymer ACS; One or more in more preferably styrene-acrylonitrile-copolymer-maleic anhydride SMA, acrylonitrile acryloid styrene ASA.
Described that resist warping filler is one or more in kaolin, diatomite, barite, wollastonite, calcite, grey gypsum, white mica, talcum powder; One or more preferably in barite, wollastonite, calcite, grey gypsum, white mica; One or more more preferably in barite, wollastonite, grey gypsum.
Described toughner can be in Ethylene-butyl acrylate-copolymer-maleic anhydride EMH, Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer PTW, methylacrylate-butadiene-styrol copolymer MBS, ethylene/methyl acrylate copolymer EMA, ethylene-octene copolymer grafted maleic anhydride POE-G-MAH one or more; One or more in preferably Ethylene-butyl acrylate-copolymer-maleic anhydride EMH, Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer PTW; One or more more preferably in Ethylene-butyl acrylate-copolymer-maleic anhydride, Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer.
Described coupling agent is one or more in 3-aminopropyl triethoxysilane, γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-(methacryloxypropyl) propyl trimethoxy silicane, gamma-mercaptopropyltriethoxysilane, γ-mercaptopropyl trimethoxysilane, 3-[(2,3)-epoxy third oxygen] hydroxypropyl methyl dimethoxysilane; One or more preferably in 3-aminopropyl triethoxysilane, γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-(methacryloxypropyl) propyl trimethoxy silicane, gamma-mercaptopropyltriethoxysilane; One or more more preferably in 3-aminopropyl triethoxysilane, γ-glycidyl ether oxygen propyl trimethoxy silicane;
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, 2'-thiobis [3-(3, 5-di-tert-butyl-hydroxy phenyl) ethyl propionate], N, N ＇-bis-[3-(3, 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, preferably 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, 2,2'-thiobis [3-(3,5-di-tert-butyl-hydroxy phenyl) ethyl propionate], one or more in tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester, one or more in more preferably β-positive octadecanol ester of (4-hydroxy phenyl-3,5-di-t-butyl) propionic acid, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester,
Optional, other described auxiliary agent is at least one in commercially available common dispersants, lubricant.
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. after the shaping assembling of described low warpage flame-retardant reinforced PBT rly. PP Pipe Compound.
The invention reside in and adopt resin based on PBT, using glass fibre and fire retardant and fire retarding synergist as fire-retardant enhancing system, formed resisted shrinkage warpage system with resisted shrinkage warpage resin and filler, other about auxiliary agent as the cooperation of toughner, coupling agent, oxidation inhibitor and processing aid under obtained existing superior mechanical physicals have again superior dimensional to stablize low warpage flame-retardant reinforced PBT rly. PP Pipe Compound.
PBT resin model of the present invention can be melting index (MI) 15 ~ 95g/10min (250 DEG C, 2.16Kg), limiting viscosity (IV) 0.65 ± 0.015 ~ 1.10 ± dl/g, is more preferably melting index (MI) 45 ~ 85g/10min (250 DEG C, 2.16Kg), limiting viscosity (IV) 0.65 ± 0.015 ~ 0.90 ± dl/g more than one or more than one.One or more preferably in melting index (MI) 55 ~ 80g/10min (250 DEG C, 2.16Kg), limiting viscosity (IV) 0.75 ± 0.015 ~ 0.90 ± 0.015dl/g.
Fire retardant of the present invention can be 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 phthalimide of ethylene one or more.One or more even more preferably in brominated Polystyrene, brominated epoxy resin, phenoxy group tetrabromobisphenol A carbonic ester oligopolymer, three (tribromophenoxy) cyanurate, the two tetrabromo phthalimide of ethylene.One or more preferably in brominated Polystyrene, brominated epoxy resin, three (tribromophenoxy) cyanurate.
Fire retarding synergist of the present invention can be in antimonous oxide, antimony peroxide, sodium pyroantimoniate, zinc borate, zinc, zinc hydroxyl stannate, sodium wolframate, Sodium orthomolybdate one or more.One or more even more preferably in antimonous oxide, antimony peroxide, sodium pyroantimoniate, zinc borate, zinc.One or more preferably in antimonous oxide, sodium pyroantimoniate, zinc borate.
Toughener of the present invention can be in the chopped strand of alkali-free plying Non-twisting glass fibre diameter is 8 ~ 18 μm, linear density is 1000 ~ 2800 rove, alkali free glass fibre diameter 8 ~ 16 μm, length 2.5 ~ 6.5 ± 1.0mm one or more.One or more in the chopped strand of even more preferably alkali free glass fibre diameter 10 ~ 15 μm, length 2.5 ~ 6.5 ± 1.0mm.One or more in the chopped strand of preferably alkali free glass fibre diameter 11 ~ 13 μm, length 3.0 ~ 4.5 ± 1.0mm.
That resist warping resin of the present invention can be in styrene/acrylonitrile/copolymer-maleic anhydride (SMA), acrylonitrile/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.
One or more even more preferably in styrene/acrylonitrile/copolymer-maleic anhydride (SMA), acrylonitrile/acrylate/styrol copolymer (ASA), vinyl cyanide/styrol copolymer (AS), vinyl cyanide/chlorinatedpolyethylene/styrol copolymer (ACS).One or more preferably in styrene/acrylonitrile/copolymer-maleic anhydride (SMA), acrylonitrile/acrylate/styrol copolymer (ASA).
That resist warping filler of the present invention is one or more in kaolin, diatomite, barite, wollastonite, calcite, grey gypsum, white mica, talcum powder.One or more even more preferably in barite, wollastonite, calcite, grey gypsum, white mica.One or more preferably in barite, wollastonite, grey gypsum.
Toughner of the present invention can be Ethylene-butyl acrylate-copolymer-maleic anhydride (EMH), Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer (PTW), methylacrylate-butadiene-styrol copolymer (MBS), ethylene/methyl acrylate copolymer (EMA), ethylene-octene copolymer grafted maleic anhydride (POE-G-MAH).One or more even more preferably in Ethylene-butyl acrylate-copolymer-maleic anhydride, Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer.Be preferably in Ethylene-butyl acrylate-copolymer-maleic anhydride, Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer one or more.
Coupling agent of the present invention is one or more in 3-aminopropyl triethoxysilane, γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-(methacryloxypropyl) propyl trimethoxy silicane, gamma-mercaptopropyltriethoxysilane, γ-mercaptopropyl trimethoxysilane, 3-[(2,3)-epoxy third oxygen] hydroxypropyl methyl dimethoxysilane.One or more even more preferably in 3-aminopropyl triethoxysilane, γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-(methacryloxypropyl) propyl trimethoxy silicane, gamma-mercaptopropyltriethoxysilane.One or more preferably in 3-aminopropyl triethoxysilane, γ-glycidyl ether oxygen propyl trimethoxy silicane.
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, 2'-thiobis [3-(3, 5-di-tert-butyl-hydroxy phenyl) ethyl propionate], N, N ＇-bis-[3-(3, 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.Even more preferably 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, 2,2'-thiobis [3-(3,5-di-tert-butyl-hydroxy phenyl) ethyl propionate], one or more in tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester.One or more in preferably β-positive octadecanol ester of (4-hydroxy phenyl-3,5-di-t-butyl) propionic acid, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester.
Other auxiliary agent of the present invention is the processing aids such as commercially available common dispersants, 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 130 ~ 140 DEG C of drying 2 ~ 4h, that resist warping resin is placed in 80 ~ 85 DEG C of drying 2 ~ 3h, and that resist warping filler is placed in 95 ~ 110 DEG C of drying 3 ~ 4h.The present invention is by first drying the rear regenerative ratio of material, and the mechanical property of product is than the product improve about 30% of not drying material direct production.
(2). the material taken by weight percentage except alkali free glass fibre chopped strand is placed in material agitator, in 750 ~ 850 revs/min of lower high-speed stirring, 5 ~ 10 minutes blowings after the equal spoon of mixing of materials.
(3). twin screw extruder temperature 220 ~ 260 DEG C, rotating speed operates under 300 ~ 400 revs/min of states, alkali free glass fibre chopped strand is added by side direction spout, the material mixing equal spoon is introduced by twin screw extruder elevating hopper, extrudes after tape through cooling air-drying pelletizing.
In above method, the too high or rotating speed of temperature is too slow, and product all can be caused easily to be oxidized in mixing process, and temperature is too low or rotating speed is too fast, be then 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, and its Midst density is undertaken testing by ASTMD792 requirement, tensile strength is undertaken testing by ASTMD638 requirement, flexural strength and modulus are undertaken testing by ASTMD790 requirement, notch shock performance is undertaken testing by ASTMD256 requirement, heat-drawn wire is undertaken testing (state is 1.82MPa load) by ASTMD648 requirement.
Flame retardant properties adopts UL94 standard (state is 1.6mm)
Warpage performance adopts clearance gauge described in JJG62-2007 to check the logical method of stopping in products formed measured size and horizontal plane gap qualified to judge whether.
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. after the shaping assembling of low warpage flame-retardant reinforced PBT rly. PP Pipe Compound of the present invention.
Embodiments of the invention 7 result shows, by adding that resist warping resin and that resist warping filler (embodiment 1-6 fill a prescription products obtained therefrom) in right amount, every limit warpage performance and the four limit warpage performances of product improve all greatly, simultaneously for other mechanical property, as tensile strength, flexural strength, notched Izod impact strength etc., and heat-drawn wire and flame retardant resistance, can normal level be remained on and not decline.
Embodiment
Be described below in detail embodiments of the invention, 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 technology described by the document in this area or condition or carry out according to product description.Agents useful for same or the unreceipted production firm person of instrument, being can by the conventional products of commercial acquisition.
Embodiment main agents used
PBT resin adopts commercially available melting index (MI) 55 ~ 80g/10min (250 DEG C, 2.16Kg) limiting viscosity (IV) 0.85 ± 0.015dl/g, and manufacturer is three Fang Xiang group or Xingchen Synthetic Matrials Co., Ltd., Nantong.
Fire retardant adopts model to be the brominated Polystyrene (BPS) of GREATBAYXZ-6700 and model to be the brominated epoxy resin (BEO) of BEO-1, and manufacturer is respectively Shandong Xiongdi Science & Technology Co., Ltd. and Shandong Chemical Co., Ltd. of Futong.
Fire retarding synergist adopts model to be the antimonous oxide of Sb2O3-99.90, and manufacturer is Anhua Hua Yuti industry company limited.
Toughener employing model is the alkali free glass fibre chopped strand of 534W (Fibre diameter 13 μm, length 4.5mm), and manufacturer is Jushi Group Co., Ltd..
Acrylonitrile/acrylate/styrol copolymer (ASA) that styrene/acrylonitrile/copolymer-maleic anhydride (SMA) that resist warping resin employing model is SMA3000, model are XC-200, manufacturer is respectively Cray Willie chemical company and Jin Hu petroleum chemistry company.
That resist warping filler adopts model to be the acicular wollastonite of 2000M, and manufacturer is Jiangxi Ao Te fine powder company limited.
Toughner adopts model to be the Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer of PTW, and manufacturer is E.I.Du Pont Company.
Coupling agent employing model is the γ-glycidyl ether oxygen propyl trimethoxy silicane of SG-Si187, and manufacturer is Nanjing dawn Chemical Co., Ltd..
Oxidation inhibitor employing model is four (β-(3 of AT10,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester and model be the tricresyl phosphite (2 of AT168,4-di-tert-butyl-phenyl) ester, manufacturer is Jinhai-Yabao Chemical Co., Ltd., Ningbo.
Processing aid is the N of the gorgeous auxiliary agent in Shanghai hundred, 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 130 ~ 140 DEG C of drying 2 ~ 4h, that resist warping resin is placed in 80 ~ 85 DEG C of drying 2 ~ 3h, and that resist warping filler is placed in 95 ~ 110 DEG C of drying 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%, that resist warping Resin A SA3.5%, that resist warping resin SMA2.5%, that resist warping 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 taken by weight percentage except alkali free glass fibre chopped strand is placed in homogenizer, in 800 revs/min of lower high-speed stirring, 7 minutes blowings after the equal spoon of mixing of materials.Again the material after mixed spoon is placed in twin screw extruder loading hopper, twin screw extruder temperature 225 ~ 255 DEG C, rotating speed operates under 350 revs/min of states, 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 130 ~ 140 DEG C of drying 2 ~ 4h, that resist warping resin is placed in 80 ~ 85 DEG C of drying 2 ~ 3h, and that resist warping filler is placed in 95 ~ 110 DEG C of drying 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%, that resist warping Resin A SA4.0%, that resist warping resin SMA2.5%, that resist warping 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 taken by weight percentage except alkali free glass fibre chopped strand is placed in homogenizer, in 800 revs/min of lower high-speed stirring, 7 minutes blowings after the equal spoon of mixing of materials.Again the material after mixed spoon is placed in twin screw extruder loading hopper, twin screw extruder temperature 225 ~ 255 DEG C, rotating speed operates under 350 revs/min of states, 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 130 ~ 140 DEG C of drying 2 ~ 4h, that resist warping resin is placed in 80 ~ 85 DEG C of drying 2 ~ 3h, and that resist warping filler is placed in 95 ~ 110 DEG C of drying 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%, that resist warping Resin A SA5.0%, that resist warping resin SMA2.5%, that resist warping 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 taken by weight percentage except alkali free glass fibre chopped strand is placed in homogenizer, in 800 revs/min of lower high-speed stirring, 7 minutes blowings after the equal spoon of mixing of materials.Again the material after mixed spoon is placed in twin screw extruder loading hopper, twin screw extruder temperature 225 ~ 255 DEG C, rotating speed operates under 350 revs/min of states, 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 130 ~ 140 DEG C of drying 2 ~ 4h, that resist warping resin is placed in 80 ~ 85 DEG C of drying 2 ~ 3h, and that resist warping filler is placed in 95 ~ 110 DEG C of drying 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%, that resist warping Resin A SA3.5%, that resist warping resin SMA2.5%, that resist warping 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 taken by weight percentage except alkali free glass fibre chopped strand is placed in homogenizer, in 800 revs/min of lower high-speed stirring, 7 minutes blowings after the equal spoon of mixing of materials.Again the material after mixed spoon is placed in twin screw extruder loading hopper, twin screw extruder temperature 225 ~ 255 DEG C, rotating speed operates under 350 revs/min of states, 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 130 ~ 140 DEG C of drying 2 ~ 4h, that resist warping resin is placed in 80 ~ 85 DEG C of drying 2 ~ 3h, and that resist warping filler is placed in 95 ~ 110 DEG C of drying 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%, that resist warping Resin A SA4.0%, that resist warping resin SMA2.5%, that resist warping 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 taken by weight percentage except alkali free glass fibre chopped strand is placed in homogenizer, in 800 revs/min of lower high-speed stirring, 7 minutes blowings after the equal spoon of mixing of materials.Again the material after mixed spoon is placed in twin screw extruder loading hopper, twin screw extruder temperature 225 ~ 255 DEG C, rotating speed operates under 350 revs/min of states, 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 130 ~ 140 DEG C of drying 2 ~ 4h, that resist warping resin is placed in 80 ~ 85 DEG C of drying 2 ~ 3h, and that resist warping filler is placed in 95 ~ 110 DEG C of drying 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%, that resist warping Resin A SA5.0%, that resist warping resin SMA2.0%, that resist warping 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 taken by weight percentage except alkali free glass fibre chopped strand is placed in homogenizer, in 800 revs/min of lower high-speed stirring, 7 minutes blowings after the equal spoon of mixing of materials.Again the material after mixed spoon is placed in twin screw extruder loading hopper, twin screw extruder temperature 225 ~ 255 DEG C, rotating speed operates under 350 revs/min of states, alkali free glass fibre chopped strand is added by side direction spout, extrudes tape through cooling air-drying pelletizing.
Embodiment 7: compliance test result is tested
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 taken by weight percentage except alkali free glass fibre chopped strand is placed in homogenizer, in 800 revs/min of lower high-speed stirring, 7 minutes blowings after the equal spoon of mixing of materials.Again the material after mixed spoon is placed in twin screw extruder loading hopper, twin screw extruder temperature 225 ~ 255 DEG C, rotating speed operates under 350 revs/min of states, 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 taken by weight percentage except alkali free glass fibre chopped strand is placed in homogenizer, in 800 revs/min of lower high-speed stirring, 7 minutes blowings after the equal spoon of mixing of materials.Again the material after mixed spoon is placed in twin screw extruder loading hopper, twin screw extruder temperature 225 ~ 255 DEG C, rotating speed operates under 350 revs/min of states, 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, and its Midst density is undertaken testing by ASTMD792 requirement, tensile strength is undertaken testing by ASTMD638 requirement, flexural strength and modulus in flexure are undertaken testing by ASTMD790 requirement, notched Izod impact strength performance is undertaken testing by ASTMD256 requirement, heat-drawn wire is undertaken testing (state is 1.82MPa load) by ASTMD648 requirement.
Flame retardant properties adopts UL94 standard (state is 1.6mm).
Warpage performance (every limit warpage performance and surrounding warpage performance) adopts clearance gauge described in JJG62-2007 to check the logical method of stopping of products formed measured size and horizontal plane gap qualified to judge whether.
Testing inspection embodiment 1-6 and contrast, the results are shown in Table 1
As can be seen from Table 1, by adding that resist warping resin and that resist warping filler in right amount, every limit warpage performance and the four limit warpage performances of product improve all greatly, simultaneously for other mechanical property, as tensile strength, flexural strength, notched Izod impact strength etc., and heat-drawn wire and flame retardant resistance, can normal level be remained on and not decline.
Although illustrate and describe 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 when not departing from principle of the present invention and aim, revising, replacing and modification.
Claims (19)
1. a low warpage flame-retardant reinforced PBT rly. PP Pipe Compound, is characterized in that, the weight percent that composition presses following ingredients is formed, and includes:
Described that resist warping resin is styrene-acrylonitrile-copolymer-maleic anhydride SMA and acrylonitrile acryloid styrene ASA;
Described PBT resin is one or more under melting index 250 DEG C, 2.16Kg condition in 15 ~ 95g/10min, limiting viscosity 0.65 ± 0.015 ~ 1.10 ± 0.015dl/g;
Described fire retardant is brominated Polystyrene or brominated epoxy resin;
Described toughener can be in the chopped strand of alkali-free plying Non-twisting glass fibre diameter is 8 ~ 18 μm, linear density is 1000 ~ 2800 rove, alkali free glass fibre diameter 8 ~ 16 μm, length 2.5 ~ 6.5 ± 1.0mm one or more;
Described that resist warping filler is acicular wollastonite.
2. low warpage flame-retardant reinforced PBT rly. PP Pipe Compound according to claim 1, it is characterized in that, described PBT resin be 45 ~ 85g/10min under melting index 250 DEG C, 2.16Kg condition, limiting viscosity (IV) 0.65 ± 0.015 ~ 0.90 ± 0.015dl/g one or more.
3. low warpage flame-retardant reinforced PBT rly. PP Pipe Compound according to claim 2, it is characterized in that, described PBT resin is one or more under melting index 250 DEG C, 2.16Kg condition in 55 ~ 80g/10min, limiting viscosity 0.75 ± 0.015 ~ 0.90 ± 0.015dl/g.
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 in antimonous oxide, antimony peroxide, sodium pyroantimoniate, zinc borate, zinc, zinc hydroxyl stannate, sodium wolframate, Sodium orthomolybdate one or more.
5. low warpage flame-retardant reinforced PBT rly. PP Pipe Compound according to claim 4, is characterized in that, described fire retarding synergist is one or both in antimonous oxide, antimony peroxide, sodium pyroantimoniate, zinc borate, zinc.
6. low warpage flame-retardant reinforced PBT rly. PP Pipe Compound according to claim 5, is characterized in that, described fire retarding synergist is one or more in antimonous oxide, sodium pyroantimoniate, zinc borate.
7. low warpage flame-retardant reinforced PBT rly. PP Pipe Compound according to claim 1, is characterized in that, described toughener is one or more in the chopped strand of alkali free glass fibre diameter 10 ~ 15 μm, length 2.5 ~ 6.5 ± 1.0mm.
8. low warpage flame-retardant reinforced PBT rly. PP Pipe Compound according to claim 7, is characterized in that, described toughener is one or more in the chopped strand of alkali free glass fibre diameter 11 ~ 13 μm, length 3.0 ~ 4.5 ± 1.0mm.
9. low warpage flame-retardant reinforced PBT rly. PP Pipe Compound according to claim 1, it is characterized in that, described toughner can be in Ethylene-butyl acrylate-copolymer-maleic anhydride EMH, Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer PTW, methylacrylate-butadiene-styrol copolymer MBS, ethylene/methyl acrylate copolymer EMA, ethylene-octene copolymer grafted maleic anhydride POE-G-MAH one or more.
10. low warpage flame-retardant reinforced PBT rly. PP Pipe Compound according to claim 9, it is characterized in that, described toughner is one or more in Ethylene-butyl acrylate-copolymer-maleic anhydride EMH, Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer PTW.
11. low warpage flame-retardant reinforced PBT rly. PP Pipe Compound according to claim 10, it is characterized in that, described toughner is one or more in Ethylene-butyl acrylate-copolymer-maleic anhydride, Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer.
12. low warpage flame-retardant reinforced PBT rly. PP Pipe Compound according to claim 1, it is characterized in that, described coupling agent is one or more in 3-aminopropyl triethoxysilane, γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-(methacryloxypropyl) propyl trimethoxy silicane, gamma-mercaptopropyltriethoxysilane, γ-mercaptopropyl trimethoxysilane, 3-[(2,3)-epoxy third oxygen] hydroxypropyl methyl dimethoxysilane.
13. according to warpage flame-retardant reinforced PBT rly. PP Pipe Compound low described in claim 12, it is characterized in that, described coupling agent is one or more in 3-aminopropyl triethoxysilane, γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-(methacryloxypropyl) propyl trimethoxy silicane, gamma-mercaptopropyltriethoxysilane.
14., according to warpage flame-retardant reinforced PBT rly. PP Pipe Compound low described in claim 13, is characterized in that, described coupling agent is one or more in 3-aminopropyl triethoxysilane, γ-glycidyl ether oxygen propyl trimethoxy silicane.
15. low warpage flame-retardant reinforced PBT rly. PP Pipe Compound according to claim 1, it is characterized in that, described coupling agent 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, 2'-thiobis [3-(3, 5-di-tert-butyl-hydroxy phenyl) ethyl propionate], N, N ＇-bis-[3-(3, 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.
16. according to warpage flame-retardant reinforced PBT rly. PP Pipe Compound low described in claim 15, it is characterized in that, described coupling agent 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, 2,2'-thiobis [3-(3,5-di-tert-butyl-hydroxy phenyl) ethyl propionate], one or more in tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester.
17. according to warpage flame-retardant reinforced PBT rly. PP Pipe Compound low described in claim 16, it is characterized in that, described coupling agent is β-(4-hydroxy phenyl-3,5-di-t-butyl) the positive octadecanol ester of propionic acid, one or more in tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester.
18. low warpage flame-retardant reinforced PBT rly. PP Pipe Compound according to claim 1, it is characterized in that, other described auxiliary agent is at least one in commercially available common dispersants, lubricant.
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 is can be used for after the shaping assembling of the arbitrary described low warpage flame-retardant reinforced PBT rly. PP Pipe Compound of 19. claim 1-18.
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| CN107141733A (en) * | 2017-06-26 | 2017-09-08 | 宁波市特尔佳塑料科技有限公司 | A kind of ABS strengthens modified PBT composition |
| CN110029407A (en) * | 2019-05-10 | 2019-07-19 | 江苏恒宇纺织集团有限公司 | A kind of porous PBT fiber DTY, which is washed, leads silk and preparation method thereof |
| 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 |
| CN111154241A (en) * | 2020-02-14 | 2020-05-15 | 中广核瑞胜发（厦门）新材料有限公司 | Reinforced flame-retardant low-warpage PBT (polybutylene terephthalate) composite material and preparation method thereof |
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Denomination of invention: A low warpage flame retardant reinforced PBT relay special material and its application Effective date of registration: 20210414 Granted publication date: 20160217 Pledgee: Xiamen Haicang Financing Guarantee Co.,Ltd. Pledgor: XIAMEN TIANYU PLASTIC INDUSTRY Co.,Ltd. Registration number: Y2021980002648 |
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Address after: 361000 Room 501, No.9 Xinkang Road, Xinyang street, Haicang District, Xiamen City, Fujian Province Patentee after: Xiamen Tianyu New Material Technology Co.,Ltd. Address before: 361000 Room 501, No.9 Xinkang Road, Xinyang street, Haicang District, Xiamen City, Fujian Province Patentee before: XIAMEN TIANYU PLASTIC INDUSTRY Co.,Ltd. |