CN101265348B - Nano barium tungstate synergism expansibility flame-proof polypropylene and preparation method thereof - Google Patents
Nano barium tungstate synergism expansibility flame-proof polypropylene and preparation method thereof Download PDFInfo
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- CN101265348B CN101265348B CN2008100255734A CN200810025573A CN101265348B CN 101265348 B CN101265348 B CN 101265348B CN 2008100255734 A CN2008100255734 A CN 2008100255734A CN 200810025573 A CN200810025573 A CN 200810025573A CN 101265348 B CN101265348 B CN 101265348B
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Abstract
The invention discloses a nanometer barium tungstate synergistic intumescent flame-retardant polypropylene and a preparation method thereof. The nanometer barium tungstate synergistic expandable flame-retardant polypropylene is prepared by polypropylene granules accounting for 60 to 80 percent by mass, neopentyl glycol phosphate melamine salt as a mono-component intumescent flame retardant accounting for 19.5 to 35 percent by mass, and a nanometer flame retardant synergistic agent accounting for 0.5 to 5 by mass through the steps of mixing at high speed, extrusion and granulation. The method for preparing the flame-retardant polypropylene is simple with high flame retardant efficiency. A compact coal layer is formed on the surface of the material during combustion, which insulates heat, oxygen, and prevents flame from spreading. Little fume and much coal are produced. The flame-retardant polypropylene and the preparation procedure are innoxious, and do little harm to human bodies and the environment with low pollution level.
Description
Technical field
The invention belongs to the flame-retarded technology of polypropylene material, particularly a kind of nano barium tungstate synergism expansibility flame-proof polypropylene and preparation method.
Background technology
Polypropylene (PP) is a kind of thermoplastics of excellent property, has at aspects such as automotive industry, household electrical appliance, electronics, packing and building materials furniture widely to use, and its tempo occupies first of the various general-purpose plastics always.Global polyacrylic overall throughput was about 4,208 ten thousand t/a in 2004, year increased approximately 6.0%, and aggregate consumption reaches 3925.9 ten thousand t/a, predicts that global overall throughput in 2010 will reach 6,100 ten thousand t/a.The polyacrylic output of China is about 474.9 ten thousand t/a, and about 764.7 ten thousand t/a of apparent consumption predict that domestic apparent consumption in 2010 will reach about 1,160 ten thousand t/a.Polyacrylic oxygen index generally between 17%～19%, can continue spontaneous combustion behind fire, belong to inflammable material.Along with the continuous developing of polyacrylic Application Areas and the continuous increase of number of applications, the fire hazard that brings thus is also increasing, and it is very important and necessary therefore giving the polypropylene material flame retardant properties.Particularly in Application Areass such as automotive industry, electric industry and textiles industry, more and more higher to the requirement of polyacrylic flame retardant properties.According to the data from abroad report, because the inexpensive and superior performance of PP, the PP part that uses on the market has accounted for 42% of the plastic paste market share now, and is expected the speed increment with annual 8%.
Anti-flaming polypropylene material is the same with other most of flame retardant plastics, is just experiencing the progressively evolution of Halogen-low halogen-Halogen.Along with the application of Halogen fire retardant material progressively is restricted, impel people actively to seek can be used for polyacrylic Halogen, low cigarette, low toxicity and environment amenable new and effective flame retardant systems.In recent years, low halogen such as the fire-retardant PP of inorganic combustion inhibitor, the fire-retardant PP of organophosphorous fire retardant, nano flame retardant PP, the development of Halogen material are rapidly.Particularly the halogen-free expansion type flame-proof polypropylene material receives much attention, because synergy and synergy between its phosphorus-nitrogen element make this class fire retardant material have good flame retardancy, and the amount of being fuming are little, Poisonous Gas is also less, is considered to one of main developing direction of fire retardant material from now on.
Continuous development along with fire-retardantization of high polymer material treatment technology, requirement to the over-all properties of fire retardant is also more and more higher, should reach the fire-retardant rank of regulation, good physical mechanical strength, non-corrosibility, low cigarette, nontoxicity and thermostability etc. also will be arranged.Bigger fire retardant particle can damage the physical and mechanical properties of material, fire retardant miniaturization, nanometer, and the contact area that both can increase fire retardant and material can reduce the consumption of fire retardant again to improve consistency.Nanometer is the main direction of studying of inorganic combustion inhibitor exploitation.
Fire retarding synergist is main flame retardant to be played synergistic auxiliary agents such as catalysis or synergy, and its addition is generally lower, usually between O.1%～5%.Metallic compound obtains further investigation as fire retarding synergist in the Halogen flame-retardant system, the synergistic effect between phosphonium flame retardant and the metal oxide also has report, but the report of using in the expandable flame retardant system seldom.Lewin etc. have studied zinc, manganic compound and nano metal powder in APP/PER expandable flame retardant system catalysis synergistic effect (Lewin, Menachem, Endo, Makoto.Polymers for Advanced Technologies, 2003,14 (1): 3-11).Systematic studyes such as Tian Chunming zinc oxide, manganese oxide and the rare earth oxide synergy in the expanded flame-retardant polypropylene system.Experimental result shows, adds 1% ZnO, MnO
2, TiO
2, ZrO
2, CdO can make the oxygen index of the fire-retardant PP material of APP/PER improve 5%, 3.5%, 3.5%, 2.5%, 3.0% respectively, and surplus charcoal rate increases to some extent, the thermostability of degraded resistates is improved.Simultaneously, the adding of metal oxide makes thermal degradation process apparent activation energy Ea rise to some extent, and to esterification and become the charcoal reaction have obvious catalysis (Tian Chunming thanks to the lucky star. University Of Shanxi's journal, 26 (3): 231-234).Lin Xiaodan etc. have studied the cooperative flame retardant effect of zinc borate in expansion type inflaming retarding polypropylene, and have analyzed cooperative flame retardant mechanism.The result shows the oxygen index that can significantly increase expansion type inflaming retarding polypropylene (PP) when consumption hangs down that is added in of zinc borate, and after consumption surpasses certain value, then sharply reduction of oxygen index (Lin Xiaodan, the Judd people. plastics industry, 2002,30 (2): 41-42).
At present, people do not understand as yet fully to synergy mechanism in the flame-retardant system, and its reason is that the cooperation mechanism of various synergists has nothing in common with each other.But the common synergist to weisspiessglanz, zinc oxide, zinc borate and so on has more consistent view.This class synergist stops burning by catch free radical in gas phase on the one hand; They can promote material surface to form compact carbon layer in condensed phase on the other hand, and heat insulation, oxygen barrier stops the further propagation of flame, and this point is one of cooperative flame retardant mechanism of many synergists in the expandable flame retardant system just.People have found a series of novel synergist in the process of research expandable flame retardant system at present, though synergistic mechanism is not quite similar, can both significantly improve the flame retardant properties of fire retardant material.It is broadly divided into into charcoal synergist (as Mierocrystalline cellulose, PA etc.) and catalysis synergist (as metal oxide, zeolite, tungstosilicic acid etc.) two classes.
Summary of the invention
The object of the present invention is to provide a kind of nano barium tungstate synergism expansibility flame-proof polypropylene, not only can satisfy the required flame retardant properties of material, and burning back material surface forms compact carbon layer, heat insulation, oxygen barrier, stop the further propagation of flame, low-smoke, high neat coal amout, nontoxicity is low to the harm and the pollution level of human body and environment.
Another object of the present invention provides a kind of preparation method of above-mentioned nano barium tungstate synergism expansibility flame-proof polypropylene.
The technical solution that realizes the object of the invention is: a kind of nano barium tungstate synergism expansibility flame-proof polypropylene, by polypropylene granules, mix and form as the neopentyl glycol phosphoric acid fat melamine salt of single component expansion type flame retardant, nano flame retardant synergist, wherein fire retarding synergist is a nano barium tungstate, and the mass percent of polypropylene granules, neopentyl glycol phosphoric acid fat melamine salt and nano barium tungstate is 60～80: 19.5～35: 0.5～5.
The present invention compared with prior art, its remarkable advantage: among (1) expansion type flame-retarding PP, the increase of expansion type flame retardant addition can improve the oxygen index of system, but after addition surpasses to a certain degree, not only the flame retardant properties of system improves and to be tending towards slowly, and addition is crossed and may well be caused declining to a great extent of system mechanical property and processing characteristics.The present invention adds a spot of nano flame retardant synergist in system, in the flame retardant properties that improves system simultaneously, guarantee that the physics, mechanical property etc. of fire-retardant PP are not affected substantially.(2) use the single component expansion type flame retardant, main design philosophy is the synergy of utilizing between phosphorus-nitrogen element, and the carbon-collecting source that synthetic thermostability and polymer phase coincide, acid source, source of the gas are in the unit molecule compound of one.(3) single component expansion type flame retardant neopentyl glycol phosphoric acid fat melamine salt and polypropylene have good consistency.(4) fire retarding synergist is a nano barium tungstate, and nanometer had both increased the contact area of fire retardant and material to improve consistency, can reduce the consumption of fire retardant again, had improved collaborative efficient.(5) fire retarding synergist is a nano barium tungstate, it can form the compound of heteropolyacid formula in combustion processes, and can form chemical bonds such as M-O-P, thereby energy catalytic esterification and the reaction of one-tenth charcoal in combustion processes, participate in forming charcoal layer, so the efficient height with big foam structure, densification, good stability.(6) employed single component expansion type flame retardant neopentyl glycol phosphoric acid fat melamine salt and fire retarding synergist nano barium tungstate do not produce secondary pollution, its Heat stability is good, nontoxic, non-volatile when burning.The foam carbide that generates when (7) burning forms thermofin, and big foam structure, densification, good stability appear in thermofin.(8) toxicity is low, and itself does not produce deleterious halogen gas; The amount of being fuming is low during burning, CO and CO in the time of suppressing burning
2Generation.(9) prescription, technology is simple, the flame retarding efficiency height.
Below in conjunction with accompanying drawing the present invention is described in further detail.
Description of drawings
Fig. 1 is a nano barium tungstate pattern synoptic diagram.
Fig. 2 is a nano barium tungstate crystal phase structure graphic representation.
Embodiment
Nano barium tungstate synergism expansibility flame-proof polypropylene of the present invention is by polypropylene granules, mix and form as the neopentyl glycol phosphoric acid fat melamine salt of single component expansion type flame retardant, nano flame retardant synergist.The single component expansion type flame retardant is a neopentyl glycol phosphoric acid fat melamine salt, is a white powder.Structure is as follows:
Wherein, fire retarding synergist is a nano barium tungstate.Nano barium tungstate is thread, its pattern and crystal phase structure such as Fig. 1 and Fig. 2.
Nano barium tungstate synergism expansibility flame-proof polypropylene preparation method of the present invention is as follows: be 60～80: 19.5～35 by mass percentage: 0.5～5 with the polypropylene powder pellet, single component expansion type flame retardant neopentyl glycol phosphoric acid fat melamine salt, fire retarding synergist nano barium tungstate high-speed mixing and extruding pelletization.In order to understand better and to implement, describe the preparation process of nano barium tungstate synergism expansibility flame-proof polypropylene of the present invention in detail below in conjunction with comparative example and embodiment.
Comparative example: take by weighing polypropylene powder pellet 650 grams, single component expansion type flame retardant neopentyl glycol phosphoric acid fat melamine salt 350 grams, above-mentioned pellet combination treatment in high-speed mixer is good, under the condition of feed rate, temperature and the screw speed of routine, add twin screw extruder, through extrude, cooling, pelletizing, make expansibility flame-proof polypropylene.Do not adding under the fire retarding synergist situation, carrying out the determination limit oxygen index by GB/T 2406-93 standard test methods is 23.8%, by the thermal weight loss testing method, at 600 ℃ of charring rates 3%.
Embodiment 1: take by weighing polypropylene powder pellet 650 grams, single component expansion type flame retardant neopentyl glycol phosphoric acid fat melamine salt 340 grams, fire retarding synergist nano barium tungstate 10 grams, above-mentioned pellet combination treatment in high-speed mixer is good, under the condition of feed rate, temperature and the screw speed of routine, add twin screw extruder, through extrude, cooling, pelletizing, make nano barium tungstate synergism expansibility flame-proof polypropylene of the present invention.29.8%, 600 ℃ of charring rate 10.5% of limiting oxygen index(LOI).
Embodiment 2: take by weighing polypropylene powder pellet 700 grams, single component expansion type flame retardant neopentyl glycol phosphoric acid fat melamine salt 290 grams, fire retarding synergist nano barium tungstate 10 grams, above-mentioned pellet combination treatment in high-speed mixer is good, under the condition of feed rate, temperature and the screw speed of routine, add twin screw extruder, through extrude, cooling, pelletizing, make nano barium tungstate synergism expansibility flame-proof polypropylene of the present invention.31.2%, 600 ℃ of charring rate 13.5% of limiting oxygen index(LOI).
Embodiment 3: take by weighing polypropylene powder pellet 750 grams, single component expansion type flame retardant neopentyl glycol phosphoric acid fat melamine salt 245 grams, fire retarding synergist nano barium tungstate 5 grams, above-mentioned pellet combination treatment in high-speed mixer is good, under the condition of feed rate, temperature and the screw speed of routine, add twin screw extruder, through extrude, cooling, pelletizing, make nano barium tungstate synergism expansibility flame-proof polypropylene of the present invention.28.3%, 600 ℃ of charring rate 9.7% of limiting oxygen index(LOI).
Embodiment 4: take by weighing polypropylene powder pellet 600 grams, single component expansion type flame retardant neopentyl glycol phosphoric acid fat melamine salt 350 grams, fire retarding synergist nano barium tungstate 50 grams, above-mentioned pellet combination treatment in high-speed mixer is good, under the condition of feed rate, temperature and the screw speed of routine, add twin screw extruder, through extrude, cooling, pelletizing, make nano barium tungstate synergism expansibility flame-proof polypropylene of the present invention.27.3%, 600 ℃ of charring rate 8.5% of limiting oxygen index(LOI).
Embodiment 5: take by weighing polypropylene powder pellet 800 grams, single component expansion type flame retardant neopentyl glycol phosphoric acid fat melamine salt 195 grams, fire retarding synergist nano barium tungstate 5 grams, above-mentioned pellet combination treatment in high-speed mixer is good, under the condition of feed rate, temperature and the screw speed of routine, add twin screw extruder, through extrude, cooling, pelletizing, make nano barium tungstate synergism expansibility flame-proof polypropylene of the present invention.26.3%, 600 ℃ of charring rate 7.6% of limiting oxygen index(LOI).
Claims (7)
1. nano barium tungstate synergism expansibility flame-proof polypropylene, it is characterized in that: by polypropylene granules, mix and form as the neopentyl glycol phosphoric acid fat melamine salt of single component expansion type flame retardant, nano flame retardant synergist, wherein fire retarding synergist is a nano barium tungstate, and the mass percent of polypropylene granules, neopentyl glycol phosphoric acid fat melamine salt and nano barium tungstate is 60～80: 19.5～35: 0.5～5.
2. nano barium tungstate synergism expansibility flame-proof polypropylene according to claim 1 is characterized in that: the mass percent of polypropylene granules is 65～80.
3. nano barium tungstate synergism expansibility flame-proof polypropylene according to claim 1 is characterized in that: the mass percent of neopentyl glycol phosphoric acid fat melamine salt is 20～30.
4. nano barium tungstate synergism expansibility flame-proof polypropylene according to claim 1 is characterized in that: the mass percent of nano barium tungstate is 0.5～2.5.
5. nano barium tungstate synergism expansibility flame-proof polypropylene according to claim 1 is characterized in that: the mass percent of polypropylene powder pellet, neopentyl glycol phosphoric acid fat melamine salt and nano barium tungstate is 70: 29: 1.
6. nano barium tungstate synergism expansibility flame-proof polypropylene according to claim 1 is characterized in that: nano barium tungstate is thread.
7. method for preparing the described nano barium tungstate synergism expansibility flame-proof polypropylene of claim 1 is characterized in that: be 60～80: 19.5～35 by mass percentage: 0.5～5 obtains nano barium tungstate synergism expansibility flame-proof polypropylene with polypropylene, neopentyl glycol phosphoric acid fat melamine salt and fire retarding synergist high-speed mixing and extruding pelletization.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001010944A1 (en) * | 1999-08-06 | 2001-02-15 | Pabu Services, Inc. | Intumescent polymer compositions |
| CN101139455A (en) * | 2007-10-17 | 2008-03-12 | 深圳市科聚新材料有限公司 | Flame-proof reinforced polypropylene material and method for preparing same |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001010944A1 (en) * | 1999-08-06 | 2001-02-15 | Pabu Services, Inc. | Intumescent polymer compositions |
| CN101139455A (en) * | 2007-10-17 | 2008-03-12 | 深圳市科聚新材料有限公司 | Flame-proof reinforced polypropylene material and method for preparing same |
Non-Patent Citations (2)
| Title |
|---|
| 何淑琴,胡源,宋磊,唐勇.阻燃聚丙烯/蒙脱土纳米复合材料的燃烧性能.中国科学技术大学学报36 4.2006,36(4),408-412. * |
| 康兴川,金滟,蔡涛.氧化锌对膨胀阻燃聚丙烯的影响.现代塑料加工应用18 2.2006,18(2),40-43. * |
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