CN1935905A - Age-resistant modified asphalt and its preparing method - Google Patents
Age-resistant modified asphalt and its preparing method Download PDFInfo
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- CN1935905A CN1935905A CN 200610124675 CN200610124675A CN1935905A CN 1935905 A CN1935905 A CN 1935905A CN 200610124675 CN200610124675 CN 200610124675 CN 200610124675 A CN200610124675 A CN 200610124675A CN 1935905 A CN1935905 A CN 1935905A
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Abstract
The invention relates to modified asphalt and the preparing method. Its components mass percent are as follows: asphalt 84-98.4, polymer modifier 1-10, layer silicate clay 0.5-5, and organic amine layer inserting auxiliary agent by which it can make common layer silicate and polymer modified asphalt to form nanometer compound with delaminating structure. The produced aging resistance modified asphalt has greatly ageing resistance property, and high quality price ratio.
Description
Technical field
The present invention relates to a kind of modifying asphalt and preparation method thereof.
Background technology
Ageing of asphalt is the important factor that influences the road bitumen use properties.Bituminous is aging to typically refer to pitch at a series of physics and the chemical transformation storing, transport, mix and stir, take place in construction and the life-time service process, causes the process of its performance degradation.Aging light constituent volatilization and the deterioration by oxidation of mainly showing of bituminous.In bituminous pavement life-time service process, oxidation can slowly take place when pitch contacts with air, the polarity oxy radical of formation is coupled to the high-molecular weight micelle gradually and impels the raising of bituminous viscosity, ductility to reduce.Therefore, bituminous pavement very easily takes place aging under solar radiation and in the hot environment, breakoff phenomenons such as hardening, cracking can occur, and these have all greatly damaged the use properties of bituminous pavement, have shortened its work-ing life.
With polymkeric substance to asphalt modification, existing at home and abroad history for many years, polymer modifiers also has multiple, using maximum is styrene-butadiene-styrene inlay section thermal plastic elastic body (SBS) and styrene-butadiene rubber(SBR) (SBR).The SBS modifying asphalt has good high-and low-temperature resistance performance and elastic recovery properties, is one of kind of consumption maximum in the present polymer modified asphalt.The SBR relative low price, it can obviously improve bituminous low temperature use properties.But because these two kinds of properties-correcting agent all contain the two keys of a certain amount of C=C, the two keys of C=C are easy to degradation with aging under oxygen, action of ultraviolet ray, therefore, improve the aging resistance of SBS modifying asphalt, SBR modifying asphalt and are paid close attention to widely.Yet, still do not have effective means about the aging resistance that improves SBS or SBR modifying asphalt so far.
Chinese patent 200410069166.5 proposes to improve bituminous high temperature and ageing resistance by interpolation calcium-base bentonite or the sodium-ionized bentonite or the wilkinite that organises in the powder styrene butadiene rubber modifying asphalt.Yet because common layered silicate sheet surfaces presents wetting ability, compound can only to form intercalation nano compound with pitch, very limited to bituminous ageing resistance improvement effect.And the layered silicate sheet surfaces that organises has good lipophilicity, can form exfoliated nano combinedly with pitch, and it is good that the bituminous ageing resistance is improved effect.But the layered silicate complicated process of preparation that organises costs an arm and a leg, and using it for asphalt modification has by a relatively large margin raising to the cost of modifying asphalt, has limited its application.
Summary of the invention
The object of the present invention is to provide a kind of ageing-resistant performance height, age-resistant modified asphalt that cost is low and preparation method thereof.
To achieve these goals, technical scheme of the present invention is: a kind of age-resistant modified asphalt is characterized in that it is made up of pitch, polymer modifiers, clay of laminar silicate and organic amine intercalation auxiliary agent; The shared mass percent of each raw material is: pitch 84～98.4, polymer modifiers 1～10, clay of laminar silicate 0.5～5, organic amine intercalation auxiliary agent 0.1～1.
Described pitch is bi tumenf orr oad, and its softening temperature is 40～65 ℃, and 25 ℃ of penetration degrees are greater than 40dmm.
Described polymer modifiers is the mixture of a kind of in styrene-butadiene-styrene inlay section thermal plastic elastic body, the styrene-butadiene rubber(SBR) or two kinds, during mixing be arbitrarily than.
Described clay of laminar silicate is sodium-based montmorillonite or tires out and take off stone that the fineness of sodium-based montmorillonite is 200～600 orders, and tired fineness of taking off stone is 200～600 orders.
Described organic amine intercalation auxiliary agent is any one or any one the above mixture in n-Laurylamine, cetylamine, octadecane amine, the hexanolactam, during mixing be any than.
The shared mass percent of above-mentioned each raw material is: pitch 88～94, polymer modifiers 3～8, clay of laminar silicate 1～4, organic amine intercalation auxiliary agent 0.3～0.8.
The preparation method of above-mentioned age-resistant modified asphalt is characterized in that carrying out as follows:
(1) by the shared mass percent of each raw material be: pitch 84～98.4, polymer modifiers 1～10, clay of laminar silicate 0.5～5, organic amine intercalation auxiliary agent 0.1～1 are chosen pitch, polymer modifiers, clay of laminar silicate and organic amine intercalation auxiliary agent, and be standby;
(2) add heated bitumen to 150～180 ℃, add polymer modifiers, start shear mixer, high-speed stirring is 0.5～1 hour under the rotating speed of 2000～6000rpm, and keeping temperature is 150～180 ℃;
(3) add organic amine intercalation auxiliary agent, keeping temperature is 150～180 ℃, stirring reaction 0.5～1 hour;
(4) add clay of laminar silicate, keeping temperature is 150～180 ℃, and high-speed stirring is 0.5～1 hour under the rotating speed of 2000～6000rpm;
(5) stirring velocity is reduced to 500～1000rpm, keeping temperature is 150～180 ℃, continues to stir 2～3 hours, makes age-resistant modified asphalt.
Beneficial effect of the present invention is as follows:
One. by in polymer modified asphalt, adding organic amine intercalation auxiliary agent, the reaction product of utilizing organic amine intercalation auxiliary agent and asphaltous acid and asphaltous acid anhydrides reaction generation is as intercalator, the surface that makes layered silicate lamella (as common sodium-based montmorillonite or the common tired stone that takes off) is by the hydrophilic oleophylic that is converted into, being beneficial to pitch and polymer molecule enters in the silicate lamella, impel the silicate synusia to peel off, it is compound to realize that common layered silicate and polymer modified asphalt form stripping nano, significantly improve the polymer modified asphalt ageing-resistant performance, prolong the work-ing life of bituminous pavement.
They are two years old. because under organic amine intercalation promoter effect, only need use common layered silicate to form exfoliated nano combined with polymer modified asphalt, than the layered silicate that organises, cost significantly reduces, thereby prepared age-resistant modified asphalt has high cost performance.
Description of drawings
Fig. 1 is the imvite modified bituminous XRD figure spectrum of embodiments of the invention 1
Among the figure: the common polynite of a-; B-does not add the imvite modified pitch of organic amine; C-adds the imvite modified pitch of organic amine; 2 θ,
0Scanning angle when being the XRD test.
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to the following examples.
Embodiment 1:
With 4.8 parts of (mass parts, below identical) styrene-butadiene rubber(SBR) (SBR) is added to 92.9 parts of pitch (47 ℃ of softening temperatures that have been warming up to 160 ℃, penetration degree 75dmm) in, keeping temperature is 160～170 ℃, under the rotating speed of 5000rpm, stir 1h, add 0.2 part of n-Laurylamine and 0.1 part of hexanolactam, keeping temperature is 160～170 ℃, stirring reaction is 0.5 hour under the rotating speed of 3000rpm, adds 2 parts of common sodium-based montmorillonites (particle diameter is 325 orders) again, keeps temperature to be 160～170 ℃ and continues to stir 1h, then stirring velocity is transferred to 1000rpm, keeping temperature is 160～170 ℃, stirs 2h, promptly obtains a kind of age-resistant modified asphalt.This modifying asphalt is carried out pressure ageing tank test (PAV), and 135 ℃ of viscosity before and after modifying asphalt is aging are increased to 2650cp by 2130cp, have increased 520cp, and 5 ℃ of ductilities are reduced to 27.8cm by 42.3cm, have reduced 14.5cm.And do not add the common sodium-based montmorillonite modifying asphalt of organic amine intercalation auxiliary agent, and before and after PAV was aging, 135 ℃ of viscosity were increased to 3300cp by 2430cp, have increased 870cp, and 5 ℃ of ductilities are reduced to 26.5cm by 45.7cm, have reduced 21cm.Two compare, and the modifying asphalt that adds organic amine intercalation auxiliary agent is before and after PAV is aging, and viscosity increases and the ductility minimizing all is starkly lower than the modifying asphalt that does not add organic amine intercalation auxiliary agent, thereby has more good ageing resistance.
Be the further effect of checking organic amine intercalation auxiliary agent, to common polynite, use or do not use the imvite modified pitch of organic amine intercalation auxiliary agent to carry out X-ray diffraction analysis (XRD) respectively, the results are shown in Fig. 1.As seen from Figure 1, the interlamellar spacing of common polynite is 1.91nm, the cheating engaging layer spacing that does not add in the modifying asphalt of organic amine intercalation auxiliary agent is increased to 4.24nm, and it is compound to have formed intercalation nano, and the montmorillonite layer that adds in the modifying asphalt of organic amine intercalation auxiliary agent is stripped from.
Embodiment 2:
3.5 parts of styrene-butadiene-styrene inlay section thermal plastic elastic bodies (SBS) are added to 94.2 parts of pitch (47 ℃ of softening temperatures that have been warming up to 180 ℃, penetration degree 75dmm) in, keeping temperature is 170～180 ℃, under the rotating speed of 5000rpm, stir 1h, add 0.3 part of octadecane amine, keeping temperature is 170～180 ℃, stirring reaction is 1 hour under the rotating speed of 3000rpm, add 2 parts of common sodium-based montmorillonites (particle diameter is 325 orders) again, keeping temperature is 170～180 ℃, continues high-speed stirring 1h, then stirring velocity is transferred to 1000rpm, keeping temperature is 170～180 ℃, stirs 2h, promptly obtains a kind of age-resistant modified asphalt.135 ℃ of viscosity before and after this modifying asphalt PAV is aging are increased to 3020cp by 2490cp, have increased 530cp, and softening temperature is reduced to 64.2 ℃ by 67.1 ℃, has reduced 2.9 ℃.And do not add the sodium-based montmorillonite modifying asphalt of organic amine intercalation auxiliary agent, and before and after PAV was aging, 135 ℃ of viscosity were increased to 2950cp by 2170cp, have increased 780cp, and softening temperature is reduced to 61.6 ℃ by 66.4 ℃, has reduced 4.8 ℃.Similar with embodiment 1, the modifying asphalt that adds organic amine intercalation auxiliary agent has better ageing resistance.
Embodiment 3:
4 parts of SBS and 2 parts of SBR are added to 88.5 parts have been warming up in 180 ℃ the pitch (47 ℃ of softening temperatures, penetration degree 75dmm), keeping temperature is 170～180 ℃, stirs 1h under the rotating speed of 5000rpm; Add 0.5 part of cetylamine, keeping temperature is 170～180 ℃, and stirring reaction is 1 hour under the rotating speed of 3000rpm; Add 5 parts of common tired stones (particle diameter is 400 orders) that take off again, keeping temperature is 170～180 ℃, continues high-speed stirring 1h; Then stirring velocity is transferred to 1000rpm, keeping temperature is 170～180 ℃, stirs 2h, promptly obtains a kind of age-resistant modified asphalt.This modifying asphalt is carried out 30 days thermal ageings in 70 ℃ of hot air aging casees, 135 ℃ of viscosity of aging front and back are increased to 6720cp by 5900cp, have increased 820cp, and 5 ℃ of ductilities are reduced to 18.4cm by 25.7cm, have reduced 7.3cm.And do not add the common tired stone modifying asphalt that takes off of organic amine intercalation auxiliary agent, and before and after the thermal ageing, 135 ℃ of viscosity are increased to 6635cp by 5420cp, have increased 1215cp, and 5 ℃ of ductilities are reduced to 16cm by 30cm, have reduced 14cm.Similar with embodiment 1, the modifying asphalt that adds organic amine intercalation auxiliary agent has better ageing resistance.
Embodiment 4:
6 parts of SBR are added to 90.6 parts have been warming up in 160 ℃ the pitch (47 ℃ of softening temperatures, penetration degree 75dmm), keeping temperature is 160～170 ℃, stirs 1h under the rotating speed of 5000rpm; Add 0.2 part of hexanolactam, 0.1 part of cetylamine and add 0.1 part of n-Laurylamine, keeping temperature is 160～170 ℃, and stirring reaction is 1 hour under the rotating speed of 3000rpm; Add 3 parts of common tired stones (particle diameter is 300 orders) that take off again, keeping temperature is 160～170 ℃, continues high-speed stirring 1h; Then stirring velocity is transferred to 1000rpm, keeping temperature is 160～170 ℃, stirs 2h, promptly obtains a kind of age-resistant modified asphalt.135 ℃ of viscosity of this modifying asphalt 30 days front and back of thermal ageing in 70 ℃ of hot air aging casees are increased to 3786cp by 2910cp, have increased 876cp, and 5 ℃ of ductilities are reduced to 37cm by 47.5cm, have reduced 10.5cm.And do not add the common tired stone modifying asphalt that takes off of organic amine intercalation auxiliary agent, and before and after the thermal ageing, 135 ℃ of viscosity are increased to 4852cp by 3660cp, have increased 1192cp, and 5 ℃ of ductilities are reduced to 27cm by 48cm, have reduced 21cm.
Embodiment 5:
The preparation method of age-resistant modified asphalt, carry out as follows:
(1) by the shared mass percent of each raw material be: pitch 84, polymer modifiers 10, clay of laminar silicate 5, organic amine intercalation auxiliary agent 1, choose pitch, polymer modifiers, clay of laminar silicate and organic amine intercalation auxiliary agent;
Described pitch is bi tumenf orr oad, and its softening temperature is 40～65 ℃, and 25 ℃ of penetration degrees are greater than 40dmm; Described polymer modifiers is the styrene-butadiene-styrene inlay section thermal plastic elastic body; Described clay of laminar silicate is a sodium-based montmorillonite, and the fineness of sodium-based montmorillonite is 200 orders; Described organic amine intercalation auxiliary agent is a n-Laurylamine;
(2) add heated bitumen to 150 ℃, add polymer modifiers, start shears, high-speed stirring is 0.5 hour under the rotating speed of 2000rpm, and keeping temperature is 150 ℃;
(3) add organic amine intercalation auxiliary agent, keeping temperature is 150 ℃, stirring reaction 0.5 hour;
(4) add clay of laminar silicate, keeping temperature is 150 ℃, and high-speed stirring is 0.5 hour under the rotating speed of 2000rpm;
(5) stirring velocity is reduced to 500rpm, keeping temperature is 150 ℃, continues to stir 2 hours, makes age-resistant modified asphalt.
Embodiment 6:
The preparation method of age-resistant modified asphalt, carry out as follows:
(1) by the shared mass percent of each raw material be: pitch 88, polymer modifiers 8, clay of laminar silicate 3.5, organic amine intercalation auxiliary agent 0.5, choose pitch, polymer modifiers, clay of laminar silicate and organic amine intercalation auxiliary agent, standby;
Described pitch is bi tumenf orr oad, and its softening temperature is 40～65 ℃, and 25 ℃ of penetration degrees are greater than 40dmm; Described polymer modifiers is styrene-butadiene-styrene inlay section thermal plastic elastic body and styrene-butadiene rubber(SBR), and wherein the shared mass percent of styrene-butadiene-styrene inlay section thermal plastic elastic body is 4, and the shared mass percent of styrene-butadiene rubber(SBR) is 4; Described clay of laminar silicate is the tired stone that takes off, and tired fineness of taking off stone is 200 orders; Described organic amine intercalation auxiliary agent is octadecane amine and hexanolactam, and the shared mass percent of octadecane amine is 0.3, and the shared mass percent of hexanolactam is 0.2;
(2) add heated bitumen to 150 ℃, add polymer modifiers, start shears, high-speed stirring is 0.5 hour under the rotating speed of 2000rpm, and keeping temperature is 150 ℃;
(3) add organic amine intercalation auxiliary agent, keeping temperature is 150 ℃, stirring reaction 0.5 hour;
(4) add clay of laminar silicate, keeping temperature is 150 ℃, and high-speed stirring is 0.5 hour under the rotating speed of 2000rpm;
(5) stirring velocity is reduced to 500rpm, keeping temperature is 150 ℃, continues to stir 2 hours, makes age-resistant modified asphalt.
Embodiment 7:
The preparation method of age-resistant modified asphalt, carry out as follows:
(1) by the shared mass percent of each raw material be: pitch 94, polymer modifiers 3, clay of laminar silicate 2.6, organic amine intercalation auxiliary agent 0.4 are chosen pitch, polymer modifiers, clay of laminar silicate and organic amine intercalation auxiliary agent;
Described pitch is bi tumenf orr oad, and its softening temperature is 40～65 ℃, and 25 ℃ of penetration degrees are greater than 40dmm; Described polymer modifiers is styrene-butadiene-styrene inlay section thermal plastic elastic body and styrene-butadiene rubber(SBR), and wherein the shared mass percent of styrene-butadiene-styrene inlay section thermal plastic elastic body is 1, and the shared mass percent of styrene-butadiene rubber(SBR) is 2; Described clay of laminar silicate is the tired stone that takes off, and tired fineness of taking off stone is 600 orders; Described organic amine intercalation auxiliary agent is n-Laurylamine, cetylamine, octadecane amine and hexanolactam, wherein the shared mass percent of n-Laurylamine is 0.1, the shared mass percent of cetylamine is 0.1, and the shared mass percent of octadecane amine is 0.1, and the shared mass percent of hexanolactam is 0.1;
(2) add heated bitumen to 180 ℃, add polymer modifiers, start shears, high-speed stirring is 1 hour under the rotating speed of 6000rpm, and keeping temperature is 180 ℃;
(3) add organic amine intercalation auxiliary agent, keeping temperature is 180 ℃, stirring reaction 1 hour;
(4) add clay of laminar silicate, keeping temperature is 180 ℃, and high-speed stirring is 1 hour under the rotating speed of 6000rpm;
(5) stirring velocity is reduced to 1000rpm, keeping temperature is 180 ℃, continues to stir 3 hours, makes age-resistant modified asphalt.
Embodiment 8:
The preparation method of age-resistant modified asphalt, carry out as follows:
(1) by the shared mass percent of each raw material be: pitch 98.4, polymer modifiers 1, clay of laminar silicate 0.5, organic amine intercalation auxiliary agent 0.1 are chosen pitch, polymer modifiers, clay of laminar silicate and organic amine intercalation auxiliary agent;
Described pitch is bi tumenf orr oad, and its softening temperature is 40～65 ℃, and 25 ℃ of penetration degrees are greater than 40dmm; Described polymer modifiers is styrene-butadiene-styrene three inlay section thermal plastic elastic bodies; Described clay of laminar silicate is a sodium-based montmorillonite, and the fineness of sodium-based montmorillonite is 600 orders; Described organic amine intercalation auxiliary agent is a cetylamine;
(2) add heated bitumen to 180 ℃, add polymer modifiers, start shears, high-speed stirring is 1 hour under the rotating speed of 6000rpm, and keeping temperature is 180 ℃;
(3) add organic amine intercalation auxiliary agent, keeping temperature is 180 ℃, stirring reaction 1 hour;
(4) add clay of laminar silicate, keeping temperature is 180 ℃, and high-speed stirring is 1 hour under the rotating speed of 6000rpm;
(5) stirring velocity is reduced to 1000rpm, keeping temperature is 180 ℃, continues to stir 3 hours, makes age-resistant modified asphalt.
Claims (7)
1. age-resistant modified asphalt is characterized in that it is made up of pitch, polymer modifiers, clay of laminar silicate and organic amine intercalation auxiliary agent; The shared mass percent of each raw material is: pitch 84～98.4, polymer modifiers 1～10, clay of laminar silicate 0.5～5, organic amine intercalation auxiliary agent 0.1～1.
2. a kind of age-resistant modified asphalt according to claim 1 is characterized in that: described pitch is bi tumenf orr oad, and its softening temperature is 40～65 ℃, and 25 ℃ of penetration degrees are greater than 40dmm.
3. a kind of age-resistant modified asphalt according to claim 1 is characterized in that: described polymer modifiers is the mixture of a kind of in styrene-butadiene-styrene three inlay section thermal plastic elastic bodies, the styrene-butadiene rubber(SBR) or two kinds, during mixing be arbitrarily than.
4. a kind of age-resistant modified asphalt according to claim 1 is characterized in that: described clay of laminar silicate is sodium-based montmorillonite or tires out and take off stone that the fineness of sodium-based montmorillonite is 200～600 orders, and tired fineness of taking off stone is 200～600 orders.
5. a kind of age-resistant modified asphalt according to claim 1, it is characterized in that: described organic amine intercalation auxiliary agent is any one or any one the above mixture in n-Laurylamine, cetylamine, octadecane amine, the hexanolactam, during mixing be any than.
6. a kind of age-resistant modified asphalt according to claim 1 is characterized in that: the shared mass percent of each raw material is: pitch 88～94, polymer modifiers 3～8, clay of laminar silicate 1～4, organic amine intercalation auxiliary agent 0.3～0.8.
7. the preparation method of age-resistant modified asphalt as claimed in claim 1 is characterized in that carrying out as follows:
(1) by the shared mass percent of each raw material be: pitch 84～98.4, polymer modifiers 1～10, clay of laminar silicate 0.5～5, organic amine intercalation auxiliary agent 0.1～1 are chosen pitch, polymer modifiers, clay of laminar silicate and organic amine intercalation auxiliary agent, and be standby;
(2) add heated bitumen to 150～180 ℃, add polymer modifiers, start shear mixer, high-speed stirring is 0.5～1 hour under the rotating speed of 2000～6000rpm, and keeping temperature is 150～180 ℃;
(3) add organic amine intercalation auxiliary agent, keeping temperature is 150～180 ℃, stirring reaction 0.5～1 hour;
(4) add clay of laminar silicate, keeping temperature is 150～180 ℃, and high-speed stirring is 0.5～1 hour under the rotating speed of 2000～6000rpm;
(5) stirring velocity is reduced to 500～1000rpm, keeping temperature is 150～180 ℃, continues to stir 2～3 hours, makes age-resistant modified asphalt.
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