Enhancing polyethylene terephthalate engineering plastics of halogen-free high flame-retardant performance and preparation method thereof
Technical field
The present invention relates to enhancing polyethylene terephthalate engineering plastics of a kind of halogen-free high flame-retardant performance and preparation method thereof, belong to the modified engineered plastic technical field.
Background technology
Polyethylene terephthalate (PET) is one of topmost kind in the thermoplastic polyester.Have advantages such as good mechanical performance, electrical insulation capability, chemical proofing, and a low price, therefore widespread usage in life not only also begins a large amount of uses in industry.Along with the fast development of China's engineering plastics, the PET plastics have become the fifth-largest engineering plastics after nylon, polycarbonate, polyoxymethylene, polyphenylene oxide, and its demand increases year by year in recent years.PET can be used for industries such as electric appliance and electronic, automobile, machinery, home appliances, electrical equipment as engineering plastics, and these industries have strict requirement to material combustion and safety performance, and the flame retardant properties that therefore improves PET is one of basic demand of PET engineering plastics application.Improving effective, the most economic means of PET flame retardant properties is to add fire retardant.The halogen-free flame retardants that is used for matrix material should possess following performance: the flame retarding efficiency height, and can give matrix material good flame retardancy; Has good intermiscibility, can be in the PET matrix uniform and stable dispersion; Decomposition temperature is higher; Nontoxic pollution-free; Good endurance etc.
In halogen-free flame retardants, red phosphorus is a kind of fire retardant preferably, has advantages such as addition is few, purposes is wide.But red phosphorus combustion inhibitor is darker reddish-brown or red-purple under normal conditions, and this has limited the scope of its use greatly.Development along with red phosphorus combustion inhibitor, the exploitation of whiteness microcapsule red phosphorus fire retardant, overcome the limits of color that red phosphorus combustion inhibitor is used in material, have, in use not general red, advantage such as addition few, flame retarding efficiency high, toxicity little good, be suitable for the production of begin-color flame-proof PET engineering plastics with resin compatible.The exploitation of nano inorganic powder receives much concern nanocomposite applications recently in flame-retarded technology, and polynite is as a class natural clay mineral of China high yield receiving publicity gradually.Its nano composite material is the most potential class nano composite material in current numerous inorganic nano particle modified matrix materials, has excellent flame-retardant, mechanical property, thermal characteristics and other physicalies.In view of the premium properties of red phosphorus and polynite, the present invention adopts whiteness microcapsule red phosphorus and modified Nano polynite to prepare the PET engineering plastics with high flame resistance as composite flame-retardant agent.
Summary of the invention
The object of the present invention is to provide a kind of enhancing polyethylene terephthalate engineering plastics of halogen-free high flame-retardant performance.
Another object of the present invention is to provide a kind of preparation method of enhancing polyethylene terephthalate engineering plastics of halogen-free high flame-retardant performance.
For achieving the above object, the present invention adopts following technical proposals:
A kind of enhancing polyethylene terephthalate engineering plastics of halogen-free high flame-retardant performance is characterized in that its composition counts by weight:
(1) polyethylene terephthalate is 50~80 parts
(2) compound flame retardant is 1~20 part
(3) toughener is 20~40 parts
(4) nucleator is 1~5 part
(5) lubricant is 0.1~0.5 part
(6) compound antioxidant is 0.1~0.5 part
(7) toughner is 1~5 part
(8) expanding material is 5~15 parts
(9) chainextender is 0.1~2 part
In the above-mentioned prescription, compound flame retardant is the mixture of red phosphorus and polynite, and red phosphorus is whiteness microcapsule red phosphorus, and polynite is the polynite of modified Nano level, and the weight ratio of red phosphorus and polynite is 1~4: 1.Toughener is a kind of in unmodified alkali-free long glass fibres, unmodified alkali-free short glass fiber, organically-modified long glass fibres and the organically-modified short glass fiber.Nucleator is one or more in talcum, mica, lime carbonate, the nano-sized magnesium hydroxide, and wherein lime carbonate, nano-sized magnesium hydroxide are through surface modification treatment.Lubricant is pentaerythritol stearate (PETS).
The enhancing polyethylene terephthalate engineering plastics of described halogen-free high flame-retardant performance, it is characterized in that described compound antioxidant be Irganox 245 and Irganox 1010 weight ratios be 1: 1 mixture; Described toughner is one or more among MBS, EVA, the ABS; Described expanding material is one or more among POE-g-MAH, PPO-g-MAH, the PP-g-MAH.Described chainextender is equal benzene dianhydride (PMDA), Pyrogentisinic Acid's dihydroxyl ether (HQEE), 1, and the 4-butyleneglycol (1,4-BD), 3,3 '-two chloro-4, one or more in 4 '-diamino-ditan (MOCA).
The preparation method who is used for the enhancing polyethylene terephthalate engineering plastics of halogen-free high flame-retardant performance, its technological process is as follows: the polyethylene terephthalate master batch that drying is good, fire retardant, nucleator, lubricant, oxidation inhibitor, toughner and chainextender auxiliary agent are in high-speed mixer behind the thorough mixing, add in the twin screw extruder, when melt extruding, second charging opening adding glass at twin screw melt extrudes, the temperature of forcing machine is set at 240~275 ℃ of scopes, head temperature is 250~260 ℃, vacuum tightness is-0.08Pa extruding pelletization; Extruded material after the drying, promptly gets the enhancing polyethylene terephthalate engineering plastics of halogen-free high flame-retardant performance through cooling, air-dry, pelletizing.
Fire retardant mechanism relevant among the present invention is as follows:
1. red phosphorus: red phosphorus flame-retardant is effective, and usage quantity is less.When burning took place, frosting took fire, and red phosphorus generates phosphoric acid, condensed into solid phosphoric acid and the hydrogen of incendiary frosting and oxygen was removed and plastics are transformed into carbon-coating.
2. polynite: polynite not only can with the compound nano composite material of producing high physicals of polymer, and give product good flame performance.Its fire retardant mechanism is to have good promotion material and becomes carbon, and heat insulation fire insulation stops burning.It is a kind of fire-retardant collaborative auxiliary agent of very potential and superior performance.Almost can have good synergism, flame retardant properties is significantly improved with all organic and inorganic fire retardants.
These PET engineering plastics have excellent flame-retardant, low warpage, high-modulus, high heat-resisting and high impact property.And have low cigarette, nontoxic, flame propagation velocity is slow, flame retardant properties reaches characteristics such as UL 94 V-0 levels.In addition, this project plastics are owing to adopted whiteness microcapsule red phosphorus, and its color is more shallow, can add the desired toner of product arbitrarily in the middle of the process of using, thereby have wide development and application prospect.Can be used for fields such as electronics, electric, automobile.
Embodiment
In conjunction with following specific embodiment, the present invention is described in further detail.
Embodiment 1
PET master batch dry 10h in 100 ℃ of vacuum drying ovens with 2kg; Take by weighing the alkali-free short glass fiber of 600g with the modification of KH550 organo silane coupling agent; Take by weighing 100g whiteness microcapsule red phosphorus and the polynite of 60g nano modification; Take by weighing the 10g talcum; Take by weighing 6g PETS; Take by weighing 3g Irganox 245 and 3g Irganox1010; 60gABS; 200gPOE-g-MAH; The equal benzene dianhydride of 10g; With various auxiliary agents dry 3h in 60 ℃ vacuum drying oven.Various auxiliary agents and PET master batch except glass are mixed in high-speed mixer, be added in first charging opening adding that twin screw is extruded, glass adds at second charging opening of twin screw extruder, melt extrudes.The temperature of twin screw extruder heating zone (℃) be set at: a district 240; Two districts 245; Three districts 250; Four districts 255; Five districts 260; Six districts 260; Seven districts 260; Eight districts 260; Nine districts 260; The head Heating temperature (℃): 250, vacuum tightness-0.08Pa.Extruding pelletization; Extruded material after the drying, promptly gets the enhancing polyethylene terephthalate engineering plastics of halogen-free high flame-retardant performance through cooling, air-dry, pelletizing.
Embodiment 2
PET master batch dry 4h in 120 ℃ of vacuum drying ovens with 3kg; Take by weighing the alkali-free roving glass fiber of 880gKH570 organo silane coupling agent modification; Take by weighing 120g whiteness microcapsule red phosphorus and the polynite of 40g nano modification; Take by weighing the 12g talcum; Take by weighing 9gPETS; Take by weighing 4.5g Irganox 245 and 4.5g Irganox1010; 150gABS; 220gPOE-g-MAH; 20g 3,3 '-two chloro-4,4 '-diamino-ditan (MOCA); With various auxiliary agents dry 12h in 60 ℃ vacuum drying oven.Various auxiliary agents and PET master batch except glass are mixed in high-speed mixer, be added in first charging opening adding that twin screw is extruded, glass adds at second charging opening of twin screw extruder, melt extrudes.The temperature of twin screw extruder heating zone (℃) be set at: a district 245; Two districts 250; Three districts 255; Four districts 260; Five districts 265; Six districts 270; Seven districts 265; Eight districts 260; Nine districts 255; The head Heating temperature (℃): 255, vacuum tightness-0.08Pa.Extruding pelletization; Extruded material after the drying, promptly gets the enhancing polyethylene terephthalate engineering plastics of halogen-free high flame-retardant performance through cooling, air-dry, pelletizing.
Embodiment 3
PET master batch dry 5h in 100 ℃ of vacuum drying ovens with 2Kg; Take by weighing the roving glass fiber of 700g with the modification of KH550 organo silane coupling agent; Take by weighing 150g whiteness microcapsule red phosphorus and the polynite of 40g nano modification; Take by weighing the 10g talcum; Take by weighing 6gPETS; Take by weighing 3g Irganox 245 and 3g Irganox1010; 100gEVA; 200gPPO-g-MAH; 6g Pyrogentisinic Acid dihydroxyl ether (HQEE); With whiteness microcapsule red phosphorus, nano modification polynite, talcum dry 3h in 80 ℃ vacuum drying oven, all the other auxiliary agents are dry 2h in 60 ℃ vacuum drying oven.Various auxiliary agents and PET master batch except glass are mixed in high-speed mixer, and feed intake at first charging opening that twin screw is extruded, glass adds at second charging opening of twin screw extruder, melt extrudes.The temperature of twin screw extruder heating zone (℃) be set at: a district 240; Two districts 245; Three districts 250; Four districts 255; Five districts 260; Six districts 260; Seven districts 260; Eight districts 260; Nine districts 260; The head Heating temperature (℃): 250, vacuum tightness-0.08Pa.Extruding pelletization; Extruded material after the drying, promptly gets the enhancing polyethylene terephthalate engineering plastics of halogen-free high flame-retardant performance through cooling, air-dry, pelletizing.
Embodiment 4
PET master batch dry 10h in 120 ℃ of vacuum drying ovens with 3kg; Take by weighing the alkali-free short glass fiber of 880gKH570 organo silane coupling agent modification; Take by weighing 180g whiteness microcapsule red phosphorus and the polynite of 60g nano modification; Take by weighing the 12g talcum; Take by weighing 9gPETS; Take by weighing 4.5g Irganox 245 and 4.5g Irganox1010; 90gABS; 20geEVA; 300gPP-g-MAH; 30g1, and the 4-butyleneglycol (1,4-BD); Alkali-free short glass fiber, whiteness microcapsule red phosphorus, nano modification polynite dry 5h in 80 ℃ vacuum drying oven with the organo silane coupling agent modification; All the other auxiliary agents are dry 2h in 50 ℃ vacuum drying oven.Various auxiliary agents and PET master batch except glass are mixed in high-speed mixer, be added in first charging opening adding that twin screw is extruded, glass adds at second charging opening of twin screw extruder, melt extrudes.The temperature of twin screw extruder heating zone (℃) be set at: a district 245; Two districts 250; Three districts 255; Four districts 260; Five districts 265; Six districts 270; Seven districts 265; Eight districts 260; Nine districts 255; The head Heating temperature (℃): 255, vacuum tightness-0.08Pa.Extruding pelletization; Extruded material after the drying, promptly gets the enhancing polyethylene terephthalate engineering plastics of halogen-free high flame-retardant performance through cooling, air-dry, pelletizing.
Embodiment 5
PET master batch dry 6h in 120 ℃ of vacuum drying ovens with 2Kg; Take by weighing the short fiber of 400g with the modification of KH550 organo silane coupling agent; Take by weighing 80g whiteness microcapsule red phosphorus and the polynite of 60g nano modification; Take by weighing the 10g talcum; Take by weighing 6gPETS; Take by weighing 3g Irganox 245 and 3g Irganox1010; 100gABS; 100gPOE-g-MAH; 100gPP-g-MAH; The equal benzene dianhydride of 10g; 10g 3,3 '-two chloro-4,4 '-diamino-ditan (MOCA).Alkali-free short glass fiber, whiteness microcapsule red phosphorus, nano modification polynite dry 4h in 80 ℃ vacuum drying oven with the organo silane coupling agent modification; All the other auxiliary agents are dry 2h in 50 ℃ vacuum drying oven.Various auxiliary agents and PET master batch except glass are mixed in high-speed mixer, be added in first charging opening adding that twin screw is extruded, glass adds at second charging opening of twin screw extruder, melt extrudes.The temperature of twin screw extruder heating zone (℃) be set at: a district 240; Two districts 245; Three districts 250; Four districts 255; Five districts 260; Six districts 260; Seven districts 260; Eight districts 260; Nine districts 260; The head Heating temperature (℃): 250, vacuum tightness-0.08Pa.Extruding pelletization; Extruded material after the drying, promptly gets the enhancing polyethylene terephthalate engineering plastics of halogen-free high flame-retardant performance through cooling, air-dry, pelletizing.
The product of preparing according to the method described above, through carrying out performance test after the injection moulding:
Test event |
Testing method |
Unit |
Embodiment 1 |
Embodiment 2 |
Tensile strength |
ASTM?D?638 |
MPa |
115 |
135 |
Modulus in flexure |
ASTM?D?790 |
MPa |
9800 |
10300 |
Flexural strength |
ASTM?D?790 |
MPa |
180 |
190 |
The cantilever notched Izod impact strength |
ASTM?D?256 |
J/m |
80 |
90 |
Flame retardant rating |
UL-94 |
- |
V-0 |
V-0 |
Oxygen index |
ASTM?D?2863 |
% |
29 |
31 |
The foregoing description for explanation technical conceive of the present invention and characteristics, is not in order to limit claim of the present invention only.All equivalences that spirit is done according to the present invention change or improve, and all should be included within protection scope of the present invention.