CN104845184A - Flame-retardant and high-impact PET/PTT/carbon nanotube composite material - Google Patents
Flame-retardant and high-impact PET/PTT/carbon nanotube composite material Download PDFInfo
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- CN104845184A CN104845184A CN201410761690.2A CN201410761690A CN104845184A CN 104845184 A CN104845184 A CN 104845184A CN 201410761690 A CN201410761690 A CN 201410761690A CN 104845184 A CN104845184 A CN 104845184A
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Abstract
The invention discloses a flame-retardant and high-impact PET/PTT/carbon nanotube composite material, which comprises the following components in mass percentage: 25-50% of PET, 20-30% of PTT, 2-5% of modified carbon nanotubes, 2-4% of compatilizer, 8-12% of glass fibers, 5-8% of impact modifier, 1-3% of nano silica, 0.1-0.5% of anti-oxidant, 0.1-1% of lubricant and 6-10% of flame retardant. The impact modifier is composed of MBS/ACR. The flame retardant is a compound of bis-phenol A-bis (diphenyl phosphate), PDMS and polytetrafluoroethylene, wherein the mass ratio of the bis-phenol A-bis (diphenyl phosphate), the PDMS and the polytetrafluoroethylene is 5:4:1. According to the technical scheme of the invention, the flame-retardant and high-impact PET/PTT/carbon nanotube composite material integrates the original advantages of PET and PTT, and is excellent in heat-conductive, antistatic and flame-retardant properties at the same time. Meanwhile, the flame-retardant and high-impact PET/PTT/carbon nanotube composite material is high in notch impact strength, good in mechanical performance, low in cost, and wide in adaptability.
Description
Technical field
The present invention relates to technical field of polymer materials, specifically a kind of flame-retardant high-impact PET/PTT/ carbon nano tube compound material.
Background technology
Polyethylene terephthalate (PET)/Poly(Trimethylene Terephthalate) (PTT) belongs to a kind of novel plastic alloy material, it has excellent physicochemical property and processing characteristics, and cost is low, thus will have broad application prospects in automobile, electric, the field such as household electrical appliances, fiber.But the PET/PTT of non-modified exists the problem of poor fire, mechanical strength instability, this will strongly limit its effect and Application Areas.In order to obtain high performance PET/PTT alloy, often needing to add three components in PET/PTT, being intended to improve PET/PTT performance, with expansive approach field better.Carbon nanotube is as a kind of excellent heat conduction antistatic filler, with carbon nano-tube modification PET/PTT alloy, not only can improve the heat conduction antistatic performance of PET/PTT significantly, but also have and obviously promote the advantages such as the strength of materials, Young's modulus, thermotolerance, wear-resisting and antifatigue corrosive nature, thus there is good social effect and economic worth.
Summary of the invention
The object of the present invention is to provide the flame-retardant high-impact PET/PTT/ carbon nano tube compound material of a kind of high comprehensive performance and wide adaptability.
The technical solution adopted for the present invention to solve the technical problems is: a kind of flame-retardant high-impact PET/PTT/ carbon nano tube compound material, and its component by mass percent proportioning is: PET 25% ~ 50%, PTT 20% ~ 30%, modified carbon nano-tube 5% ~ 10%, compatilizer 2% ~ 4%, glass fibre 8% ~ 12%, impact modifier 5% ~ 8%, nano silicon 1% ~ 3%, oxidation inhibitor 0.1% ~ 0.5%, lubricant 0.1% ~ 1%, fire retardant 6% ~ 10%.
Described PET is polyethylene terephthalate.
Described PTT is Poly(Trimethylene Terephthalate).
Described modified carbon nano-tube be surface through preoxidation and the process of silane coupling agent activation modification and particle diameter in 0.5 ~ 200nm, length at the carbon nanotube of 5 ~ 20 μm.
Described compatilizer is ethylene-ethylacrylate-glycidyl methacrylate triblock copolymer.
Described glass fibre is the alkali-free short glass fiber of surface through silane coupling agent process.
Described impact modifier is the core-shell copolymerized thing of esters of acrylic acid, is selected from styrene-butadiene-methyl acrylic ester terpolymers MBS or Methylacrylate-Acrylate Copolymer ACR.
Described nano silicon is the aerosil nanoparticle of particle diameter at 20 ~ 40nm.
Described oxidation inhibitor is the one in the compound of antioxidant 1010, antioxidant 1076, antioxidant 1010 or antioxidant 1076 and irgasfos 168.
Described lubricant is modification ethylene bis-fatty acid amides.
Described fire retardant is the compound of dihydroxyphenyl propane-bis-(diphenyl phosphoester) of mass ratio 5:4:1, polydimethylsiloxane and tetrafluoroethylene.
The preparation method of above-mentioned a kind of flame-retardant high-impact PET/PTT/ carbon nano tube compound material, comprises the following steps:
(1), by PET and PTT in forced air circulation baking oven at 110 DEG C ~ 120 DEG C temperature dry 6 ~ 8 hours, fire retardant at 60 DEG C ~ 85 DEG C temperature dry 30 ~ 45 minutes, stand-by;
(2), by particle diameter at 0.5 ~ 200nm, length reaches in the mass content that the carbon nanotube of 5 ~ 20 μm is placed in volume ratio 3:1 the mixed acid solution that more than 98% sulfuric acid and mass content reach more than 60% nitric acid, under ultra-sonic oscillation and mechanical stirring, process 2 ~ 4h, then use a large amount of washed with de-ionized water to neutral, again the carbon nanotube obtained is placed in mass content 0.1% ~ 1% the deionized water solution ultrasonic disperse 2 ~ 4h of silane coupling agent, then filter, and by gained much filtrate in 120 DEG C ~ 150 DEG C vacuum drying oven drying 12 ~ 36h, obtain described modified carbon nano-tube,
(3) PTT and the fire retardant that, take drying by weight ratio add in super mixer, and add impact modifier, nano silicon, oxidation inhibitor, lubricant by weight ratio, make to be mixed together 3 ~ 5 minutes, after fully mixing, discharging adds twin screw extruder and melt extrudes pelletizing and dry, i.e. a kind of PTT composite master batch;
(4), taking dry PET by weight ratio adds in super mixer, add the obtained modified carbon nano-tube of step (2) and the obtained PTT composite master batch of step (3) again, and add compatilizer by weight ratio, make to be mixed together 3 ~ 5 minutes, after fully mixing, discharging adds the main spout of twin screw extruder, add described glass fibre by weight ratio from the side spout of twin screw extruder simultaneously, by twin screw extruder melting mixing 1 ~ 2 minute, screw speed controls at 150 ~ 500r/min, processing temperature is 210 DEG C ~ 280 DEG C scopes, then extruding pelletization, obtain a kind of flame-retardant high-impact PET/PTT/ carbon nano tube compound material of the present invention.
The invention has the beneficial effects as follows, the present invention have PET, PTT separately former advantageous while, also have excellent heat conduction antistatic performance and flame retardant properties, and notched Izod impact hit intensity is high, mechanical property is good, and cost is low, wide adaptability.
Embodiment
Technical scheme of the present invention is further illustrated below in conjunction with specific embodiment.
Embodiment 1:
A kind of flame-retardant high-impact PET/PTT/ carbon nano tube compound material, its component by mass percent proportioning is: PET 45%, PTT 20%, modified carbon nano-tube 10%, ethylene-ethylacrylate-glycidyl methacrylate triblock copolymer 3%, glass fibre 8%, MBS 5%, nano silicon 2.5%, antioxidant 1010 0.1%, modification ethylene bis-fatty acid amides 0.4%, fire retardant 6%, described modified carbon nano-tube is that surface is through preoxidation and the process of silane coupling agent activation modification, and particle diameter is at 0.5 ~ 200nm, length is at the carbon nanotube of 5 ~ 20 μm, described glass fibre is the alkali-free short glass fiber of surface through silane coupling agent process, described nano silicon is the aerosil nanoparticle of particle diameter at 20 ~ 40nm, described fire retardant is dihydroxyphenyl propane-bis-(diphenyl phosphoester) of mass ratio 5:4:1, the compound of polydimethylsiloxane and tetrafluoroethylene.
Preparation method: (1), by PET and PTT in forced air circulation baking oven at 110 DEG C ~ 120 DEG C temperature dry 6 ~ 8 hours, fire retardant at 60 DEG C ~ 85 DEG C temperature dry 30 ~ 45 minutes, stand-by, (2), by particle diameter at 0.5 ~ 200nm, length reaches in the mass content that the carbon nanotube of 5 ~ 20 μm is placed in volume ratio 3:1 the mixed acid solution that more than 98% sulfuric acid and mass content reach more than 60% nitric acid, under ultra-sonic oscillation and mechanical stirring, process 2 ~ 4h, then use a large amount of washed with de-ionized water to neutral, again the carbon nanotube obtained is placed in mass content 0.1% ~ 1% the deionized water solution ultrasonic disperse 2 ~ 4h of silane coupling agent, then filter, and by gained much filtrate in 120 DEG C ~ 150 DEG C vacuum drying oven drying 12 ~ 36h, obtain described modified carbon nano-tube, (3) PTT and the fire retardant that, take drying by weight ratio add in super mixer, and add MBS, nano silicon, antioxidant 1010, modification ethylene bis-fatty acid amides by weight ratio, make to be mixed together 3 ~ 5 minutes, after fully mixing, discharging adds twin screw extruder and melt extrudes pelletizing and dry, i.e. a kind of PTT composite master batch, (4), taking dry PET by weight ratio adds in super mixer, add the obtained modified carbon nano-tube of step (2) and the obtained PTT composite master batch of step (3) again, and add ethylene-ethylacrylate-glycidyl methacrylate triblock copolymer by weight ratio, make to be mixed together 3 ~ 5 minutes, after fully mixing, discharging adds the main spout of twin screw extruder, add described glass fibre by weight ratio from the side spout of twin screw extruder simultaneously, by twin screw extruder melting mixing 1 ~ 2 minute, screw speed controls at 150 ~ 500r/min, processing temperature is 210 DEG C ~ 280 DEG C scopes, then extruding pelletization, obtain a kind of flame-retardant high-impact PET/PTT/ carbon nano tube compound material of the present invention.
Embodiment 2:
A kind of flame-retardant high-impact PET/PTT/ carbon nano tube compound material, its component by mass percent proportioning is: PET 25%, PTT 30%, modified carbon nano-tube 8%, ethylene-ethylacrylate-glycidyl methacrylate triblock copolymer 3%, glass fibre 12%, ACR 8%, nano silicon 3%, the compound 0.5% of antioxidant 1076 and irgasfos 168, modification ethylene bis-fatty acid amides 0.5%, fire retardant 10%, described modified carbon nano-tube is that surface is through preoxidation and the process of silane coupling agent activation modification, and particle diameter is at 0.5 ~ 200nm, length is at the carbon nanotube of 5 ~ 20 μm, described glass fibre is the alkali-free short glass fiber of surface through silane coupling agent process, described nano silicon is the aerosil nanoparticle of particle diameter at 20 ~ 40nm, described fire retardant is dihydroxyphenyl propane-bis-(diphenyl phosphoester) of mass ratio 5:4:1, the compound of polydimethylsiloxane and tetrafluoroethylene.
Preparation method: (1), by PET and PTT in forced air circulation baking oven at 110 DEG C ~ 120 DEG C temperature dry 6 ~ 8 hours, fire retardant at 60 DEG C ~ 85 DEG C temperature dry 30 ~ 45 minutes, stand-by, (2), by particle diameter at 0.5 ~ 200nm, length reaches in the mass content that the carbon nanotube of 5 ~ 20 μm is placed in volume ratio 3:1 the mixed acid solution that more than 98% sulfuric acid and mass content reach more than 60% nitric acid, under ultra-sonic oscillation and mechanical stirring, process 2 ~ 4h, then use a large amount of washed with de-ionized water to neutral, again the carbon nanotube obtained is placed in mass content 0.1% ~ 1% the deionized water solution ultrasonic disperse 2 ~ 4h of silane coupling agent, then filter, and by gained much filtrate in 120 DEG C ~ 150 DEG C vacuum drying oven drying 12 ~ 36h, obtain described modified carbon nano-tube, (3) PTT and the fire retardant that, take drying by weight ratio add in super mixer, and add compound, the modification ethylene bis-fatty acid amides of ACR, nano silicon, antioxidant 1076 and irgasfos 168 by weight ratio, make to be mixed together 3 ~ 5 minutes, after fully mixing, discharging adds twin screw extruder and melt extrudes pelletizing and dry, i.e. a kind of PTT composite master batch, (4), taking dry PET by weight ratio adds in super mixer, add the obtained modified carbon nano-tube of step (2) and the obtained PTT composite master batch of step (3) again, and add ethylene-ethylacrylate-glycidyl methacrylate triblock copolymer by weight ratio, make to be mixed together 3 ~ 5 minutes, after fully mixing, discharging adds the main spout of twin screw extruder, add described glass fibre by weight ratio from the side spout of twin screw extruder simultaneously, by twin screw extruder melting mixing 1 ~ 2 minute, screw speed controls at 150 ~ 500r/min, processing temperature is 210 DEG C ~ 280 DEG C scopes, then extruding pelletization, obtain a kind of flame-retardant high-impact PET/PTT/ carbon nano tube compound material of the present invention.
Claims (10)
1. a flame-retardant high-impact PET/PTT/ carbon nano tube compound material, it is characterized in that, its component by mass percent proportioning is: PET 25% ~ 50%, PTT 20% ~ 30%, modified carbon nano-tube 5% ~ 10%, compatilizer 2% ~ 4%, glass fibre 8% ~ 12%, impact modifier 5% ~ 8%, nano silicon 1% ~ 3%, oxidation inhibitor 0.1% ~ 0.5%, lubricant 0.1% ~ 1%, fire retardant 6% ~ 10%.
2. a kind of flame-retardant high-impact PET/PTT/ carbon nano tube compound material according to claim 1, it is characterized in that, described modified carbon nano-tube be surface through preoxidation and the process of silane coupling agent activation modification and particle diameter in 0.5 ~ 200nm, length at the carbon nanotube of 5 ~ 20 μm.
3. a kind of flame-retardant high-impact PET/PTT/ carbon nano tube compound material according to claim 1, is characterized in that, described compatilizer is ethylene-ethylacrylate-glycidyl methacrylate triblock copolymer.
4. a kind of flame-retardant high-impact PET/PTT/ carbon nano tube compound material according to claim 1, is characterized in that, described glass fibre is the alkali-free short glass fiber of surface through silane coupling agent process.
5. a kind of flame-retardant high-impact PET/PTT/ carbon nano tube compound material according to claim 1, it is characterized in that, described impact modifier is the core-shell copolymerized thing of esters of acrylic acid, is selected from MBS or ACR.
6. a kind of flame-retardant high-impact PET/PTT/ carbon nano tube compound material according to claim 1, is characterized in that, described nano silicon is the aerosil nanoparticle of particle diameter at 20 ~ 40nm.
7. a kind of flame-retardant high-impact PET/PTT/ carbon nano tube compound material according to claim 1, it is characterized in that, described oxidation inhibitor is the one in the compound of antioxidant 1010, antioxidant 1076, antioxidant 1010 or antioxidant 1076 and irgasfos 168.
8. a kind of flame-retardant high-impact PET/PTT/ carbon nano tube compound material according to claim 1, is characterized in that, described lubricant is modification ethylene bis-fatty acid amides.
9. a kind of flame-retardant high-impact PET/PTT/ carbon nano tube compound material according to claim 1, it is characterized in that, described fire retardant is the compound of dihydroxyphenyl propane-bis-(diphenyl phosphoester) of mass ratio 5:4:1, polydimethylsiloxane and tetrafluoroethylene.
10. the preparation method of a kind of flame-retardant high-impact PET/PTT/ carbon nano tube compound material according to claim 1, is characterized in that, comprise the following steps:
(1), by PET and PTT in forced air circulation baking oven at 110 DEG C ~ 120 DEG C temperature dry 6 ~ 8 hours, fire retardant at 60 DEG C ~ 85 DEG C temperature dry 30 ~ 45 minutes, stand-by;
(2), by particle diameter at 0.5 ~ 200nm, length reaches in the mass content that the carbon nanotube of 5 ~ 20 μm is placed in volume ratio 3:1 the mixed acid solution that more than 98% sulfuric acid and mass content reach more than 60% nitric acid, under ultra-sonic oscillation and mechanical stirring, process 2 ~ 4h, then use a large amount of washed with de-ionized water to neutral, again the carbon nanotube obtained is placed in mass content 0.1% ~ 1% the deionized water solution ultrasonic disperse 2 ~ 4h of silane coupling agent, then filter, and by gained much filtrate in 120 DEG C ~ 150 DEG C vacuum drying oven drying 12 ~ 36h, obtain described modified carbon nano-tube,
(3) PTT and the fire retardant that, take drying by weight ratio add in super mixer, and add impact modifier, nano silicon, oxidation inhibitor, lubricant by weight ratio, make to be mixed together 3 ~ 5 minutes, after fully mixing, discharging adds twin screw extruder and melt extrudes pelletizing and dry, i.e. a kind of PTT composite master batch;
(4), taking dry PET by weight ratio adds in super mixer, add the obtained modified carbon nano-tube of step (2) and the obtained PTT composite master batch of step (3) again, and add compatilizer by weight ratio, make to be mixed together 3 ~ 5 minutes, after fully mixing, discharging adds the main spout of twin screw extruder, add described glass fibre by weight ratio from the side spout of twin screw extruder simultaneously, by twin screw extruder melting mixing 1 ~ 2 minute, screw speed controls at 150 ~ 500r/min, processing temperature is 210 DEG C ~ 280 DEG C scopes, then extruding pelletization, obtain a kind of flame-retardant high-impact PET/PTT/ carbon nano tube compound material of the present invention.
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| CN115785624A (en) * | 2021-09-13 | 2023-03-14 | 南亚塑胶工业股份有限公司 | Conductive polyester composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115785624A (en) * | 2021-09-13 | 2023-03-14 | 南亚塑胶工业股份有限公司 | Conductive polyester composition |
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Application publication date: 20150819 |