Background technology
In highway industry ground surface material, hot mixed rubber asphalt mixture still occupies most ratios at present.The mix temperature of General Purpose Rubber asphalt is 165 ℃ of left and right, and modified rubber asphalt mixture temperature is 175 ℃ of left and right, uses at present more and more widely the multifunctional type such as SMA, OGFC road surface mix temperature 190 ℃ of left and right.Rubber asphalt and mineral aggregate are heated to so high temperature, not only consumed a large amount of energy, aggravation rubber asphalt is aging, and can give off a large amount of greenhouse gases, rubber asphalt smog, dust in producing and constructing, and endangers greatly workmen's safety, contaminate environment.
If the temperature of rubber-asphalt mixture can reduce by 20 ℃, rubber-asphalt mixture per ton can fuel saving 1.5-2.0 kilogram, carbonic acid gas and smoke discharge amount reduce by 50% left and right, the toxic substances such as the gases such as sulfurous gas, nitrogen protoxide, nitrogen peroxide can reduce by 70% left and right, rubber asphalt smog can reduce by 80% left and right.
Therefore the mix temperature that, how to reduce rubber-asphalt mixture is current study hotspot.Prior art mainly contains cold mixing rubber-asphalt mixture and two kinds of methods of warm-mixing rubber-asphalt mixture.Although and cold mixing rubber-asphalt mixture has some superiority aspect environmental protection and energy saving, its pavement performance is poor, can only, as urgent repairing prediction scheme, be difficult to meet the big area making of high grade pavement.
And that warm mix technology mainly contains mineral zeolite process, South Africa SOSABIT method, surfactant method etc. is several, the technical study of tensio-active agent was more in recent years.
Chinese patent 201020233760.9 has been recorded rubber asphalt warm-mixing agent and by the rubber-asphalt mixture of its mix and the preparation method of the two, wherein rubber asphalt warm-mixing agent is comprised of alkyl amine cats product, amides cats product, quaternaries cation, tensio-active agent, calcium chloride water, wherein the ratio of water accounts for 81.5%-90%, and water vapour is very serious to the equipment corrosion of rubber-asphalt mixture mixing building under high temperature, simultaneously, a large amount of water also can make rubber-asphalt mixture foaming, reduces rubber asphalt and the adhesivity of gathering materials.
201,010,129,727 1 kinds of build road surface rubber-asphalt mixture warm-mixing additives of Chinese patent are comprised of xylogen amine salt, polyoxyethylene octylphenol ether, amine antistripping agent, hydrochloric acid, service water, and wherein service water accounts for 80.46-86.33%.In this warm-mixing additive, contain hydrochloric acid, the storage of warm-mixing agent with add in can etching apparatus, though amine antistripping agent can improve rubber asphalt and the adhesivity of gathering materials, but a large amount of water still can corrode rubber-asphalt mixture mixing equipment, the weather resistance of rubber-asphalt mixture makes fastidious simultaneously.
Rubber asphalt warm-mixing agent or the additive of these patents, add and use inconvenience, water in component at high temperature forms water vapour, can corrode mixing building equipment, simultaneously, the water stability of warm-mixing rubber-asphalt mixture can be reduced with high-temperature behavior, be difficult to reach the effect of hot mixed rubber asphalt mixture.
Summary of the invention
The object of this invention is to provide a kind of rubber asphalt high-temperature viscosity reducer, its preparation method and application thereof.
For solving the problems of the technologies described above, technical scheme of the present invention is:
A rubber asphalt high-temperature viscosity reducer, its raw material comprises: 100 parts of oxidized polyethlene wax, higher fatty acid 5-40 part, metal hydroxides 10-50 part, described umber is mass fraction.
In order to enhance product performance, described higher fatty acid is the mixture of stearic acid or oleic acid or both any proportionings; Described metal hydroxides is calcium hydroxide.
The preparation method of above-mentioned rubber asphalt high-temperature viscosity reducer, comprises the following steps:
A, 100 parts of oxidized polyethlene wax and higher fatty acid 5-40 part are mixed, and be dissolved in organic solvent;
B, to adding quality consumption in steps A gained material, be the acid catalyst of the 1-12% of steps A gained quality of material, at 120-150 ℃, reaction 1-5h;
C, the organic solvent in step B gained material is steamed;
D, the water of 5-15 times that is metal hydroxides quality by metal hydroxides 10-50 part and quality mix;
E, residuum and step D gained material that step C is steamed to organic solvent mix, and at 30-80 ℃, reaction 1h-3h, obtains rubber asphalt high-temperature viscosity reducer;
Described organic solvent is toluene, dimethylbenzene, hexanaphthene or hexane.
As long as the consumption of above-mentioned organic solvent, so that material dissolution is as the criterion,, by the material dissolution adding in them, is considered the problem of cost and speed of reaction, and the consumption of organic solvent is not too much.
Above-mentioned steps C refers to: during the organic solvent in step B gained material is steamed.
In order to improve product purity, improve product performance, the preparation method of above-mentioned rubber asphalt high-temperature viscosity reducer, also comprises step e, by step e gained rubber asphalt high-temperature viscosity reducer, purification by liquid extraction; Above-mentioned acid catalyst is the vitriol oil or concentrated hydrochloric acid; Above-mentioned metal hydroxides is calcium hydroxide; Above-mentioned organic solvent is toluene.
Above-mentioned concentrated hydrochloric acid refers to that mass fraction surpasses 37% hydrochloric acid; The vitriol oil refers to the sulphuric acid soln that mass concentration is greater than 70%.
In order to improve extraction efficiency, during purification by liquid extraction, solvent for use is that volume ratio is water and the ethyl acetate of (1:2)-(1:1), the quality of solvent for use be rubber asphalt high-temperature viscosity reducer raw material total mass 2-4 doubly; Collect upper strata liquid, upper strata liquid is distilled and removes ethyl acetate, and residuum is dried, is milled.
Above-mentioned upper strata liquid refers to after extraction concussion, stratification, can form water layer under, ethyl acetate is at upper layered structure.
Above-mentioned a kind of rubber asphalt high-temperature viscosity reducer, when it is used for production warm mix type rubber modified bitumen, its production technique is: first rubber modified bitumen is heated to 170 ℃ of molten states, then add the rubber asphalt high-temperature viscosity reducer (accounting for the mass percent of rubber modified bitumen) of 5%-10% to carry out stirring at low speed 10-30min, stirring velocity is 400-1000 rev/min, then adopt colloidal mill to grind 20-40min, after grinding finishes, again rubber asphalt temperature is reduced to 140 ℃ and carries out accumulating, can make warm mix type rubber modified bitumen.
Above-mentioned a kind of rubber asphalt high temperature viscosity reduction modifier, when it is directly used for production warm mix type rubber-asphalt mixture, its production technique is:
To gather materials and be warming up to 150 ℃, then add in agitator kettle, then spray into hot rubber asphalt, after stirring 30s, drop into the rubber asphalt high-temperature viscosity reducer (accounting for the mass ratio of rubber asphalt) of 5%-10%, continue mix 5-10s, then add breeze to stir 5-10s and can make warm mix type rubber-asphalt mixture.
Rubber asphalt high-temperature viscosity reducer of the present invention is pressed powder, adds easy to use.Applicant finds after deliberation, at toluene etc., as solvent, the vitriol oil etc., under the condition as catalyzer, there is esterification in the oxidized polyethlene wax in its component and higher fatty acid, hydroxyl in oxidized polyethlene wax and the carboxyl in the higher fatty acid generation derivative that reacts, has reduced the bonding state of rubber asphalt and surface of aggregate greatly.OH in the metal hydroxidess such as the carboxyl in this derivative (have carboxyl in oxidized polyethlene wax, react also carboxyl of incomplete higher fatty acid) and calcium hydroxide
-under condition at water as solvent, there is neutralization reaction, the salt producing not only can make the Van der Waals force between divide-colloid of rubber asphalt matter-fragrance reduce, can make the Van der Waals force between divide-rubber asphalt matter of properties-correcting agent-fragrance reduce simultaneously, there is inside and outside lubricated effect, thereby reduce the viscosity of rubber asphalt self.And oxidized polyethlene wax viscosity is low, softening temperature is high, in reaction process, its softening temperature does not reduce, and the reaction product of production does not interrupt the intermolecular chemical bond of rubber asphalt, and therefore, the high-temperature behavior of rubber asphalt and low-temperature performance are also uninfluenced.
In the preparation of rubber asphalt high-temperature viscosity reducer of the present invention, in reaction, the equal recyclable recycling of organic solvents such as toluene used, acid catalyst, water, ethyl acetate, does not have environmental pollution, and cost is low.While adopting rubber asphalt high-temperature viscosity reducer of the present invention for the production of warm mix type rubber asphalt, also can improve the stability in storage of rubber asphalt, reduce the aging of rubber asphalt.
Rubber asphalt high-temperature viscosity reducer of the present invention; preparation technology is simple; easy to use; can reduce the high temperature viscosity of General Purpose Rubber pitch and rubber modified bitumen; reduce the intermolecular surface and interface tension force of rubber asphalt; thereby reduce the mix temperature of rubber-asphalt mixture, play the object that reduces energy consumption protection of the environment.
Embodiment
In order to understand better the present invention, below in conjunction with embodiment, further illustrate content of the present invention, but content of the present invention is not only confined to the following examples.
The performance index detection method of rubber asphalt is carried out with reference to < < highway engineering pitch and Asphalt Mixture Experiment rules > > JTGE20-2011, the porosity of rubber-asphalt mixture, Marshall stability, immersion residual stability ratio, dynamic stability, the rut degree of depth, the testing method of-10 ℃ of flexural-tensile strains is carried out with reference to < < highway engineering pitch and Asphalt Mixture Experiment rules > > JTG E20-2011.
Embodiment 1:
A rubber asphalt high-temperature viscosity reducer, it is prepared from by oxidized polyethlene wax, higher fatty acid, calcium hydroxide raw material; Each raw material mass mixture ratio is: oxidized polyethlene wax: higher fatty acid: calcium hydroxide=100: 5: 10.
Oxidized polyethlene wax is from sky, Nanjing poem experiment micro mist company limited, and model is PEWO-0502; Higher fatty acid is stearic acid, comes from Shijiazhuang Tai Xin Chemical Co., Ltd., technical grade; Calcium hydroxide is from Jiande City, Zhejiang Province Cheng Shi Gai Ye company limited, and fineness is 300 orders.
The preparation method of above-mentioned rubber asphalt high-temperature viscosity reducer is as follows:
(1) weighed respectively in proportion oxidized polyethlene wax, higher fatty acid, calcium hydroxide, total mass is 300g.
(2) oxidized polyethlene wax and higher fatty acid are added in the there-necked flask that skimmer is housed, then add the toluene of 50ml and the vitriol oil of 10ml, be heated to 70 ℃ and make its dissolving, open electric mixer, be warmed up to rapidly 120 ℃, the reaction times is 1h, then changeing back flow point liquid device is water distilling apparatus, be heated to 150 ℃, steam toluene, obtain initial esterification products.
(3) calcium hydroxide is added 150ml water be configured to suspension liquid, then esterification products step (2) being prepared adds the calcium hydroxide suspension liquid configuring, high-speed stirring at 30 ℃, the stirring reaction time is 1h, obtain target product, after thick product is extracted, distills, is dried, is milled, obtain the finished product.Wherein extract 3 times, in extraction liquid, the volume ratio of water and ethyl acetate is 1:1, and each extraction liquid quality is 600g.
Select homemade rubber asphalt evaluation to think the action effect of asphalt high-temperature viscosity-depression agent, homemade rubber asphalt preparation technology is: SK-70 heavy traffic paving asphalt is heated to 180 ℃ of molten states, then add 18% 40 object waste rubber powders (accounting for the mass ratio of heavy traffic paving asphalt), can make rubber asphalt stir 1h under the rotating speed of 800 revs/min after.
The rubber asphalt high-temperature viscosity reducer of preparing is added into the warm mix type rubber modified bitumen of preparing in homemade rubber asphalt, its preparation technology is: by homemade rubber asphalt heating to 170 ℃, add 5% rubber asphalt high-temperature viscosity reducer, then stirring at low speed is 10 minutes, rotating speed is 800 revs/min, adopt and then colloidal mill to grind 20min, then stirring at low speed is 10 minutes, rotating speed is 800 revs/min, when stirring at low speed, make rubber asphalt temperature be reduced to 140 ℃, after taking the dish out of the pot, make warm mix type rubber modified bitumen.The technical indicator of prepared warm mix type rubber modified bitumen is as shown in table 2.
The performance of the warm mix type rubber modified bitumen that the rubber asphalt high-temperature viscosity reducer of table 1 different addition quantity is prepared
(weight ratio that rubber asphalt high-temperature viscosity reducer volume ratio is rubber modified bitumen)
As can be seen from Table 1, adopt after rubber asphalt high-temperature viscosity reducer, the high temperature viscosity of rubber asphalt (135 ℃) obviously reduces, and 60 ℃ of viscosity influences are very little, increase along with rubber asphalt high-temperature viscosity reducer volume, 60 ℃ of viscosity of rubber asphalt have increased slightly, and this high-temperature behavior to rubber asphalt is good.Meanwhile, the high-temperature behavior of rubber asphalt (softening temperature), low-temperature performance (ductility), stability in storage do not weaken, and are also slightly improved on the contrary.
For the action effect of rubber asphalt high-temperature viscosity reducer in rubber-asphalt mixture in the present invention is better described, adopted 2 simultaneous tests and embodiment 1 to compare, contrast 1 is hot mixed rubber asphalt mixture (not using rubber asphalt high-temperature viscosity reducer), contrast 2 is warm-mixing rubber-asphalt mixture (not using rubber asphalt high-temperature viscosity reducer), embodiment 1 is warm-mixing rubber-asphalt mixture (having used 5% rubber asphalt high-temperature viscosity reducer of embodiment 1 gained), heat is mixed, the difference of warm mix is the difference of mix temperature, the mix temperature of two comparative examples and embodiment 1 is as shown in table 2, the performance of rubber-asphalt mixture is as shown in table 3.
The preparation technology of rubber-asphalt mixture is: mineral aggregate is added in agitator kettle, then spray into hot rubber asphalt, after stirring 30s, drop into a certain amount of rubber asphalt high-temperature viscosity reducer (accounting for the mass ratio of rubber asphalt), continue mix 5-10s, after adding again breeze to stir 5-10s, can make warm mix type rubber-asphalt mixture, wherein gather materials, the mass ratio of rubber asphalt, breeze is 98:6:2.
Table 2 rubber-asphalt mixture mix temperature is controlled
Classification |
Contrast 1 |
Contrast 2 |
Embodiment 1 |
Rubber asphalt high-temperature viscosity reducer volume (%) |
0 |
0 |
5 |
Gather materials Heating temperature (℃) |
190 |
160 |
160 |
Rubber asphalt heating temperature (℃) |
180 |
150 |
150 |
Mix temperature (℃) |
180 |
150 |
150 |
Compaction temperature (℃) |
175 |
145 |
145 |
Table 3 rubber-asphalt mixture mix performance comparison
Project |
Contrast 1 |
Contrast 2 |
Embodiment 1 |
Porosity (%) |
4.7 |
8.2 |
4.72 |
Marshall stability (kN) |
9.56 |
8.45 |
10.58 |
Immersion residual stability is than (%) |
88.6 |
72.1 |
89.2 |
Dynamic stability (inferior/mm) |
3600 |
1500 |
4200 |
The rut degree of depth (mm) |
1.625 |
4.816 |
1.438 |
-10 ℃ of flexural-tensile strains (10
-6)
|
3342 |
2670 |
3468 |
From table 3, embodiment 1 performance is suitable with contrast 1 performance, high-temperature behavior (dynamic stability, the rut degree of depth) and low-temperature performance (10 ℃ of flexural-tensile strains) slight superiority, show thus to adopt after the rubber asphalt high-temperature viscosity reducer of this patent invention, the mix temperature of rubber-asphalt mixture can reduce by 30 ℃, and pavement performance can meet or exceed hot mixed rubber asphalt mixture completely.From contrast 2 with embodiment 1 to recently, while not adopting rubber asphalt high-temperature viscosity reducer, the porosity of rubber-asphalt mixture is large, water stability energy, high-temperature behavior, low-temperature performance are all very poor, are difficult to meet Pavement Condition.Therefore, the effect of rubber asphalt high-temperature viscosity reducer of the present invention is fairly obvious, and environmental protection and energy saving effect is remarkable.
Embodiment 2:
A rubber asphalt high-temperature viscosity reducer, it is prepared from by oxidized polyethlene wax, higher fatty acid, calcium hydroxide raw material; Each raw material mass mixture ratio is: oxidized polyethlene wax: higher fatty acid: calcium hydroxide=100: 5: 50.
Oxidized polyethlene wax comes from sky, Nanjing poem experiment micro mist company limited, and model is PEWO-0502; Higher fatty acid is oleic acid, and from Jiangsu Golden Horse oil technology Development Co., Ltd, model is RLYS-I; Calcium hydroxide is from Jiande City, Zhejiang Province Cheng Shi Gai Ye company limited, and fineness is 300 orders.
The preparation method of above-mentioned rubber asphalt high-temperature viscosity reducer is as follows:
(1) weighed respectively in proportion oxidized polyethlene wax, higher fatty acid, calcium hydroxide, total mass is 300g.
(2) oxidized polyethlene wax and higher fatty acid are added in the there-necked flask that skimmer is housed, then add the toluene of 60ml and the vitriol oil of 30g, be heated to 70 ℃ and make its dissolving, open electric mixer, be warmed up to rapidly 130 ℃, the reaction times is 2.5h, then changeing back flow point liquid device is water distilling apparatus, be heated to 150 ℃, steam toluene, obtain initial esterification products.
(3) calcium hydroxide is added 600ml water be configured to suspension liquid, the esterification products so step (2) being prepared adds the calcium hydroxide suspension liquid configuring, high-speed stirring at 40 ℃, the stirring reaction time is 2h, obtain target product, after thick product is extracted, distills, is dried, is milled, obtain the finished product.Wherein extract 3 times, in extraction liquid, the volume ratio of water and ethyl acetate is 1:2, and each extraction liquid quality is 1200g.
Embodiment 3:
A rubber asphalt high-temperature viscosity reducer, it is prepared from by oxidized polyethlene wax, higher fatty acid, calcium hydroxide raw material; Each raw material mass mixture ratio is: oxidized polyethlene wax: higher fatty acid: calcium hydroxide=100: 40: 50; Higher fatty acid is stearic acid, comes from Shijiazhuang Tai Xin Chemical Co., Ltd., technical grade; Calcium hydroxide is from Jiande City, Zhejiang Province Cheng Shi Gai Ye company limited, and fineness is 300 orders.
The preparation method of above-mentioned rubber asphalt high-temperature viscosity reducer is as follows:
(1) weighed respectively in proportion oxidized polyethlene wax, higher fatty acid, calcium hydroxide, total mass is 300g.
(2) oxidized polyethlene wax and higher fatty acid are added in the there-necked flask that skimmer is housed, then add the toluene of 80ml and the vitriol oil of 40g, be heated to 70 ℃ and make its dissolving, open electric mixer, be warmed up to rapidly 150 ℃, the reaction times is 5h, then changeing back flow point liquid device is water distilling apparatus, be heated to 150 ℃, steam toluene, obtain initial esterification products.
(3) calcium hydroxide is added 750ml water be configured to suspension liquid, the finished product of the esterification products then step (2) being prepared adds the calcium hydroxide suspension liquid configuring, high-speed stirring at 80 ℃, the stirring reaction time is 3h, obtain target product, after thick product is extracted, distills, is dried, is milled, obtain the finished product.Wherein extract 3 times, in extraction liquid, the volume ratio of water and ethyl acetate is 1:1.5, and each extraction liquid quality is 800g.
Embodiment 4:
A rubber asphalt high-temperature viscosity reducer, it is prepared from by oxidized polyethlene wax, higher fatty acid, calcium hydroxide raw material; Each raw material mass mixture ratio is: oxidized polyethlene wax: higher fatty acid: calcium hydroxide=100: 40: 10.
Oxidized polyethlene wax is from sky, Nanjing poem experiment micro mist company limited, and model is PEWO-0505; Higher fatty acid is oleic acid, comes from Dongying sea, Shandong Chemical Co., Ltd. of Futong; Calcium hydroxide is from Zibo Han Xiang Trade Co., Ltd., and fineness is 325 orders.
The preparation method of above-mentioned rubber asphalt high-temperature viscosity reducer is as follows.
(1) weighed respectively in proportion oxidized polyethlene wax, higher fatty acid, calcium hydroxide, total mass is 300g.
(2) oxidized polyethlene wax and higher fatty acid are added in the there-necked flask that skimmer is housed, then add the toluene of 60ml and the vitriol oil of 40g, be heated to 70 ℃ and make its dissolving, open electric mixer, be warmed up to rapidly 150 ℃, the reaction times is 1h, then changeing back flow point liquid device is water distilling apparatus, be heated to 150 ℃, steam toluene, obtain initial esterification products.
(3) calcium hydroxide is added 300ml water be configured to suspension liquid, the finished product of the esterification products then step (2) being prepared adds the calcium hydroxide suspension liquid configuring, high-speed stirring at 70 ℃, the stirring reaction time is 2.5h, obtain target product, after thick product is extracted, distills, is dried, is milled, obtain the finished product.Wherein extract 3 times, in extraction liquid, the volume ratio of water and ethyl acetate is 1:1, and each extraction liquid quality is 1000g.
Embodiment 5:
A rubber asphalt high-temperature viscosity reducer, it is prepared from by oxidized polyethlene wax, higher fatty acid, calcium hydroxide raw material; Each raw material mass mixture ratio is: oxidized polyethlene wax: higher fatty acid: calcium hydroxide=100: 20: 30, total mass was 300g.
Oxidized polyethlene wax is from Yangzhou rowland novel material company limited, and model is OPE; Higher fatty acid is stearic acid, comes from Shijiazhuang Tai Xin Chemical Co., Ltd., technical grade; Calcium hydroxide is from Zibo Han Xiang Trade Co., Ltd., and fineness is 325 orders.
The preparation method of above-mentioned rubber asphalt high-temperature viscosity reducer as described in Example 2.
Embodiment 6:
A rubber asphalt high-temperature viscosity reducer, it is prepared from by oxidized polyethlene wax, higher fatty acid, calcium hydroxide raw material; Each raw material mass mixture ratio is: oxidized polyethlene wax: higher fatty acid: calcium hydroxide=100: 40: 40, total mass was 300g.
Oxidized polyethlene wax is from Yangzhou rowland novel material company limited, and model is OPE; Higher fatty acid is oleic acid, and from Jiangsu Golden Horse oil technology Development Co., Ltd, model is RLYS-I; Calcium hydroxide is from Zibo Han Xiang Trade Co., Ltd., and fineness is 325 orders.
The preparation method of above-mentioned rubber asphalt high-temperature viscosity reducer as described in Example 3.
The rubber asphalt high-temperature viscosity reducer of above embodiment is as shown in table 4 to the viscosity reducing effect of rubber modified bitumen:
The performance of the warm mix type rubber modified bitumen that the rubber asphalt high-temperature viscosity reducer of each embodiment of table 4 is prepared
(rubber asphalt high-temperature viscosity reducer volume ratio be rubber modified bitumen weight 6%)
When the rubber asphalt high-temperature viscosity reducer of several embodiment is used for preparing warm-mixing rubber-asphalt mixture, its temperature is controlled as shown in table 5:
Table 5 rubber-asphalt mixture mix temperature is controlled
Rubber asphalt high-temperature viscosity reducer is as shown in table 6 to the action effect of rubber-asphalt mixture:
Table 3 rubber-asphalt mixture mix performance comparison
Each raw material that the present invention is cited and the bound value of each raw material, can realize the present invention, at this, do not enumerate embodiment.