CN103880998A - Additive for thermosetting asphalt mixture, and preparation method and application thereof - Google Patents
Additive for thermosetting asphalt mixture, and preparation method and application thereof Download PDFInfo
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- CN103880998A CN103880998A CN201410107006.9A CN201410107006A CN103880998A CN 103880998 A CN103880998 A CN 103880998A CN 201410107006 A CN201410107006 A CN 201410107006A CN 103880998 A CN103880998 A CN 103880998A
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- additive
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- dicyclopentadiene
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Abstract
The invention relates to an additive for a thermosetting asphalt mixture, which is prepared by performing ring-opening polymerization on dicyclopentadiene in an organic solvent under the action of a catalyst. When being used in an asphalt mixture, the polymer greatly enhances the bearing property of the asphalt mixture, lowers the crack, prevents water from infiltration, and achieves the goal of favorable stable repair of road surfaces.
Description
Technical field
The present invention relates to a kind of additive for thermoset asphalt and its preparation method and application, belong to Material Field.
Background technology
Due to the developing rapidly of communications and transportation, the volume of traffic and automobile shafts carry and increase sharply, the canalization of travelling, and the performance of pitch aggregate is had higher requirement in recent years.Require pitch aggregate to have high-temperature stability on the one hand, do not produce rut; Require on the other hand to there is low-temperature cracking-resistance, fatigue resistance, and extend the working life on road surface.For improving the use properties of pitch aggregate, reach the quality index of engine request, people constantly improve pitch aggregate.
Often utilize at present epoxy resin both at home and abroad, urethane, phenolic aldehyde, the materials such as polyester improve the intensity of pitch aggregate as thermosetting resin.Chinese patent CN101255276A carries out modification to pitch makes pitch graft reaction functional group improve the consistency of epoxy and pitch, become a part for epoxy hardener, again with solidifying agent, the composition such as promotor A component, taking epoxy resin as B component, two components are mixed in proportion prepares modifying asphalt.CN1952012A discloses a kind of dedicated compatibilizer raising epoxy of thermosetting epoxy asphalt material and the consistency of pitch, need, by lipid acid and epoxy resin pyroreaction 2 hours under the catalysis of quaternary amine, then add polyvalent alcohol and stannic chloride catalyst to continue at high temperature to react to make for 4 hours.But applicant studies discovery, above-mentioned preparation method not only operates complicated, and cost is high, is difficult for suitability for industrialized production, and the stability of modifying asphalt is difficult to control in actual applications.
Therefore, need a kind of additive for thermoset asphalt of exploitation badly, can avoid the existence of the problems referred to above can realize again operation readiness, simplify construction technology, reduce modification cost, stablize control performance.
Polydicyclopentadiene (being called for short PDCPD) is the thermoset cross-linked polymkeric substance of one being obtained by dicyclopentadiene (being called for short DCPD) ring-opening polymerization.It can keep very high shock strength in very wide temperature range, and modulus in flexure is than nylon and good many of urethane, and PDCPD do not have affinity interaction to water, can be very not large because of the humidity difference performance change of environment.Based on its each side premium properties, be widely used in automobile external product, ship structural component, especially large-sized structural component, in addition, in the application of the aspects such as telecommunications, electric machine, farming machine, sports equipment also in developing.Although PDCPD has good physicals, still there is larger gap apart from the standard of modifying asphalt in road engineering, up to now, also do not have it should had no to report aspect road engineering field.
Summary of the invention
The technological deficiency existing for modifying asphalt in current road engineering, the invention provides a kind of additive for thermoset asphalt, and the high-modulus that it can improve pitch aggregate, reduces its crackle, stops the infiltration of water, realizes the good stable reparation in road surface.
To achieve these goals, the present invention adopts following technical scheme:
For an additive for thermoset asphalt, be in organic solvent, under catalyst action, ring-opening polymerization obtains dicyclopentadiene.
Wherein, described organic solvent is selected from toluene or methylene dichloride, preferably toluene.
Described organic solvent is the 0.5W%-5W% of dicyclopentadiene, preferably 1W%-4W%.
Described catalyzer is selected from first-generation Grubbs catalyst, second generation Grubbs catalyst, first-generation Hoveyda-Grubbs catalyzer, the carbene complex catalyzer such as s-generation Hoveyda-Grubbs catalyzer or schrock catalyzer.
Described catalyzer is the 0.005w%-0.5w% of dicyclopentadiene, preferably 0.01w%-0.1w%.
In the present invention, dicyclopentadiene ring-opening polymerization under specific organic solvent and catalyst action obtains thermoset additive used for asphalt mixture.Catalyzer is dissolved in after solvent, phosphine groups dissociation, form 14e-center, active centre, after mixing with dicyclopentadiene monomer, form metal ring butane structure with cycloolefin coordination, then tetramethylene structure breaking, constantly inserts with cycloolefin monomers, tetramethylene structure constantly forms and breaks, and finally forms polymkeric substance.Simultaneously, because dicyclopentadiene has two cycloolefin structures, in forming linear long chain structure, also can form branched structure, this has given polydicyclopentadiene and has had concurrently the unique material characteristic of rigidity and toughness.When resulting polymers of the present invention is applied to asphalt, greatly improve the load-bearing property of asphalt, reduce crackle, stop the infiltration of water, realize the good stable reparation object in road surface.And additive good weatherability of the present invention, operational use time are long, can be in 100min, normal use within the scope of-30-70 DEG C.
The present invention also provides the preparation method of above-mentioned thermoset asphalt mixture additive, and catalyzer is dissolved in organic solvent, stirs, and obtains mixed solution, then mixed solution is added in dicyclopentadiene and mixed.
As the preferred embodiment of the present invention, when temperature is during at-30 DEG C-10 DEG C, preferably first-generation Hoveyda-Grubbs catalyzer and/or s-generation Hoveyda-Grubbs catalyzer.Catalyzer usage quantity is the 0.005w%-0.05w% of dicyclopentadiene monomer.
When temperature is during at 10 DEG C-40 DEG C, preferably first-generation Grubbs catalyst and/or second generation Grubbs catalyst.Catalyzer usage quantity is the 0.05w%-0.5w% of dicyclopentadiene monomer.
In the time that temperature is more than 40 DEG C, preferably first-generation Grubbs catalyst and/or second generation Grubbs catalyst.
In order to extend the pot life of additive of the present invention, prevent that it from condensing too early, also can in above-mentioned additive formulations, add properties-correcting agent 1 and/or properties-correcting agent 2.
Described properties-correcting agent 1 is selected from triphenylphosphine, Resorcinol, a trinitrobenzene, para benzoquinone, toluhydroquinone, toluhydroquinone, 2-Tert. Butyl Hydroquinone, one or more in 2,5 di tert butyl hydroquinone.When DEG C-10 DEG C, temperature-10, be selected from para benzoquinone, toluhydroquinone, one or more in Resorcinol or a trinitrobenzene, preferably between trinitrobenzene.In the time that temperature is more than 40 DEG C, be selected from toluhydroquinone, triphenylphosphine, one or more in 2-Tert. Butyl Hydroquinone or 2,5 di tert butyl hydroquinone, preferably between triphenylphosphine.
Described properties-correcting agent 1 consumption is dicyclopentadiene 0.00075w%-0.15w%, preferably 0.025 w%.
Concrete addition means is: in mixed solution, add after properties-correcting agent 1, then gained mixed solution is joined to polyreaction in dicyclopentadiene obtain additive.
Described properties-correcting agent 2 is selected from one or more in maleic anhydride, C9 petroleum fractions, norbornylene, vinylbenzene, 1,3-butadiene.
Described properties-correcting agent 2 consumptions are dicyclopentadiene 0.5w%-20w%, preferably 10W%.
Concrete addition means is: properties-correcting agent 2 is mixed with dicyclopentadiene, then gained mixed solution is joined to polyreaction in dicyclopentadiene obtain additive.
The present invention also provides the application of above-mentioned additive at the making of Steel Bridge Deck, tunnel, airport, high-grade highway and arterial street and in repairing.While being particularly applied to the making of highway and arterial street: smear asphalt mixed soil surface or in be fed into and need to repair or need in 20-40min, complete when the position of reinforcement.For atarting material solidifies, complete after perfusion simultaneously, can be by mildly heating to be carried out in perfusion position, Heating temperature is 40-70 DEG C.
Additive of the present invention has following technique effect:
1. suitability widely
Additive of the present invention is to existing road surface, newly quick reinforcement all can be carried out in the road surfaces such as face, finish coat, micro-table place, wearing course, mend of repairing the roads, to AC, SMA, OGFC grade is equipped with different porosities asphalt all excellent reinforcing effect, can promote its intensity, anti-rut and the performance such as anti-aging.
good environment friendly
Additive of the present invention only has slight irritating smell, and after using, the residual volatilization very soon of smell, substantially harmless to human body; This material does not contain aldehydes carcinogenic substance and other organic solvents, water insoluble, is the environment-friendly and green material of advocating at present.When additive simultaneously of the present invention uses, add without hot mix, the not consume fuel energy, does not produce smog dust yet, the engineering construction of real realization " zero release zero consumes zero is polluted ".
3.
adhesivity perfectly mixes
Under additive normal temperature of the present invention, be liquid, water white transparency, can melt mutually with existing bituminous material perfection, infiltrate asphalt deep inside, increase the adhesive property of bonding part, in continuous gap, form reticulated structure simultaneously, provide structure-type to support, increase asphalt entirety modulus.For finish coat, micro-table place, mend etc., this material can mix with new and old bituminous material simultaneously, has significantly increased the adhesivity of agglutinate, effectively improves coming off of aged asphalt agglutinate cracked, has thoroughly avoided coming off the phenomenons such as grain.
of short duration construction period
Additive of the present invention abandoned conventional thermoplastic material heating operation, etc. disadvantage to be cooled, also overcome the drawback of emulsified bitumen, cold-repairing material equal solvent type road material require very long time solvent flashing simultaneously.Under additive normal temperature state of the present invention, be liquid, convenient operation; After use, can fast setting in the short period of time, do not stay any residual.This has improved working efficiency greatly, " without health, repaiies logical ", significantly shortens construction period, and the large section of traffic pressure, airport, first-aid repair construction etc. are significant.
construction technology easily
Additive construction technology of the present invention is simple, does not need existing installation to carry out any transformation, and workmen carries out simple training can grasp constructional method.Only need at the construction field (site) simply the allotment of different components material, Samburu cloth is to position, required road surface, whether suitable or use calorifier to carry out simple heating depending on meteorological conditions.
water shutoff reliably
Additive of the present invention, after entering asphalt and pitch and mixing, still keeps extremely low viscosity, can infiltrate in the space of compound, and even adhesion coating between penetrating layer, is reaching after set time fast setting.In the dense-graded mix such as AC, SMA, can rest in mixture gap, isolated bituminous cements contacts with water.In the open mixs such as OGFC, can, along under its macropore flow, rest on surface layer bottom adhesion coating, repair breakage, stop moisture content to enter, can form protective membrane at the place's asphalt surface of flowing through simultaneously, when exclusion of water erosion, as supporting binding material, improve intensity.
high mechanical property
Additive of the present invention possesses the high strength of materials, after it solidifies, and more than modulus in flexure 1800MPa, tensile strength 35MPa, heat-drawn wire is more than 180 DEG C, more than socle girder notched Izod impact strength 400J/m.Due to solvent-free existence, so material only has minimum shrinkability, internal stress is minimum.Through the asphalt of reinforcement, modulus significantly promotes, and the performances such as anti-rut, antireflection crackle are greatly improved.
excellent anti-aging erosion resistance hydrophobicity
Additive of the present invention has excellent anti-aging anticorrosive and hydrophobic performance, can resistance to general soda acid and the corrosion of organic solvent, and anti-aging and anti-ultraviolet property excellence, significantly improve the life-span of ground surface material, especially be useful in airfield runway, service station, waits between chemical plant and easily pollutes road surface.
splendid climate adaptability
Additive of the present invention is constructed applicable to various extreme climates, especially low temperature adaptability is fabulous, rapid construction under can the temperature condition below-30 DEG C, ignores chill, and this performance is tantamount to increase for northern low temperature severe cold weather in a large number can the engineering time.
Embodiment
Following examples are used for illustrating the present invention, but are not used for limiting the scope of the invention.
embodiment 1
0.5g first-generation Grubbs catalyst is dissolved in 20g toluene, after fully stirring, mixed solution is added in 500g dicyclopentadiene, mix, polyreaction obtains the additive for thermoset asphalt.
Get in the open gradation cold-repairing material standard rut test piece that 300g mixed solution pours into prior moulding, get in the open gradation cold-repairing material standard marshal piece that 30g pours into prior moulding, under 20 DEG C of environment, solidify and need 20min.
embodiment 2
0.5g s-generation Hoveyda-Grubbs catalyst dissolution, in 20g toluene, is added mixed solution in 500g dicyclopentadiene after fully handing over to the next shift, mix, polyreaction obtains the additive for thermoset asphalt.
Get in the open gradation cold-repairing material standard rut test piece that 300g mixed solution pours into prior moulding, get in the open gradation cold-repairing material standard marshal piece that 30g pours into prior moulding, under-20 DEG C of environment, solidify and need 10min.
embodiment 3
Method according to embodiment 1 is prepared additive.Difference is: in catalyzer and organic solvent, add 0.125g triphenylphosphine, under 40 DEG C of environment, solidify and need 15min.
embodiment 4
Method according to embodiment 2 is prepared additive.Difference is: in catalyzer and organic solvent, add 0.125g trinitrobenzene.Under 10 DEG C of environment, solidify and need 5min.
embodiment 5
Method according to embodiment 1 is prepared additive.Difference is: 50 grams of vinylbenzene are added in dicyclopentadiene, under 20 DEG C of environment, solidify and need 20min.
embodiment 6
Method according to embodiment 2 is prepared additive.Difference is: 50 grams of 1,3-butadienes are added in dicyclopentadiene, under-20 DEG C of environment, solidify and need 10min.
experimental example 1 performance test
The test specimen that contains embodiment of the present invention 1-6 gained additive is carried out to performance test.And adopt the test specimen that contains asphalt concrete to test as a comparison.Measurement result is in table 1.
Table 1 test specimen test result
Although above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, all belong to the scope of protection of present invention.
Claims (10)
1. for an additive for thermoset asphalt, it is characterized in that, in organic solvent, under catalyst action, ring-opening polymerization obtains dicyclopentadiene.
2. additive according to claim 1, it is characterized in that, described catalyzer is selected from first-generation Grubbs catalyst, second generation Grubbs catalyst, first-generation Hoveyda-Grubbs catalyzer, s-generation Hoveyda-Grubbs catalyzer or schrock catalyzer.
3. additive according to claim 2, is characterized in that, when temperature is during at-30 DEG C-10 DEG C, described catalyzer is selected from first-generation Hoveyda-Grubbs catalyzer and/or s-generation Hoveyda-Grubbs catalyzer;
When temperature is during at 10 DEG C-40 DEG C, described catalyzer is selected from first-generation Grubbs catalyst and/or second generation Grubbs catalyst;
In the time that temperature is more than 40 DEG C, described catalyzer is selected from first-generation Grubbs catalyst and/or second generation Grubbs catalyst.
4. additive according to claim 1, is characterized in that, described catalyst levels is dicyclopentadiene 0.005w%-0.5w%.
5. additive according to claim 1, is characterized in that, described organic solvent is selected from toluene or methylene dichloride.
6. additive according to claim 1, is characterized in that, described consumption of organic solvent is dicyclopentadiene 0.5W%-5W%.
7. additive according to claim 1, is characterized in that, also contains properties-correcting agent 1 and/or properties-correcting agent 2 in described additive.
8. additive according to claim 7, is characterized in that, described properties-correcting agent 1 is selected from triphenylphosphine, Resorcinol, between trinitrobenzene, para benzoquinone, toluhydroquinone, toluhydroquinone, 2-Tert. Butyl Hydroquinone, one or more in 2,5 di tert butyl hydroquinone;
Described properties-correcting agent 2 is selected from one or more in maleic anhydride, C9 petroleum fractions, norbornylene, vinylbenzene, 1,3-butadiene.
9. the preparation method of the arbitrary described additive of claim 1-8, is characterized in that, catalyzer is dissolved in organic solvent, stirs and obtains mixed solution, then mixed solution is added in dicyclopentadiene and mixed.
10. the application of the arbitrary described additive of claim 1-8 in making and the repairing of Steel Bridge Deck, tunnel, airport, high-grade highway and arterial street.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410107006.9A CN103880998A (en) | 2014-03-21 | 2014-03-21 | Additive for thermosetting asphalt mixture, and preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410107006.9A CN103880998A (en) | 2014-03-21 | 2014-03-21 | Additive for thermosetting asphalt mixture, and preparation method and application thereof |
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| CN201410107006.9A Pending CN103880998A (en) | 2014-03-21 | 2014-03-21 | Additive for thermosetting asphalt mixture, and preparation method and application thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1928025A (en) * | 2006-08-30 | 2007-03-14 | 中国石油兰州石油化工公司 | Prepolymer containing mixture of C10, C15, C20 olefin, preparation and application thereof |
| CN101117443A (en) * | 2006-08-04 | 2008-02-06 | 深圳市海川实业股份有限公司 | Modified asphalt material and preparation method thereof |
| US20110293954A1 (en) * | 2010-04-29 | 2011-12-01 | The Regents Of The University Of California | Application of high toughness, low viscosity nano-molecular resin for reinforcing pothole patching materials in asphalt and concrete base pavement |
-
2014
- 2014-03-21 CN CN201410107006.9A patent/CN103880998A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101117443A (en) * | 2006-08-04 | 2008-02-06 | 深圳市海川实业股份有限公司 | Modified asphalt material and preparation method thereof |
| CN1928025A (en) * | 2006-08-30 | 2007-03-14 | 中国石油兰州石油化工公司 | Prepolymer containing mixture of C10, C15, C20 olefin, preparation and application thereof |
| US20110293954A1 (en) * | 2010-04-29 | 2011-12-01 | The Regents Of The University Of California | Application of high toughness, low viscosity nano-molecular resin for reinforcing pothole patching materials in asphalt and concrete base pavement |
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Application publication date: 20140625 |
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