CN100419026C - Fire-retardant and modified asphalt mixture - Google Patents
Fire-retardant and modified asphalt mixture Download PDFInfo
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- CN100419026C CN100419026C CNB031332668A CN03133266A CN100419026C CN 100419026 C CN100419026 C CN 100419026C CN B031332668 A CNB031332668 A CN B031332668A CN 03133266 A CN03133266 A CN 03133266A CN 100419026 C CN100419026 C CN 100419026C
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Abstract
The present invention relates to bituminous mixture, particularly to modified bituminous mixture which is suitable for paving a road surface in a vehicular tunnel and has a flame retardant effect. The bituminous mixture comprises bituminous substrates, thermoplastic elastomer, inertial filling material, halogen flame retardant, a smoke suppressing agent, metal oxide hydrates and flame retardant containing nitrogen heterocycle, wherein the flame retardant containing nitrogen heterocycle comprises at least six atoms, and at least three of the six atoms are nitrogen atoms. The components are mixed according to a certain proportion, so that various kinds of retardant can have synergistic action mutually. Compared with common bituminous, a bituminous road surface paved by the present invention has the better characteristics of high-temperature performance, antiaging performance, temperature sensing performance, etc. When the bituminous mixture is used on the road surfaces of tunnels, the flame retardant effect and the smoke suppressing effect are obvious, and the processing performance of material is raised obviously.
Description
Technical field
The present invention relates to a kind of asphalt, particularly be applicable to the asphalt of the risen flame retardant effect of paving in the vcehicular tunnel.
Background technology
Be accompanied by the fast development of China's motorway, the quantity of vcehicular tunnel is also in continuous increase.Vcehicular tunnel is as a special road section of highway, length does not wait to several kilometers from hundreds of rice, imagination is at this special road section, in case the automobile circuit fire takes place, automobile goods fire and traffic accident car collision, goods automobile (particularly tank wagon) are overturned the fire that causes, it is big smog to occur, temperature height, smoke evacuation difficulty; Evacuate difficulty; Phenomenons such as fire attack difficulty, its consequence is hardly imaginable.A lot of these class accidents had taken place in China and foreign countries' highway circle, suffered heavy losses.This shows,, should do one's utmost from all kinds of disaster hidden-troubles of source elimination based on strick precaution for the fire safety problem of vcehicular tunnel.
At present, domestic most of tunnel road surface generally adopts cement concrete or pitch to mat formation, though to a certain extent, the relative bituminous concrete pavement of cement concrete pavement is better than bituminous concrete pavement at aspects such as water tolerance, the feature of environmental protection, and can also avoid obnoxious flavour that pitch comes out to harm that human body caused when mating formation.But, according to domestic and international many studies show that, advantages such as cement concrete has been difficult to satisfy the requirement on road surface in the modern tunnel, and bituminous concrete pavement is comfortable with its driving, noise is little, airborne dust is few, easy to maintenance are widely used, and are the major project materials that is used for Road construction at present.
The same with most of synthetic polymers, pitch has combustibility in air, along with its widespread use of behavior material of construction on engineering, is just progressively risen by the danger of the fire that it caused.Especially as long pavement material apart from road surface in the tunnel, in case vehicle fire takes place, bituminous pavement also can be on fire simultaneously or be generated dense smoke, thereby in the difficulty that has increased the weight of fire and personnel escape virtually.For example, the second in the world long tunnel Switzerland St.Gotthard Tunnel fire disaster tragic incident, because the on-the-spot various a large amount of toxic gases that discharge without the material combustion of fire-retardant finish that use, thereby making the very fast at short notice death by suffocation of people, number is 41 people nearly.
In order to change this present situation, people reduce the combustibility of tunnel sheet pavement by taking two kinds of different modes.A kind of is to add flame-retardant additive in bituminous concrete, by in itself and the pitch during flammable organic compound burning institute decompose and produce material and react, thereby slow down or stop the incendiary chain reaction, reach fire-retardant purpose.Another kind is to adopt to smear the back-fire relief heat-resistant coating on the supercrust of asphalt concrete pavement, plays the fp purpose by isolating blacktop.
People such as Li Zuwei, Chen Huiqiang is at " research of flame-retardant pitch modification technology and fire retardant mechanism thereof " (2002, " Changsha Traffic College journal ", Vol.18, No.4, P.44-47) in, according to special environment for use in be correlated with both at home and abroad modern technique and the tunnel, proposed the technical requirements of tunnel pavement, and studied asphalt flame-retardant modification technology and its fire retardant mechanism of suitable tunnel pavement.Its relevant flame-retarded technology mainly is by add halogenated flame retardant and inorganic metal compound fire retardant in bituminous concrete, utilize halogenated flame retardant that decomposition reaction at high temperature takes place and discharge HX (X represents halogen system), radical generation chain reaction in HX and the flame, radical concentration is reduced, thereby slow down or stop the incendiary chain reaction, reach fire-retardant purpose; Inorganic metal compound is heated to certain temperature and can decomposes, and generates water, and this reaction itself is exactly thermo-negative reaction, and the water that reaction is generated also can absorb a large amount of heat, thereby reduced the temperature of system, delayed the bituminous decomposition, reached fire-retardant purpose.To a certain extent, though the mutual synergistic effect of halogenated flame retardant and inorganic metal compound fire retardant can play tangible flame retardant effect, it is relatively poor that but the thermostability of halogenated flame retardant and smoke-suppressing all compare, inorganic metal compound wants to reach the ideal flame retardant effect, must strengthen its loading level, and loading level is strengthened, must cause pitch mixing, mobile poor during moulding, the processing of material and mechanical property are descended.
Patent of invention 95117026.0 also discloses a kind of fp petroleum asphalt felt, and it is to add fire retardant such as ammonium phosphate (or ammonium sulfate), magnesium hydroxide and linking agent such as tetramethyl-thiuram disulfide in pitch simultaneously.Prepared petroleum asphalt felt can play anti-fire action.But it mainly is to be applied in the roof as water-proof material, is not applied on the road surface.
Patent of invention 92105725.3 also discloses a kind of non-combustible asphalt, malthoid, its production method is to apply fire protection flame retarding heatproof chemical industry medicines such as sodium bicarbonate in pitch, smeared one deck back-fire relief heatproof masking liquid above the malthoid that makes, thereby be applied in above the building materials, can effectively prevent fires,, this asphalt felt seldom is applied on the tunnel road surface.Though prepared non-combustible asphalt has certain flame retardant effect, but smoke suppressing effect is not clearly.
U.S. Pat 4659381 also discloses a kind of antiflaming asphalt mixture, it is by add at least a halogenated flame retardant and at least a phosphorated mineral compound in modifying asphalt, as ammonium phosphate or red phosphorus, reach the purpose of fire protection flame retarding, halogenated flame retardant has the good flame effect, and can press down the cigarette effect but is not clearly; Red phosphorus is a kind of effective fire retardant, but because it is inflammable when frictional impact, and smoke suppressing effect is also not obvious, so be difficult to satisfy ideally the particular requirement of modern fire prevention tunnel road surface.
During presence of fire, cigarette is to produce at first and the most fatal factor, and according to statistics, death toll has 80% to be due to cigarette suffocates in the fire.And in the middle of the existing flame-retarded technology, but seldom have " fire-retardant " and " pressing down cigarette " are mentioned in the same breath, moreover for some superpolymer, it is more even more important than " fire-retardant " " to press down cigarette ", especially the fire retardant of Halogen system is the main source that is fuming of smog, so, can develop a kind of can either be fire-retardant, the efficient flame-retarding agent that can press down cigarette again is the main direction and the trend of industry development from now on.
Summary of the invention
For the better useful effect of performance fire retardant in asphalt, make " fire-retardant " of fire retardant better simultaneously with the synergy of " pressing down cigarette ", the present invention discloses a kind of Fire-retardant modified asphaltum mixture on the basis of existing technology, wherein contain modifying asphalt, fire retardant, press down fumicants and corresponding inert filler etc., with each component by specific mixed with mating formation on the road surface, find that its " fire-retardant " is all quite obvious with " press down cigarette " effect.
A kind of Fire-retardant modified asphaltum mixture of the present invention, its component contains matrix pitch, thermoplastic elastomer, inert filler, halogenated flame retardant, presses down fumicants, metal oxide hydrate and nitrogen heterocyclic ring thing fire retardant, described nitrogen heterocyclic ring thing fire retardant contains 6 atoms at least, and wherein at least 3 be nitrogen-atoms; The described fumicants that presses down is selected from molybdenum compound, vanadium compound, silicon compound, lime carbonate, the potter's clay at least a kind of; Described metal oxide hydrate is selected from the Trihydrate of aluminium and the magnesian hydrate at least a kind of.
Wherein, each component accounts for the weight ratio of Fire-retardant modified asphaltum mixture and is:
Thermoplastic elastomer is 5～18%; Inert filler is 20～30%; Halogenated flame retardant is 2～30%; Pressing down fumicants is 10～20%; Metal oxide hydrate is 1～20%; Nitrogen heterocyclic ring thing fire retardant is 1～10%.
The present invention adopts and add thermoplastic elastomer in asphalt, forms the alleged modifying asphalt of the present invention, and through the pitch after the modification, than plain asphalt, its ductility, elasticity, temperature sensitivity and viscosity etc. have all obtained corresponding raising.Wherein, be selected from a kind of among SBS, SIS or the SEBS as the thermoplastic elastomer of pitch modifying agent.During preparation, adopt the high speed shear Mixingemulsificationmachine, earlier with plain asphalt dehydration 30min under 110 ℃, be warmed up to 175 ℃, and then modifying agent joined in the pitch in proportion shear 15min and get final product, in order to make the pitch after the modification can reach desired effects, the addition of thermoplastic elastomer in asphalt is 5～18%, preferably can be 6～15%; As the important component part of antiflaming asphalt mixture, the content of modifying asphalt in compound is 20～40%, and described per-cent is based on the weight percent of antiflaming asphalt mixture.
Filler is as a part indispensable in the asphalt, to the good and bad important influence of the performance of asphalt, the present invention adopts inert filler to come enhancing modified bituminous characteristic, and it is wherein at least a that described inert filler is selected from perlite, mica powder, aluminum oxide, glass fibre, lime carbonate, magnesiumcarbonate, tripoli and carbon black.It proportionally is added in the antiflaming asphalt mixture, mixes preferably in order to make other components of itself and compound, inert filler is divided into small-particle, and its median size is between 50～300 μ m.
As the important component part in the antiflaming asphalt mixture, the flame retardant effect of selection of fire retardant and product is closely related, the present invention selects halogenated flame retardant, nitrogen heterocyclic ring thing fire retardant and metal oxide hydrate acting in conjunction for use, make several different fire retardants that synergy mutually take place, produce the effect of 1+1＞2, better play fire-retardant effect.The introducing of nitrogen heterocyclic ring thing fire retardant has simultaneously reduced the consumption of poisonous halogenated flame retardant; The consistency of pitch and fire retardant obviously improves, and has reduced the generation of segregation phenomenon.
As a kind of preferred version, the weight ratio that halogenated flame retardant accounts for Fire-retardant modified asphaltum mixture is 5～10%.Described halogenated flame retardant is one of Polybrominated biphenyl oxide compound, many bromobenzenes, many bromines hexichol oxycompound, the adjacent dicarboximide of many bromobenzenes, many bromines cyclodecane, chloro alicyclic compound and many bromophenols.
As a kind of preferred version, the weight ratio that nitrogen heterocyclic ring thing fire retardant accounts for Fire-retardant modified asphaltum mixture is 2～5%.Nitrogen heterocyclic ring thing fire retardant is one of melamine, triazine and hydrogenation triazine, as Hexahydrotriazine.
The hydrate of metal oxide is used in not only can be fire-retardant in the asphalt, can also press down cigarette, except the hydrate that adopts metal oxide of the present invention, can play the hydrate that also comprises lime borate of effect same, the hydrate of barium borate or the hydrate of zinc borate, its weight ratio of being put in flame-retardant pitch modification compound was 0～20% (not comprising 0).
Thermal decomposition product and products of combustion when smog is mainly derived from burning, in order to reduce a large amount of smog that produced when superpolymer burns, therefore, the present invention takes to add in antiflaming asphalt mixture and presses down fumicants, presses down fumicants and mainly selects metallic compound for use.Can reach the ideal smoke suppressing effect, depend on the size that presses down fumicants surface-area that particle forms, particle size range be usually between 0.1～2 μ m preferably.
When preparing Fire-retardant modified asphaltum mixture of the present invention, at first in the high speed shear Mixingemulsificationmachine, matrix pitch is descended dehydration 30～40min at 120 ℃, be warmed up to 176 ℃, add thermoplastic elastomer, shear 20～30min, add fire retardant again, press down fumicants and other components, mix and shear 10～25min, evenly get final product until shear agitation.
Compared with prior art, antiflaming asphalt mixture of the present invention, not only on characteristics such as high-temperature behavior, ageing resistance and temperature-sensitive performance, improve a lot than plain asphalt, and mat formation and be applied on the tunnel road surface, its " fire-retardant " is also all very obvious with " pressing down cigarette " effect, and Drawing abillity also obviously improves simultaneously.
Embodiment
Below set forth beneficial effect of the present invention by several specific embodiments
Embodiment 1: a kind of Fire-retardant modified asphaltum mixture, and its component content is as follows:
Prepare by the high speed shear Mixingemulsificationmachine, at first with matrix pitch dehydration 30min under 120 ℃, be warmed up to 176 ℃, add thermoplastic elastomer Kraton D-1101, shear 20min, add fire retardant again: decabrominated dipheny oxide compound, melamine and magnesian hydrate and press down fumicants molybdenum dioxide, filler and other components, mix and shear 15min and get final product.
Below be the performance test to above-mentioned flame-retardant smoke inhibition asphalt, use the asphalt that does not add fire retardant, presses down fumicants to do contrast, every performance index are as shown in table 1 below:
Table 1
| Index name | Do not add fire retardant, press down the modified asphalt mixture of fumicants | Add fire retardant, pressed down the modified asphalt mixture of fumicants |
| 15 ℃ of penetration degree/0.1mm | 24.6 | 21.6 |
| 25 ℃ of penetration degree/0.1mm | 49.2 | 38.6 |
| 30 ℃ of penetration degree/0.1mm | 63.3 | 50.1 |
| Penetrative index PI | 1.9 | 2.4 |
| Softening temperature/℃ | 85 | 83.5 |
| Limiting oxygen index(LOI) | 19 | 24 |
| Ductility (5 ℃)/cm | 21.0 | 20.2 |
Embodiment 2: adopt the SBS modifying asphalt to make antiflaming asphalt mixture of the present invention.
The preparation method of similar the foregoing description 1, with preparation fire-retardant, press down the cigarette modified asphalt mixture and do not add fire retardant, the asphalt that presses down fumicants does contrast, every performance index are as shown in table 2 below:
Table 2
| Index name | Do not add fire retardant, press down the modified asphalt mixture of fumicants | Add fire retardant, pressed down the modified asphalt mixture of fumicants |
| 15 ℃ of penetration degree/0.1mm | 23.6 | 19.5 |
| 25 ℃ of penetration degree/0.1mm | 48.5 | 39.2 |
| 30 ℃ of penetration degree/0.1mm | 64.3 | 53.1 |
| Penetrative index PI | 1.8 | 2.3 |
| Softening temperature/℃ | 86 | 84.8 |
| Limiting oxygen index(LOI) | 19 | 23 |
| Ductility (5 ℃)/cm | 20.2 | 21.0 |
Embodiment 3: adopt the SIS modifying asphalt to make antiflaming asphalt mixture of the present invention.
The preparation method of similar the foregoing description 1, with preparation fire-retardant, press down the cigarette modified asphalt mixture and do not add fire retardant, the modified asphalt mixture that presses down fumicants does contrast, every performance index are as shown in table 3 below:
Table 3
| Index name | Do not add fire retardant, press down the modified asphalt mixture of fumicants | Add fire retardant, pressed down the modified asphalt mixture of fumicants |
| 15 ℃ of penetration degree/0.1mm | 25.6 | 20.5 |
| 25 ℃ of penetration degree/0.1mm | 49.0 | 40.2 |
| 30 ℃ of penetration degree/0.1mm | 66.4 | 54.2 |
| Penetrative index PI | 1.9 | 2.4 |
| Softening temperature/℃ | 88.2 | 85.6 |
| Limiting oxygen index(LOI) | 17 | 24 |
| Ductility (5 ℃)/cm | 22.4 | 23.2 |
Embodiment 4: adopt the SEBS modifying asphalt to make antiflaming asphalt mixture of the present invention.
The preparation method of similar the foregoing description 1, with preparation fire-retardant, press down the cigarette modified asphalt mixture and do not add fire retardant, the modified asphalt mixture that presses down fumicants does contrast, every performance index are as shown in table 4 below:
Table 4
| Index name | Do not add fire retardant, press down the modified asphalt mixture of fumicants | Add fire retardant, pressed down the modified asphalt mixture of fumicants |
| 15 ℃ of penetration degree/0.1mm | 23.6 | 19.5 |
| 25 ℃ of penetration degree/0.1mm | 48.5 | 39.2 |
| 30 ℃ of penetration degree/0.1mm | 64.3 | 53.1 |
| Penetrative index PI | 1.8 | 2.3 |
| Softening temperature/℃ | 86 | 84.8 |
| Limiting oxygen index(LOI) | 19 | 23 |
| Ductility (5 ℃)/cm | 20.2 | 21.0 |
Claims (9)
1. Fire-retardant modified asphaltum mixture, its component contains matrix pitch, thermoplastic elastomer, inert filler, halogenated flame retardant, presses down fumicants, metal oxide hydrate and nitrogen heterocyclic ring thing fire retardant, described nitrogen heterocyclic ring thing fire retardant contains 6 atoms at least, and wherein at least 3 be nitrogen-atoms; The described fumicants that presses down is selected from molybdenum compound, vanadium compound, silicon compound, lime carbonate, the potter's clay at least a kind of; Described metal oxide hydrate is selected from the Trihydrate of aluminium and the magnesian hydrate at least a kind of.
2. Fire-retardant modified asphaltum mixture according to claim 1 is characterized in that: the weight ratio that each component accounts for Fire-retardant modified asphaltum mixture is:
Thermoplastic elastomer is 5～18%;
Inert filler is 20～30%;
Halogenated flame retardant is 2～30%;
Pressing down fumicants is 10～20%;
Metal oxide hydrate is 1～20%;
Nitrogen heterocyclic ring thing fire retardant is 1～10%.
3. Fire-retardant modified asphaltum mixture according to claim 2 is characterized in that: the weight ratio that described thermoplastic elastomer accounts for Fire-retardant modified asphaltum mixture is 6～15%.
4. according to the arbitrary described Fire-retardant modified asphaltum mixture of claim 1-3, it is characterized in that: be selected from a kind of among SBS, SIS or the SEBS as the thermoplastic elastomer of pitch modifying agent.
5. Fire-retardant modified asphaltum mixture according to claim 1 and 2 is characterized in that: it is wherein at least a that described inert filler is selected from perlite, mica powder, aluminum oxide, glass fibre, lime carbonate, magnesiumcarbonate, tripoli and carbon black.
6. Fire-retardant modified asphaltum mixture according to claim 2 is characterized in that: the weight ratio that described halogenated flame retardant accounts for Fire-retardant modified asphaltum mixture is 5～10%.
7. according to claim 1,2 or 6 described Fire-retardant modified asphaltum mixtures, it is characterized in that: described halogenated flame retardant is one of Polybrominated biphenyl oxide compound, many bromobenzenes, many bromines hexichol oxycompound, the adjacent dicarboximide of many bromobenzenes, many bromines cyclodecane, chloro alicyclic compound and many bromophenols.
8. Fire-retardant modified asphaltum mixture according to claim 2 is characterized in that: the weight ratio that described nitrogen heterocyclic ring thing fire retardant accounts for Fire-retardant modified asphaltum mixture is 2～5%.
9. according to claim 1,2 or 8 described Fire-retardant modified asphaltum mixtures, it is characterized in that: described nitrogen heterocyclic ring thing fire retardant is one of melamine, triazine and hydrogenation triazine.
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| CN100419026C true CN100419026C (en) | 2008-09-17 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102002902A (en) * | 2010-09-17 | 2011-04-06 | 韩耀斌 | Intelligent asphalt road pavement capable of automatically controlling temperature and pavement material composition |
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| CN1935902B (en) * | 2005-09-22 | 2010-07-14 | 深圳市海川实业股份有限公司 | Road fire-resistant asphalt |
| CN1330707C (en) * | 2005-10-13 | 2007-08-08 | 武汉理工大学 | Method for preparing fire-fighting noise rreduced, skidproof material of road surface in tunnel |
| CN101077931B (en) * | 2006-05-23 | 2011-05-11 | 深圳市海川实业股份有限公司 | Flame-proof asphalt for road and preparation method thereof |
| CN101077932B (en) * | 2006-05-23 | 2011-05-25 | 深圳市海川实业股份有限公司 | Flame-proof asphalt for road and preparation method thereof |
| CN101077934B (en) * | 2006-05-23 | 2010-12-15 | 深圳市海川实业股份有限公司 | Flame-proof asphalt for road and preparation method thereof |
| CN100392018C (en) * | 2006-06-15 | 2008-06-04 | 武汉理工大学 | Halogenless fire retarded polymer modified asphalt and preparation process thereof |
| CN101153117B (en) * | 2006-09-28 | 2011-04-20 | 深圳市海川实业股份有限公司 | Bitumen flame-proof modifier |
| CN102464891B (en) * | 2010-11-04 | 2013-10-09 | 中国石油化工股份有限公司 | Road flame-retardant asphalt and preparation method |
| CN103525104A (en) * | 2013-10-08 | 2014-01-22 | 陈显鹏 | Fireproof emulsified asphalt |
| CN104559267A (en) * | 2015-02-09 | 2015-04-29 | 中核华泰建设有限公司 | Preparation method of modified asphalt |
| CN105131619A (en) * | 2015-08-21 | 2015-12-09 | 中国路桥工程有限责任公司 | Inorganic flame retardant modified asphalt and preparation process thereof |
| CN107286554A (en) * | 2017-06-28 | 2017-10-24 | 常州万博金属构件厂 | A kind of flame-retardant pitch and preparation method thereof |
| CN110183147B (en) * | 2019-04-30 | 2021-09-03 | 中国建筑土木建设有限公司 | Asphalt mixture for environment-friendly road and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102002902A (en) * | 2010-09-17 | 2011-04-06 | 韩耀斌 | Intelligent asphalt road pavement capable of automatically controlling temperature and pavement material composition |
| CN102002902B (en) * | 2010-09-17 | 2013-04-17 | 韩耀斌 | Intelligent asphalt road pavement capable of automatically controlling temperature and pavement material composition |
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| CN1569963A (en) | 2005-01-26 |
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