CN110511579A - A kind of ageing-resistant asphalt modifier and preparation method thereof and ageing-resistant pitch - Google Patents
A kind of ageing-resistant asphalt modifier and preparation method thereof and ageing-resistant pitch Download PDFInfo
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- CN110511579A CN110511579A CN201910708670.1A CN201910708670A CN110511579A CN 110511579 A CN110511579 A CN 110511579A CN 201910708670 A CN201910708670 A CN 201910708670A CN 110511579 A CN110511579 A CN 110511579A
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- hydrotalcite
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The purpose of the application is to provide a kind of ageing-resistant asphalt modifier and preparation method thereof and ageing-resistant pitch, the salicylate intercalated houghite that the hydrotalcite and mass percent that the ageing-resistant asphalt modifier is 0%~30% by mass percent are 70%~100% forms, wherein, using hydrotalcite and salicylic acid as raw material, hydrotalcite and salicylic molar ratio are 1:4 for the preparation of salicylate intercalated houghite.The ageing-resistant asphalt modifier that the application obtains is low in cost, preparation is simple, and the anti-aging property of pitch can be significantly improved after to asphalt modification, ageing-resistant asphalt modifier used in this application has good application prospect to the ageing resistance that can improve pitch after asphalt modification.
Description
Technical field
The present invention relates to field of bitumen technology, and in particular to a kind of ageing-resistant asphalt modifier and preparation method thereof and resistance to old
Change pitch.
Background technique
In recent years, Xinjiang expressway construction was developed rapidly, to the end of the year 2015, the built high speed in Xinjiang
Total mileage of highway is up to 4316 kilometers.According to planning, the year two thousand twenty is arrived, Xinjiang will strive completing Transportation Infrastructure Construction investment 10,000
Hundred million yuan, about 15.2 ten thousand kilometers of total kilometrage are built, wherein about 8500 kilometers of highway, at that time, Xinjiang will build up ten thousand kilometers of high speeds
Highway main framing.However Xinjiang their location solar energy is abundant, ultraviolet irradiation intensity is big, bituminous pavement easily aging, and then produces
Raw to destroy, not only Xinjiang is in this way, China is entire western most of regional all in ultraviolet strong irradiated site, as west area is handed over
The flat further rapid development of water flowing and its complicated special climatic environment requirement, these areas will certainly be to asphalt roads
Durability put forward higher requirements.Therefore, high performance ageing-resistant asphalt modifier is prepared for the pitch in west area
The anti-aging of road has very important significance.
Having always both at home and abroad can be carried out research to the resistance to ag(e)ing of pitch, to increase pitch ageing-resistant performance, commonly
Method is to asphalt modification.Currently used asphalt modifier is SBR modifying agent and SBS modifier.
Such as Chinese patent 200810204209.4 uses SBR modifier modification pitch, and proposes in SBR modified pitch
Middle addition can absorb the CeO of ultraviolet light2Nanoparticle or ultraviolet absorber UV531, can significantly improve SBR modified pavement asphalt
Resistance to UV aging.But CeO2Nanoparticle forms the dispersion of nanoscale in pitch, it is necessary first to using coprecipitated
Shallow lake method is subject to Mr.'s high-temperature calcination powdering modifying agent, it is also necessary to be prepared as slurries dress using ultrasonic wave dispersion in dispersing agent and change
Property agent, be used further to asphalt modification, prepare in the industrial production more difficult.
Therefore, how preparation process is simple, the significantly ageing-resistant modifying agent of effect becomes the ageing-resistant project of current pitch
Hot spot.
Summary of the invention
The shortcomings that for the above-mentioned prior art or deficiency, the application technical problems to be solved are to develop a kind of preparation process
Simple and effective asphalt modifier increases pitch ageing-resistant performance.
In order to solve the above technical problems, the ageing-resistant pitch changes this application provides a kind of ageing-resistant asphalt modifier
Property agent is by the first hydrotalcite that mass percent is 0%~30% and the salicylic acid root cutting that mass percent is 70%~100%
Layer hydrotalcite composition.
Preferably, the first hydrotalcite and 75% that the ageing-resistant asphalt modifier is 5%~25% by mass percent
~95% salicylate intercalated houghite composition.
Preferably, the first hydrotalcite and 80% that the ageing-resistant asphalt modifier is 10%~20% by mass percent
~90% salicylate intercalated houghite composition.
Preferably, first hydrotalcite is magnalium carbonate hydrotalcite, and specific molecular formula is
[Mg1-X AlX(OH)2]X+[(CO3)X/2]X-·mH2O, 0.2≤X≤0.33,0.1≤m≤0.8, wherein subscript X refers to
The changes of contents of metallic element, m represent the quantity of the crystallization water.First hydrotalcite can be the naturally occurring magnalium of nature
Carbonate hydrotalcite, or the magnalium carbonate hydrotalcite of coprecipitation preparation.
Preferably, the preparation preparation method of the salicylate intercalated houghite includes the following steps:
Weigh the second hydrotalcite and salicylic acid that molar ratio is 1:4, second hydrotalcite and first hydrotalcite
Ingredient, molecular formula are all the same；
The salicylic acid is heated to be dissolved in ethylene glycol after 40~80 DEG C and is configured to solution A；
Second hydrotalcite is added in the solution A and is uniformly dispersed, slurries B is made；
The pH value of the slurries B is adjusted to 3~4 with alkaline solution, is stirred to react 1~2h at a temperature of 140~160 DEG C,
Solid matter is obtained by filtration；
By solid matter washing, dry, grinding, salicylate intercalated houghite is made.
Preferably, the dispersing agent is ethylene glycol, propylene glycol, normal propyl alcohol, n-butanol, isobutanol, one in isoamyl alcohol
Kind is several, wherein is arbitrary proportion when several dispersants.
Preferably, the fineness of first hydrotalcite is 200~600 mesh, the fineness of the salicylate intercalated houghite
For 200~600 mesh.
Preferably, the alkaline solution is NaOH.
Present invention also provides a kind of preparation methods of ageing-resistant asphalt modifier, include the following steps:
S1: salicylate intercalated houghite is prepared.
S2: the salicylate intercalated houghite quality hundred for being 70%~100% by the mass percent being prepared in S1
Divide than being uniformly mixed for 0%~30% the first hydrotalcite.
A kind of ageing-resistant pitch, the ageing-resistant pitch are mixed by ageing-resistant asphalt modifier with pitch, wherein institute
The mass ratio for stating ageing-resistant asphalt modifier and the pitch is 0.04~0.1:1.
The present invention prepares more complicated defect for asphalt modifier in the prior art, provides a kind of ageing-resistant pitch
Modifying agent and preparation method thereof, and ageing-resistant asphalt modifier is used for modified pitch.Use hydrotalcite and salicylic acid as original
Material prepares salicylate intercalated houghite, and will make salicylate intercalated houghite and hydrotalcite than mixing according to certain mass
Carry out modified pitch for asphalt modifier, obtains ageing-resistant pitch.
It is a kind of ultraviolet-resistant haveing excellent performance since hydrotalcite is a kind of aluminium magensium silicate mineral with layer structure
Material, multistage laminate can multiple reflections and refraction ultraviolet light, play the role of physical shielding to ultraviolet light, the metal on laminate
Element and interlayer anion can play chemisorption to ultraviolet light, and therefore, hydrotalcite can be effective as asphalt modifier
Using hydrotalcite on the physical shielding and laminate of ultraviolet light metallic element and interlayer anion to the double of ultraviolet radiation absorption
Recast is used, and hydrotalcite does not need nanoscale dispersion as asphalt modifier, and preparation process is relatively simple, and hydrotalcite is as drip
Green modifying agent can significantly improve the anti-ultraviolet ageing performance of pitch, extend the service life of pitch.
In addition, salicylic acid has uv absorption property because of the feature in chemical structure, by salicylic acid in the technical program
Root introduces hydrotalcite layers as object, so that salicylate is replaced carbonate, calcining or ultrasonic wave are not needed in preparation process
The processes such as dispersion, prepare relatively simple, acquired salicylate intercalated houghite material, have biggish interlamellar spacing, good
Thermal stability and shielding absorb action of ultraviolet radiation, therefore, can be effectively sharp using salicylate intercalated houghite as asphalt modifier
The characteristic that ultraviolet light is shielded and absorbed with salicylate intercalated houghite, significantly improves the anti-ultraviolet ageing performance of pitch, extends
The service life of pitch.
Therefore, compared with prior art, a kind of ageing-resistant asphalt modifier preparation process provided in the present invention is simple, is easy to
It realizes, can significantly improve the ageing-resistant performance of pitch.
Detailed description of the invention
By reading a detailed description of non-restrictive embodiments in the light of the attached drawings below, the application's is other
Feature, objects and advantages will become more apparent upon:
Fig. 1: the XRD spectra of hydrotalcite and salicylate intercalated houghite in the application；
Specific embodiment
The present invention is further illustrated below by embodiment.It is base that 70# bi tumenf orr oad is chosen in following embodiment
Matter is mixed to prepare asphalt modifier with hydrotalcite and salicylate intercalated houghite with different quality percentage, due to the first water
The ingredient and molecular formula of talcum and the second hydrotalcite are all the same, refer to the first hydrotalcite or the in embodiment with hydrotalcite
Two hydrotalcites.
Carry out modified pitch using asphalt modifier made from different embodiments, obtains the different modified pitch of each group.
Bitumen ductility refers to the extensibility of pitch, and ductility is bigger, shows that the plasticity of pitch is better.Colloid is reduced in pitch after aging,
Asphalitine increases, and softening point increases, ductility decline.The low-temperature ductility of pitch can react plasticity of the pitch under low-temperature condition,
That is the quality of its non-deformability.The present embodiment is using 5 DEG C of ductility retention rates as the Ageing Index of pitch.
According to " highway engineering pitch and Asphalt Mixture Experiment regulation ", following embodiment record passes through various combination ingredient
Asphalt modifier before modified after 5 DEG C of ductility data being measured in ultraviolet light (UV) degradation of pitch, come with this specific
Illustrate the effect of asphalt modifier.Wherein,
Using SYD-4508C type numerical control soft pitch ductility machine, bitumen ductility is tested, tensile speed 5cm/
Min, unit are indicated with cm.
Ultraviolet light (UV) degradation uses LHX-205 type intelligent numerical control light-heat aging case, uses wavelength for 365nm's
GHF125W-03 type mercury lamp, ultraviolet light irradiation degree are 2000 μ W/m2, and temperature is controlled in (50 ± 0.5) DEG C, ageing time 14d.
Embodiment 1
Hydrotalcite, bigcatkin willow are weighed respectively with the molar ratio of hydrotalcite 0.02mol, salicylic acid 0.08mol, ethylene glycol 0.8mol
Acid and ethylene glycol, are heated to 40 DEG C for salicylic acid, are dissolved in wiring solution-forming A in ethylene glycol, and hydrotalcite is added in solution A and is sufficiently stirred
It mixes, slurries B is made in dispersion, and with the pH value of NaOH solution adjustment slurries B to after 4, slurries B is stirred to react at a temperature of 140 DEG C
It filters, wash after 2h, filtrate is dried in 70 DEG C of baking oven to constant weight, 200 mesh of fineness is ground to, obtains salicylic acid root cutting
Layer hydrotalcite.
In embodiments herein, the X-ray using the model D/max2500PC of Japanese Rigaku company production is spread out
It penetrates (XRD) instrument to characterize hydrotalcite and salicylate intercalated houghite, XRD instrument uses Cu target and K alpha ray source, operation electricity
Pressure and electric current are respectively 40kV and 100mA, and scanning range is 5 ° -90 ° of 2 θ.Since hydrotalcite is layered hydroxide, XRD
Map has the feature of highly significant, and different anion is inserted into the change that interlayer may cause the interlamellar spacing of highly significant
Change.The XRD spectra of salicylate intercalated houghite and hydrotalcite is as shown in Figure 1.A in Fig. 1 is the XRD spectra of hydrotalcite, b
For the XRD spectra of salicylate intercalated houghite.From Fig. 1 a can be seen that hydrotalcite characteristic peak (2 θ=11.6 °, 23.2 °,
34.6 °, 39.2 °, 46.3 ° and 60.7 °), with MgAl-CO on JCPDS standard card3The position of the feature cutting edge of a knife or a sword of hydrotalcite coincide.Two
A opposite biggish diffraction maximum of diffracted intensity correspond to interlamellar spacing 0.784nm (d003) and two senior reflection 0.384nm (d006),
0.257nm(d009)。
From Fig. 1 b as can be seen that relative to Fig. 1 a, 3 characteristic diffraction peaks (d003) in hydrotalcite, (d006) and
(d009) regularly mobile to the low angle of 2 θ, 5.6 °, 11.2 ° and 16.7 ° are moved to respectively, at this time (d003) corresponding layer
Spacing is 1.61nm, and characteristic peak is mobile to the low angle of 2 θ.Since salicylic acid shows that Salicylate ion enters interlayer and takes completely
For CO3 2-, form new salicylate intercalated houghite.
Using the salicylate intercalated houghite of 100% mass percent as asphalt modifier, 4 parts of asphalt modifiers are added
In the 70# bi tumenf orr oad for maintaining 170 DEG C to 96 parts of temperature, the shear rate of 4000/min is kept using high-speed shearing machine
Pitch 50min is sheared, modified pitch 1 is obtained.
Embodiment 2
The places different from embodiment 1 are that the present embodiment is with the salicylate intercalated houghite of 90% mass percent
It is uniformly mixed with 10% hydrotalcite (fineness is 200 mesh) as asphalt modifier, 4 parts of asphalt modifiers is added to 96 parts of temperature
Degree maintains in 170 DEG C of 70# bi tumenf orr oad, keeps the shear rate of 4000/min to shear pitch using high-speed shearing machine
50min obtains modified pitch 2.
Embodiment 3
The places different from embodiment 1 are that the present embodiment is with the salicylate intercalated houghite of 80% mass percent
It is uniformly mixed with 20% hydrotalcite (fineness is 200 mesh) as asphalt modifier, 4 parts of asphalt modifiers is added to 96 parts of temperature
Degree maintains in 170 DEG C of 70# bi tumenf orr oad, keeps the shear rate of 4000/min to shear pitch using high-speed shearing machine
50min obtains modified pitch 3.
Embodiment 4:
The places different from embodiment 1 are that the present embodiment is with the salicylate intercalated houghite of 70% mass percent
It is uniformly mixed with 30% hydrotalcite (fineness is 200 mesh) as asphalt modifier, 4 parts of asphalt modifiers is added to 96 parts of temperature
Degree maintains in 170 DEG C of 70# bi tumenf orr oad, keeps the shear rate of 4000/min to shear pitch using high-speed shearing machine
50min obtains modified pitch 4.
Embodiment 5
The places different from embodiment 2-4 are, the present embodiment without preparing salicylate intercalated houghite, but with
The hydrotalcite (fineness is 200 mesh) of 100% mass percent is used as asphalt modifier, and 4 parts of asphalt modifiers are added to 96 parts
Temperature maintains in 170 DEG C of 70# bi tumenf orr oad, keeps the shear rate of 4000/min to shear drip using high-speed shearing machine
Green 50min obtains modified pitch 5, is denoted as modified pitch 5.
To modified pitch 1 obtained in above-described embodiment, modified pitch 2, modified pitch 3, modified pitch 4 and it is modified
Pitch 5 carries out asphalt with ultraviolet aging test with without modified pitch (blank group).
(1) asphalt with ultraviolet aging disk diameter is 140mm, and sample mass is selected as (20 ± 0.1) g；
(2) use wavelength for the GHF125W-03 type mercury lamp of 365nm, ultraviolet light irradiation degree is 2000 μ W/m2；
(3) each group modified pitch sample is put into ultraviolet ageing case, the ultraviolet ageing time is 14 days, and test temperature is
(50 ± 0.5) DEG C, to guarantee that ultraviolet radiation intensity suffered by bitumen samples surface is identical, bitumen samples are in ultraviolet ageing case
Position carry out regularly circulation exchange.
(4) 5 DEG C ductilities of the pitch before and after degradation in different embodiments are tested and (are denoted as D respectively0And D), ductility is protected
Stay rate DRR=D/D0100%, it is as shown in the table to test obtained data:
From upper table data it is found that being tested either without modified pitch or modified pitch in ultraviolet radioactive
Afterwards, ductility reduces.Correlation data is it is found that using the salicylate intercalated houghite of 100% mass percent as asphalt modifier
Modified pitch (modified pitch 1), 5 DEG C of ductilities after aging are reduced to 27.9cm by 78.5cm, and ductility retention rate is 35.5%；
It is (modified as the modified pitch of asphalt modifier using the hydrotalcite of the salicylate intercalated houghite of 90% mass percent and 10%
Pitch 2), 5 DEG C of ductilities after aging are reduced to 27.4cm by 77.5cm, and ductility retention rate is 35.4%；With 80% mass percentage
The salicylate intercalated houghite of ratio and 20% hydrotalcite be asphalt modifier modified pitch (modified pitch 3), after aging
5 DEG C of ductilities 27.1cm is reduced to by 76.3cm, ductility retention rate is 35.5%；With the salicylic acid root cutting of 70% mass percent
Layer hydrotalcite with 30% hydrotalcite for asphalt modifier modified pitch (modified pitch 4), 5 DEG C of ductilities after aging by
76.0cm is reduced to 27.0cm, and ductility retention rate is 35.5%；Using the hydrotalcite of 100% mass percent as asphalt modifier
Modified pitch (modified pitch 5), 5 DEG C of ductilities after aging are reduced to 26.0cm by 74.4cm, and ductility retention rate is 34.9%；And
Without modified pitch (blank group), 5 DEG C of ductilities after aging are reduced to 25.5cm by 73.7cm, and ductility retention rate is
34.6%.For comparison, pitch (modified pitch) modified before ageing after ductility retention rate be all larger than without changing
Property pitch (blank group), thus have more outstanding ageing-resistant performance (anti-ultraviolet ageing performance).Therefore, hydrotalcite and water
Poplar acid group intercalated houghite has improvement effect to pitch ageing-resistant performance.
Secondly, comprising salicylate intercalated houghite asphalt modifier modified pitch (modified pitch 1, modified pitch 2,
Modified pitch 3, modified pitch 4) ductility retention rate be greater than hydrotalcite asphalt modifier modified pitch.Therefore, salicylate
Intercalated houghite is ageing-resistant to pitch as asphalt modifier better than hydrotalcite to pitch ageing-resistant performance as asphalt modifier
Performance.
In addition, (modified as the modified pitch of asphalt modifier using the salicylate intercalated houghite of 100% mass percent
Pitch 1) modified pitch (modified pitch with the salicylate intercalated houghite of 90% mass percent and 10% hydrotalcite
2), the salicylate intercalated houghite of 80% mass percent and 20% hydrotalcite modified pitch (modified pitch 3), 70%
The salicylate intercalated houghite of mass percent and 30% hydrotalcite modified pitch (modified pitch 4), ductility retention rate
Be 35.5% or so, thus ageing-resistant performance (anti-ultraviolet ageing performance) is quite, thus by salicylate intercalated houghite and
When hydrotalcite mixing is as asphalt modifier, the mass percent value 70%-100% of salicylate intercalated houghite
With preferably, the mass percent value 70% of salicylate intercalated houghite, can save cost of material.
Claims (10)
1. a kind of ageing-resistant asphalt modifier, which is characterized in that the ageing-resistant asphalt modifier by mass percent be 0%~
The salicylate intercalated houghite that 30% the first hydrotalcite and mass percent is 70%~100% forms.
2. ageing-resistant asphalt modifier according to claim 1, which is characterized in that the ageing-resistant asphalt modifier is by matter
Percentage is measured as 5%~25% the first hydrotalcite and 75%~95% salicylate intercalated houghite composition.
3. ageing-resistant asphalt modifier according to claim 1, which is characterized in that the ageing-resistant asphalt modifier is by matter
Percentage is measured as 10%~20% the first hydrotalcite and 80%~90% salicylate intercalated houghite composition.
4. ageing-resistant asphalt modifier according to claim 1, which is characterized in that first hydrotalcite is magnalium carbonic acid
Root hydrotalcite, specific molecular formula are [Mg1-XAlX(OH)2]X+[(CO3)X/2]X-·mH2O, 0.2≤X≤0.33,0.1≤m≤0.8,
Wherein, subscript X refers to the changes of contents of metallic element, and m represents the quantity of the crystallization water.
5. ageing-resistant asphalt modifier according to claim 1, which is characterized in that the salicylate intercalated houghite
Preparation method includes the following steps:
Weigh the second hydrotalcite and salicylic acid that molar ratio is 1:4, the ingredient of second hydrotalcite and first hydrotalcite,
Molecular formula is all the same；
The salicylic acid is heated to be dissolved in ethylene glycol after 40~80 DEG C and is configured to solution A；
Second hydrotalcite is added in the solution A and is uniformly dispersed, slurries B is made；
The pH value for adjusting the slurries B with alkaline solution is stirred to react 1~2h at a temperature of 140~160 DEG C, filters to 3~4
Obtain solid matter；
By solid matter washing, dry, grinding, salicylate intercalated houghite is made.
6. ageing-resistant asphalt modifier according to claim 5, which is characterized in that the dispersing agent is ethylene glycol, the third two
One or more of alcohol, normal propyl alcohol, n-butanol, isobutanol, isoamyl alcohol.
7. ageing-resistant asphalt modifier according to claim 5, which is characterized in that the fineness of first hydrotalcite is
200~600 mesh, the fineness of the salicylate intercalated houghite are 200~600 mesh.
8. ageing-resistant asphalt modifier according to claim 5, which is characterized in that the alkaline solution is that NaOH is molten
Liquid.
9. a kind of preparation method of ageing-resistant asphalt modifier, which comprises the steps of:
S1: salicylate intercalated houghite is prepared.
S2: the salicylate intercalated houghite mass percent for being 70%~100% by the mass percent being prepared in S1
It is uniformly mixed for 0%~30% the first hydrotalcite.
10. a kind of ageing-resistant pitch, which is characterized in that the ageing-resistant pitch is described in any item resistance to old by claim 1 to 8
Change asphalt modifier to mix with pitch, wherein the mass ratio of the ageing-resistant asphalt modifier and the pitch for 0.04~
0.1:1.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910708670.1A CN110511579A (en) | 2019-08-01 | 2019-08-01 | A kind of ageing-resistant asphalt modifier and preparation method thereof and ageing-resistant pitch |
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| CN201910708670.1A CN110511579A (en) | 2019-08-01 | 2019-08-01 | A kind of ageing-resistant asphalt modifier and preparation method thereof and ageing-resistant pitch |
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| CN112980087A (en) * | 2021-02-22 | 2021-06-18 | 李丽 | Insulating material of cable for new energy automobile charging pile and preparation method of insulating material |
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