Background technology
Polybutylene terephthalate (English name Polybutylene Terephthalate is called for short PBT) arrives opaque, crystalline thermoplastic polyester for oyster white is translucent.It has high heat resistance, toughness, resistance to fatigue, self-lubricating, low-friction coefficient, and weathering resistance, water-intake rate are low, still keeps various physical property (comprising electrical property), electrical insulating property, good forming ability in wet environment.Shortcoming is that notched Izod impact strength is low, and molding shrinkage is large.Therefore major part adopts glass fiber reinforcement or inorganic fill modification, its tensile strength, flexural strength can be enhanced about more than once, and heat-drawn wire also significantly improves.Can long term operation at 140 DEG C, after flame-retardant modified, Low-voltage Electronic electric components can be widely used in.
Polyethylene terephthalate (English name Polyethylene Terephthalate is called for short PET) is oyster white or polymkeric substance that is light yellow, highly crystalline, and surface smoothing is glossy.PET molecular structure high degree of symmetry, has certain crystalline orientation ability, therefore has higher film-forming properties.PET has good optical property and weathering resistance, and amorphous PET has good optical transparence.PET has excellent abrasion performance, rub resistance and dimensional stability and electrical insulating property in addition.The bottle that PET makes has that intensity is large, the transparency is good, nontoxic, impermeable, quality light, production efficiency advantages of higher, is thus widely used.
PBT and PET molecular chain structure is similar, and most of character is also the same, and just molecular backbone chain becomes four by two methylene radical, so molecule is submissiveer, processing characteristics is more excellent, but the shaping cycle of PET is longer.PBT, PET being made after alloy can comprehensive the two advantage, and improve the performance of material, domestic at present had more research.21 century electronics, electrically, communication, household electrical appliances, electromechanical equipment to high-performance microization development, more and more higher to the requirement of flame-retardant PBT/PET alloy material, meanwhile, along with the mankind are to the understanding of environmental protection, Green Product is subject to common concern.Therefore, flame-retardant PBT/PET alloy material developing direction is: performance function flame-retardant PBT/PET alloy material becomes main flow; The kind of environmental type flame-retardant PBT/PET alloy material and demand get more and more; The production of flame-retardant PBT/PET alloy material is to multi items seriation future development; The use of fire retardant is to diversification, compound development.Traditional bromide fire retardant can not meet the requirement of high standard product, some traditional fire retardant compound systems, such as glass fibre+TDE+antimonous oxide compound system, glass fibre+brominated Polystyrene+antimonous oxide compound system, CTI value (the comparative tracking index of these compound systems, relative discharge tracking index) and GWIT value (glow-wire ignition temperature, glow-wire ignition temperature) not high, be not suitable for the power utilization environment of high request.
Chinese patent literature application number 201210247433.8, publication date on October 17th, 2012, disclose a kind of flame-proof glass fibre and strengthen PBT/PET alloy composite and preparation method thereof, said composition comprises each component of following weight percent content: PET 20 ~ 41%, PBT 20 ~ 41%, compatilizer 1 ~ 10%, compositional flame-retardant master batch 1 ~ 15%, glass fibre 20 ~ 40%, oxidation inhibitor 0.1 ~ 1%, lubrication dispersing agent 0.1 ~ 1%, described compositional flame-retardant master batch comprises each component of following mass percentage content: deironing red phosphorus master batch 50%, antimigration agent 25%, high CTI auxiliary agent 25%.But have not been reported about the alloy material integrating the advantages such as high GWIT value, high CTI value, environmental protection, over-all properties equilibrium.
Summary of the invention
The object of the invention is for deficiency of the prior art, provide a kind of high CTI value, high GWIT value environment-protection flame-proof fiberglass to strengthen PBT/PET alloy material.This alloy material glow wire temperature is higher, environmental protection, and over-all properties is balanced, is applicable to Low-voltage Electronic capacitor case, load break switch, carbon brush supports, the electronic applications such as breaker of plastic casing.
Of the present invention again one object be provide a kind of high CTI value, high GWIT value environment-protection flame-proof fiberglass to strengthen the preparation method of PBT/PET alloy material.
For achieving the above object, the technical scheme that the present invention takes is:
A kind of high CTI value, high GWIT value environment-protection flame-proof fiberglass strengthen PBT/PET alloy material, and described alloy material comprises the feed composition of following weight percent content:
PBT 22.5%～41%，
PET 22.5%～41%，
Compound flame redundant 6% ~ 20%,
Antimonous oxide 3% ~ 15%,
Glass fibre 20% ~ 30%,
Toughner 2% ~ 10%,
Oxidation inhibitor 0.1% ~ 1%,
Oxide compound 0.1% ~ 1%,
Described compound flame redundant is made up of brominated Polystyrene, magnesium hypophosphite and talcum powder.
Described PBT is polybutylene terephthalate, and its limiting viscosity is 1.0 dL/g.
Described PET is polyethylene terephthalate, and its limiting viscosity is 1.0 dL/g.
Described compound flame redundant is made up of the feed composition of following weight percent content: brominated Polystyrene 50%, magnesium hypophosphite 25%, talcum powder 25%.
Described glass fibre is the alkali free glass fibre of surface through silane coupling agent process.
Described toughner is ethylene-methyl acrylate-glyceryl methacrylate random terpolymer.
Described oxidation inhibitor is Hinered phenols antioxidant.
Described oxidation inhibitor is oxidation inhibitor 1330.
Described oxide compound is ferric oxide.
For realizing above-mentioned second object, the technical scheme that the present invention takes is:
High CTI value, high GWIT value environment-protection flame-proof fiberglass strengthen a preparation method for PBT/PET alloy material, comprise the steps:
(1) each raw material is taken according to weight percent according to claim 1;
(2) the various raw materials weighed up are put into high mixer, mix 2 ~ 5 minutes, discharging, then uses twin screw extruder extruding pelletization, and the processing temperature of described twin screw extruder is 230 ~ 240 DEG C, and screw rod revolution is 30 ~ 40Hz.。
The invention has the advantages that:
1, the present invention adopts BACN compound system, compares with traditional flame-retardant system, and when fire retardant percentage composition is identical, novel built system can make the GWIT value raising 50 DEG C to 100 DEG C of material, can pass through 850 DEG C of glowing filaments;
2, the GWIT value of material can be made to significantly improve adding of glass fibre, toughner can improve the impact property of material, improves materials processing mobility, reduces frictional coefficient, improves slipping;
3, Hinered phenols antioxidant can improve the ageing resistance of matrix material in the antioxidant property and use procedure of the course of processing, adopts oxide compound as the auxiliary agent carrying high CTI value;
4, the present invention is under specific processing conditions, and stock dispersion is better, and the residence time is short, adopts and shears slightly weak combination, prevent fire retardant from decomposing, thus ensure that the steady quality of material; GWIT value and the CTI value of the matrix material prepared are higher, flame retardant effect is better, matrix material environmental protection, over-all properties is balanced, can be widely used in the product of the field of electronics such as Low-voltage Electronic capacitor case, load break switch, carbon brush supports, breaker of plastic casing.
Embodiment
Below embodiment provided by the invention is elaborated.
High CTI value of the present invention, high GWIT value environment-protection flame-proof fiberglass strengthen PBT/PET alloy material, and described PBT is commercially available polybutylene terephthalate, and its limiting viscosity is preferably 1.0 dL/g, also can be other value of 0.8 ~ 1.2 dL/g scope; Described PET is commercially available polyethylene terephthalate, and its limiting viscosity is preferably 1.0 dL/g, also can be other value of 0.8 ~ 1.2 dL/g scope; Described compound flame redundant is made up of brominated Polystyrene (being called for short BPS), magnesium hypophosphite and talcum powder, and weight percent content is preferably BPS 50%, magnesium hypophosphite 25%, talcum powder 25%, and this fire retardant effectively can improve the GWIT value of alloy material; Described glass fibre is preferably the alkali free glass fibre of surface through silane coupling agent process, and added by glass fibre in silane coupling agent, make its surface through silane coupling agent process, it can make the GWIT value of material significantly improve; Described toughner can improve the impact property of material, can be ethylene-methyl acrylate-glyceryl methacrylate random terpolymer, ethylene-methyl acrylate copolymer, ethylene-vinyl acetate copolymer etc., be preferably ethylene-methyl acrylate-glyceryl methacrylate random terpolymer; Described oxidation inhibitor is preferably the oxidation inhibitor 1330 in Hinered phenols antioxidant, can also be antioxidant 1010, antioxidant 300, thio-2 acid dibasic acid esters etc., equal energy blocks, suppresses or delays polymkeric substance oxidation or autoxidation process, can improve the antioxidant property of alloy material in the course of processing and the ageing resistance in use procedure; Described oxide compound is the auxiliary agent as carrying high CTI value, can be aluminum oxide, magnesium oxide etc., is preferably ferric oxide.
In the preparation process of PBT/PET alloy material of the present invention, the various raw materials weighed up are put into high mixer, mix 2 ~ 5 minutes, discharging, then uses twin screw extruder extruding pelletization; The processing temperature of described twin screw extruder is 230 ~ 240 DEG C, and forcing machine comprises nine warm areas, wherein one section 230 DEG C, two sections 230 DEG C, three sections 235 DEG C, four sections 235 DEG C, five sections 240 DEG C, six sections 240 DEG C, seven sections 235 DEG C, eight sections 235 DEG C, nine sections 230 DEG C, screw rod revolution is 30 ~ 40Hz.
the preparation (one) of embodiment 1 PBT/PET alloy material
The limiting viscosity of PBT is 1.0 dL/g, the limiting viscosity of PET is 1.0 dL/g, compound flame redundant by weight percent content be BPS 50%, the raw material of magnesium hypophosphite 25% and talcum powder 25% forms, glass fibre is the alkali free glass fibre of surface through silane coupling agent process, toughner is ethylene-methyl acrylate-glyceryl methacrylate random terpolymer, oxidation inhibitor is oxidation inhibitor 1330, and oxide compound is ferric oxide.
Each feed composition is taken: PBT 22.5%, PET 22.5%, compound flame redundant 20%, antimonous oxide 4%, glass fibre 20%, toughner 10%, oxidation inhibitor 0.1%, oxide compound 0.9% by following weight percent content.The each raw material weighed up is put into high mixer, and mix 2 minutes, discharging, then uses twin screw extruder extruding pelletization; The processing temperature of described twin screw extruder is 230 ~ 240 DEG C, and forcing machine comprises nine warm areas, wherein one section 230 DEG C, two sections 230 DEG C, three sections 235 DEG C, four sections 235 DEG C, five sections 240 DEG C, six sections 240 DEG C, seven sections 235 DEG C, eight sections 235 DEG C, nine sections 230 DEG C, screw rod revolution is 30Hz.
the preparation (two) of embodiment 2 PBT/PET alloy material
The limiting viscosity of PBT is 0.8 dL/g, the limiting viscosity of PET is 1.0 dL/g, compound flame redundant by weight percent content be BPS 50%, the raw material of magnesium hypophosphite 25% and talcum powder 25% forms, glass fibre is the alkali free glass fibre of surface through silane coupling agent process, toughner is ethylene-methyl acrylate-glyceryl methacrylate random terpolymer, oxidation inhibitor is antioxidant 1010, and oxide compound is ferric oxide.
Each feed composition is taken: PBT 41%, PET 23%, compound flame redundant 6%, antimonous oxide 3%, glass fibre 20%, toughner 5%, oxidation inhibitor 1%, oxide compound 1% by following weight percent content.The each raw material weighed up is put into high mixer, and mix 5 minutes, discharging, then uses twin screw extruder extruding pelletization; The processing temperature of described twin screw extruder is 230 ~ 240 DEG C, and forcing machine comprises nine warm areas, wherein one section 230 DEG C, two sections 230 DEG C, three sections 235 DEG C, four sections 235 DEG C, five sections 240 DEG C, six sections 240 DEG C, seven sections 235 DEG C, eight sections 235 DEG C, nine sections 230 DEG C, screw rod revolution is 35Hz.
the preparation (three) of embodiment 3 PBT/PET alloy material
The limiting viscosity of PBT is 1 dL/g, the limiting viscosity of PET is 0.8 dL/g, compound flame redundant by weight percent content be BPS 50%, the raw material of magnesium hypophosphite 25% and talcum powder 25% forms, toughner is ethylene-methyl acrylate copolymer, oxidation inhibitor is oxidation inhibitor 1330, and oxide compound is aluminum oxide.
Each feed composition is taken: PBT 23%, PET 23%, compound flame redundant 6%, antimonous oxide 15%, glass fibre 30%, toughner 2%, oxidation inhibitor 0.9%, oxide compound 0.1% by following weight percent content.The each raw material weighed up is put into high mixer, and mix 3 minutes, discharging, then uses twin screw extruder extruding pelletization; The processing temperature of described twin screw extruder is 230 ~ 240 DEG C, and forcing machine comprises nine warm areas, wherein one section 230 DEG C, two sections 230 DEG C, three sections 235 DEG C, four sections 235 DEG C, five sections 240 DEG C, six sections 240 DEG C, seven sections 235 DEG C, eight sections 235 DEG C, nine sections 230 DEG C, screw rod revolution is 40Hz.
the preparation (four) of embodiment 4 PBT/PET alloy material
The limiting viscosity of PBT is 1 dL/g, the limiting viscosity of PET is 1.0 dL/g, compound flame redundant by weight percent content be BPS 45%, the raw material of magnesium hypophosphite 30% and talcum powder 25% forms, glass fibre is the alkali free glass fibre of surface through silane coupling agent process, toughner is ethylene-methyl acrylate-glyceryl methacrylate random terpolymer, oxidation inhibitor is oxidation inhibitor 1330, and oxide compound is ferric oxide.
Each feed composition is taken: PBT 24%, PET 30%, compound flame redundant 18%, antimonous oxide 4%, glass fibre 20%, toughner 3%, oxidation inhibitor 0.8%, oxide compound 0.2% by following weight percent content.The each raw material weighed up is put into high mixer, and mix 4 minutes, discharging, then uses twin screw extruder extruding pelletization; The processing temperature of described twin screw extruder is 230 ~ 240 DEG C, and forcing machine comprises nine warm areas, wherein one section 230 DEG C, two sections 230 DEG C, three sections 235 DEG C, four sections 235 DEG C, five sections 240 DEG C, six sections 240 DEG C, seven sections 235 DEG C, eight sections 235 DEG C, nine sections 230 DEG C, screw rod revolution is 38Hz.
the preparation (five) of embodiment 5 PBT/PET alloy material
The limiting viscosity of PBT is 1.0 dl/g, the limiting viscosity of PET is 1.02dL/g, compound flame redundant by weight percent content be BPS 50%, the raw material of magnesium hypophosphite 25% and talcum powder 25% forms, glass fibre is the alkali free glass fibre of surface through silane coupling agent process, toughner is ethylene-methyl acrylate-glyceryl methacrylate random terpolymer, oxidation inhibitor is antioxidant 300, and oxide compound is ferric oxide.
Each feed composition is taken: PBT 23%, PET 41%, compound flame redundant 7%, antimonous oxide 3%, glass fibre 23%, toughner 2%, oxidation inhibitor 0.5%, oxide compound 0.5% by following weight percent content.The each raw material weighed up is put into high mixer, and mix 5 minutes, discharging, then uses twin screw extruder extruding pelletization; The processing temperature of described twin screw extruder is 230 ~ 240 DEG C, and forcing machine comprises nine warm areas, wherein one section 230 DEG C, two sections 230 DEG C, three sections 235 DEG C, four sections 235 DEG C, five sections 240 DEG C, six sections 240 DEG C, seven sections 235 DEG C, eight sections 235 DEG C, nine sections 230 DEG C, screw rod revolution is 30Hz.
the preparation (six) of embodiment 6 PBT/PET alloy material
The limiting viscosity of PBT is 1.0 dl/g, the limiting viscosity of PET is 1.0 dL/g, compound flame redundant by weight percent content be BPS 60%, the raw material of magnesium hypophosphite 20% and talcum powder 20% forms, toughner is ethylene-vinyl acetate copolymer, oxidation inhibitor is oxidation inhibitor 1330, and oxide compound is magnesium oxide.
Each feed composition is taken: PBT 30%, PET 30%, compound flame redundant 6%, antimonous oxide 3%, glass fibre 25%, toughner 5%, oxidation inhibitor 0.7%, oxide compound 0.3% by following weight percent content.The each raw material weighed up is put into high mixer, and mix 4 minutes, discharging, then uses twin screw extruder extruding pelletization; The processing temperature of described twin screw extruder is 230 ~ 240 DEG C, and forcing machine comprises nine warm areas, wherein one section 230 DEG C, two sections 230 DEG C, three sections 235 DEG C, four sections 235 DEG C, five sections 240 DEG C, six sections 240 DEG C, seven sections 235 DEG C, eight sections 235 DEG C, nine sections 230 DEG C, screw rod revolution is 40Hz.
the preparation (seven) of embodiment 7 PBT/PET alloy material
The limiting viscosity of PBT is 1.2 dl/g, the limiting viscosity of PET is 1.0 dL/g, compound flame redundant by weight percent content be BPS 50%, the raw material of magnesium hypophosphite 25% and talcum powder 25% forms, glass fibre is the alkali free glass fibre of surface through silane coupling agent process, toughner is ethylene-methyl acrylate-glyceryl methacrylate random terpolymer, oxidation inhibitor is oxidation inhibitor 1330, and oxide compound is ferric oxide.
Each feed composition is taken: PBT 22.5%, PET 22.5%, compound flame redundant 10%, antimonous oxide 9%, glass fibre 27%, toughner 8%, oxidation inhibitor 0.4%, oxide compound 0.6% by following weight percent content.The each raw material weighed up is put into high mixer, and mix 3 minutes, discharging, then uses twin screw extruder extruding pelletization; The processing temperature of described twin screw extruder is 230 ~ 240 DEG C, and forcing machine comprises nine warm areas, wherein one section 230 DEG C, two sections 230 DEG C, three sections 235 DEG C, four sections 235 DEG C, five sections 240 DEG C, six sections 240 DEG C, seven sections 235 DEG C, eight sections 235 DEG C, nine sections 230 DEG C, screw rod revolution is 35Hz.
It should be noted that, performance test is carried out to fiber glass reinforced PBT/PET alloy material that embodiment 1-7 obtains, adopt ASTM standard, test result shows: the PBT/PET alloy material of preparation has higher GWIT value and CTI value, and the flame retardant resistance of alloy material, tensile strength and flexural strength all meet the requirements.
embodiment 8 ~ 9 and comparative example 1 ~ 7
The limiting viscosity of PBT is the limiting viscosity of 1.0 dL/g, PET is 1.0 dL/g; Compound flame redundant by weight percent content be BPS 50%, the raw material of magnesium hypophosphite 25% and talcum powder 25% forms; Conventional flame retardant can be triphenylphosphate, TDE, decabromodiphynly oxide, magnesium hydroxide, red phosphorus etc., and the present invention all adopts TDE; Glass fibre is the alkali free glass fibre of surface through silane coupling agent process; Toughner is ethylene-methyl acrylate-glyceryl methacrylate random terpolymer; Oxidation inhibitor is oxidation inhibitor 1330; Oxide compound is ferric oxide.
Each feed composition is taken by the weight percent content (%) shown in table 1.The each raw material weighed up is put into high mixer, and mix 5 minutes, discharging, then uses twin screw extruder extruding pelletization; The processing temperature of described twin screw extruder is 230 ~ 240 DEG C, and forcing machine comprises nine warm areas, wherein one section 230 DEG C, two sections 230 DEG C, three sections 235 DEG C, four sections 235 DEG C, five sections 240 DEG C, six sections 240 DEG C, seven sections 235 DEG C, eight sections 235 DEG C, nine sections 230 DEG C, screw host revolution is 35Hz, and feeding revolution is 13 Hz.
Each composition of raw materials in table 1 embodiment 8 ~ 9 and comparative example 1 ~ 7
embodiment 10 performance test
Adopt ASTM standard, carry out performance test to the PBT/PET alloy material that embodiment 8 ~ 9, comparative example 1 ~ 7 prepare, test result is as shown in table 2.
The performance test results of table 2 alloy material
Associative list 1 and table 2, as seen from the table, the present invention adopts BACN compound system, compares with traditional conventional flame retardant, and novel built fire retardant effectively can improve the GWIT value of material; Adding of alkali free glass fibre can make the GWIT value of alloy material significantly improve, and toughner can improve the impact property of material; Ferric oxide has considerable influence to carrying high CTI value.
GWIT value and the CTI value of alloy material of the present invention are higher, flame retardant effect is better, alloy material environmental protection, over-all properties is balanced, can be widely used in the product of the field of electronics such as Low-voltage Electronic capacitor case, load break switch, carbon brush supports, breaker of plastic casing.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the prerequisite not departing from the inventive method; can also make some improvement and supplement, these improve and supplement and also should be considered as protection scope of the present invention.