CN101495576A - Asphalt composition having improved mechanical property and anti-aging property and method of preparing the same - Google Patents
Asphalt composition having improved mechanical property and anti-aging property and method of preparing the same Download PDFInfo
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- CN101495576A CN101495576A CNA200780014548XA CN200780014548A CN101495576A CN 101495576 A CN101495576 A CN 101495576A CN A200780014548X A CNA200780014548X A CN A200780014548XA CN 200780014548 A CN200780014548 A CN 200780014548A CN 101495576 A CN101495576 A CN 101495576A
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- C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
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Abstract
This invention relates to an asphalt composition having improved mechanical properties and anti-aging performance and to a method of preparing the same, and, more particularly, to a method of providing asphalt cement, which has superior mechanical properties, including penetration or ductility, and also has improved storage stability, by mixing asphalt or bitumen with a polymer at a predetermined ratio and selectively adding an additive.
Description
Technical field
The present invention relates to bituminous composition that has improved mechanical property and ageing resistance and preparation method thereof.In particular, the present invention relates to a kind of by pitch (asphalt) or pitch earth (bitumen) are also optionally added the method that additive provides bituminous cement with polymkeric substance according to predetermined mixed, this bituminous cement has excellent mechanical property, comprise penetration degree or ductility, also have improved package stability.
Background technology
In general, depend on production method and production area, pitch is divided into different types.Furtherly, pitch is by the petroleum pitch that roughly is divided into spontaneous rock asphalt and is prepared by crude oil.At present, petroleum pitch has occupied the bituminous overwhelming majority of producing at home and using, and still, still needs import sometimes and uses rock asphalt.Usually, petroleum pitch is the bituminous material that obtains from the vacuum distilling tower bottom in the crude oil purge process, perhaps derives from the oxygenizement of these bituminous materials, and petroleum pitch is mainly used in urban road laying, material of construction, coating and other industrial uses.The bituminous quality mainly is subjected to the influence of oil property.Therefore, use inappropriate crude oil will cause asphalt quality inferior.Furtherly, because pitch is very responsive to the change of temperature, therefore, should prepare the pitch that is suitable for its employed geographic climate characteristic.For example, the pitch that has good quality under the high temperature (60 ℃) may be under room temperature (15 ℃) or low temperature (4 ℃) with low quality.Therefore, select and use the pitch of the weather condition that are suitable for territory of use of institute very important.And, in order to improve the bituminous quality, used the many additives that comprise hydro carbons, still also do not obtain gratifying improvement effect in this respect.
Recently, extensive and deep the development by adding comprises that the material of polymer modifiers improves the research of bituminous character.In U.S. Patent No. 3,985,694 and No.4,130, in 516, be added in the pitch, thereby improve bituminous character such as the polymkeric substance of polyolefine or styrene butadiene rubbers, but, there is such problem, promptly the adhesivity under the room temperature (15 ℃) is not improved.In addition, US patent No.5,221,703 disclose a kind of preparation method with bitumen/polymer composition of improved character, and the improvement of this character is owing to used oil and polymer modifiers, for example styrene butadiene rubbers.In this patent, add polymer modifiers and oil, therefore improved the character that comprises viscosity.Especially, though the character under the low temperature (4 ℃) be improved, to the adhesivity under the room temperature (15 ℃) or to characterize the improvement effect of ageing resistance of ability of storage maintenance quality at high temperature very little or do not have an improvement effect.Also promptly, under the situation that styrene butadiene based polyalcohol properties-correcting agent is at high temperature stored over a long time, oxidation or rotten may take place, this will cause performance degradation.Therefore, when improving performance, prevent from the performance degradation that causes owing to long time stored from promptly to improve ageing resistance, just becoming the problem that becomes more and more important.
Summary of the invention
Correspondingly, be devoted to solve the problems referred to above that occur in the correlation technique and made the present invention, one of purpose of the present invention provides a kind of bituminous composition, and said composition at room temperature has excellent adhesivity, especially, said composition has very big improved ageing resistance.
Formulation with an aspect of of the present present invention of realizing above-mentioned purpose about a kind of method for preparing bituminous composition, this bituminous composition has improved mechanical property and ageing resistance, this method is included under 110-220 ℃, pitch or the pitch earth (component A) of 90-99.9 weight % are mixed with one or more polymkeric substance (B component) of 0.1-10 weight %, described pitch or asphaltic viscosity are 100-1,000,000 pool (60 ℃) and penetration degree are 5-400dmm (1/10mm) (25 ℃), it is 50 that described one or more polymkeric substance are selected from by weight-average molecular weight, 000-2,000,000 and styrene content be the styrene polymer of 20-50 weight %, weight-average molecular weight is 50,000-1,000,000 and ethylene content be the ethylene-methyl acrylate (ethylene methacrylate) of 40-99.7 weight %, ethylene-propylene rubber(EPR) or ethane-acetic acid ethyenyl ester random copolymers, and weight-average molecular weight is 50,000-1, in the group that 000,000 isoprene copolymer is formed.
Formulation with the another aspect of the present invention that realizes above-mentioned purpose about a kind of bituminous composition with improved mechanical property and ageing resistance, said composition contains the pitch of 90-99.9 weight % or one or more polymkeric substance (B component) of pitch earth (component A) and 0.1-10 weight %, described pitch or asphaltic viscosity are 100-1,000,000 pool (60 ℃) and penetration degree are 5-400dmm (1/10mm) (25 ℃); It is 50 that described one or more polymkeric substance are selected from by weight-average molecular weight, 000-2,000,000 and styrene content be the styrene polymer of 20-50 weight %, weight-average molecular weight is 50,000-1,000,000 and ethylene content be methacrylic vinyl acetate, ethylene-propylene rubber(EPR) or the ethylene vinyl acetate random copolymers of 40-99.7 weight %, and weight-average molecular weight is 50,000-1, the group that 000,000 isoprene copolymer is formed.
According to the present invention, comprise that by the mechanical property of polymkeric substance being added to the bituminous composition that makes in traditional pitch viscosity, softening temperature and ductility are more excellent, even at high temperature store, its ductility changes hardly, therefore can greatly improve ageing resistance and package stability.Thereby this bituminous composition can directly apply to urban road laying, also can be reprocessed into to be emulsified state, is widely used in urban road laying again or as industrial waterproof material.
Description of drawings
Figure 1 shows that the penetration test process of bituminous cement;
Figure 2 shows that the mensuration process of the ductility of bituminous cement;
Figure 3 shows that the evaluation procedure of the degree of aging of bituminous cement.
Embodiment
Below, will describe the present invention in detail.
As mentioned above, bituminous composition according to the present invention is characterised in that pitch or pitch earth (component A) is mixed mutually with one or more polymkeric substance (B component).If necessary, can also further add one or more component, described component is selected from by a) free sulfur, and b) aromatic content is 80 weight % or higher arene compound, and c) in the group formed of stablizer.
Pitch (component A) is the main component of bituminous composition of the present invention, and it is had no particular limits, as long as according to the ASTM standard, its viscosity is 100-1, and 000,000 pool (60 ℃) and penetration degree are that 5-400dmm (1/10mm) (25 ℃) gets final product.Pitch comprises various types of straight-run pitches (straight-run asphalt) by crude oil preparation, with the straight-run pitch of thinner dilution and oxidized straight-run pitch, described thinner is selected from paraffinic hydrocarbons, aromatic hydrocarbon, naphthenic hydrocarbon and their mixture.Furtherly, also can comprise the concrete pitch except that petroleum pitch, comprise the pitch of coal-tar pitch or Trinidad asphalt.Further preferred, use flash-point be at least 230 ℃ (COC type, ASTM D-92) and wherein asphalt content be that (analytical procedure: pitch ASTM D 4142) is effective to 2-40 weight %.
The bituminous amount that contains in the composition of the present invention is 90-99.9 weight %.In the time of outside the bituminous amount drops on above-mentioned scope, will the DeGrain of improvement in performance or the problem that snappiness descends take place.
Function at the polymkeric substance that uses as the accessory constituent of asphalt polymer of the present invention is to improve the bituminous quality as polymer modifiers.Polymer modifiers is divided into usually: (1) thermoplastic polymer, (2) natural and synthetic rubber, (3) thermoplastic elastomer, and (4) thermosetting polymer.Improved as required mechanical property is selected properties-correcting agent for use.That is to say,, can use polyolefin resin (polyolefin resin) in order to improve quality at high temperature.Furtherly, use rubber to improve the quality under high temperature and the low temperature simultaneously.At this moment, to have a styrene polymer of high-compatibility just particularly useful with pitch.
The polymkeric substance of Shi Yonging comprises that specifically weight-average molecular weight is 50 in the present invention, 000-2,000,000 and styrene content be the styrene polymer of 20-50 weight %, weight-average molecular weight is 50,000-1,000,000 and ethylene content be ethylene-methyl acrylate, ethylene-propylene rubber(EPR) or the ethane-acetic acid ethyenyl ester random copolymers of 40-99.7 weight %, or weight-average molecular weight is 50,000-1,000,000 isoprene copolymer, above-mentioned polymkeric substance can use two or more the mixture that also can use in them separately.
The amount of the polymkeric substance that contains among the present invention is preferably 0.1-10 weight %.When the amount of polymkeric substance drops on outside the above-mentioned scope, will take place with the improvement in performance DeGrain or not have the relevant problem of additional improvement effect.
Polymkeric substance can use with the form of solid or latex.Among the present invention, when being target to improve mechanical property and antioxidant property simultaneously, the polymkeric substance that preferably contains very small particles mixes mutually with pitch.
Specifically, when using the polymkeric substance of solid form, should use the high speed shear mixing tank, for example homogenizer is worn into superfine little particle with polymkeric substance.Worn into as far as possible little size if solid polymer is preceding in adding pitch to, can shorten polymkeric substance so and mix the needed time with pitch.
On the other hand, when using the polymkeric substance of latex form, because this polymkeric substance has very little size of particles and therefore to exist with water blended state, the mode that such polymkeric substance is only removed water after mixing with pitch is used.Wherein, can be by the whole bag of tricks known in the art except that anhydrating.Furtherly, when the styrene polymer of latex form mixes with pitch, can remove by the form of heating evaporation and anhydrate.
Among the present invention, when using the styrene polymer of latex form, preferable solids content is that 5-70 weight % and molecular weight are 50,000-2,000, the styrene polymer of 000g/mol.When using the isoprene copolymer of latex form, preferable solids content is that 30-70 weight % and molecular weight are 50,000-1,000, the isoprene copolymer of 000g/mol.
Among the present invention, consider the mixing and the oxygenizement of pitch or pitch earth (component A) and polymkeric substance (B component), the 110-220 ℃ of mixing that can implement above-mentioned two components down effectively.
Furtherly, in order to improve the mechanical property of bitumen/polymer composition better, before adding polymkeric substance or after adding, can distinguish or add the hydro carbons of 1-10 weight % and the free sulfur of 0.01-5 weight % simultaneously, wherein the aromatic content that has of hydro carbons is 80 weight % or higher.Preferably under 110-220 ℃, carry out this mixing, more preferably under 130-200 ℃, carry out.Can implement each mixing process by stirring, and as required the scope of mixing time was controlled at 10 minutes to 10 hours.
When the polymkeric substance that contains the water that mixes and solid latex form mixed with pitch, water can evaporate in mixing process or boil over.The reason that this boil-over phenomenon takes place is considered to owing to mix too a large amount of latex in the short period of time.Therefore, be necessary to control the amount of latex to be mixed.Preferably adding speed of polymkeric substance in the latex is to be 0.1-1.0 weight % per hour based on pitch weight, and more preferably is 0.1-0.5 weight % per hour based on pitch weight.
Outside demonomerization sulphur and the arene compound, additive can also comprise stablizer.When bitumen/polymer composition according to the present invention was at high temperature stored, its performance may be owing to oxygenizement and aging the reduction.If such phenomenon occurs, in composition of the present invention, use suitable stabilizers can overcome this problem.The concrete example of stablizer comprises: amine compound comprises N-(1, the 3-dimethylbutyl)-N '-diphenyl-para-phenylene diamine or N-sec.-propyl-N-diphenyl-para-phenylene diamine (N-isopropyl-N-phenyl-p-phenylenediamine); Phosphite compound comprises three (2, the 4-di-tert-butyl-phenyl) phosphite (tris (2,4-di-t-butylphenyl) phosphite); Oxybenzene compound comprises 2-methyl-4, two [(the sulfo-octyl group)-methyl] phenol of 6-(2-methyl-4,6-bis[(octylthio)-methyl] phenol); And propionic ester compound, comprise that tetramethylolmethane base-four-[3-(3, the 5-di-tert-butyl-hydroxy phenyl)-and propionic ester] (pentaerythrityl-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)-and propionate], above-claimed cpd can use two or more the mixture that also can use in them separately.
Based on pitch or asphaltic amount, the usage quantity of stablizer is preferably 0.001-1 weight %.When the amount of stablizer dropped on beyond the above-mentioned scope, additional improvement effect did not take place with not obvious in the aged improvement effect yet.
Zhi Bei bituminous composition can be estimated by traditional standard test thus.Assessment item is listed in the table below in 1.
Table 1
In the present invention, by before measure storing with store after performance, particularly the ductility of measuring the mensuration behind the Thin Film Oven Test TFOT according to ASTMD-1754 is estimated the improvement degree of ageing resistance.That is to say that when the performance difference after storing preceding and storage was very little, ageing resistance was evaluated as excellence.
According to the present invention, bitumen/polymer composition or the bitumen/polymer/stabiliser composition that contains stablizer can be directly used in urban road laying.Furtherly, composition of the present invention is reprocessed into is emulsified state, and therefore can be used for urban road laying or as industrial waterproof material.
Embodiment
Below, will the present invention be described more specifically by following examples, still, scope of the present invention is not limited in this.Among below the embodiment and Comparative Examples, each amount of substance is to use based on the weight of the gross weight of bitumen/polymer/stablizer to represent.
Comparative Examples 1
Preparation contains 100% bituminous composition, and the ductility at room temperature after measuring penetration degree, softening temperature, viscosity, the PI (penetrative index) of said composition and heating preceding and heating, and the result is as shown in table 2 below.Described pitch makes by the distillation Middle East (Middle Eastern) crude oil, and according to ASTM (U.S. material association) standard, this penetration of bitumens is 70 (25 ℃).
Comparative Examples 2
Preparation contains 100% bituminous composition, and the performance identical with Comparative Examples 1 of measuring said composition, and the result is as shown in table 2 below.Described pitch is by distilling Chinese crude oil but not middle-eastern crude makes, and according to the ASTM standard, this penetration of bitumens is 72 (25 ℃).
Comparative Examples 3
Preparation contains 100% bituminous composition, and the performance identical with Comparative Examples 1 of measuring said composition, and the result is as shown in table 2 below.Described pitch makes by distilling Chinese crude oil, and according to the ASTM standard, this penetration of bitumens is 85 (25 ℃).
Comparative Examples 4
Preparation contains 100% bituminous composition, and the performance identical with Comparative Examples 1 of measuring said composition, and the result is as shown in table 2 below.Described pitch makes by distilling Chinese crude oil, and according to the ASTM standard, this penetration of bitumens is 35 (25 ℃).
Comparative Examples 5
In 180 ℃ reactor, in the Comparative Examples 3 of 99 weight %, add the rock asphalt of 1 weight % in the pitch of preparation, stirred then 1 hour, make bituminous composition.
Comparative Examples 6
Add the hydrocarbon of 9 weight % in 150 ℃ reactor in the Comparative Examples 4 of 91 weight % in the pitch of preparation, aromatic content is 91% in this hydrocarbon, stirs then 1 hour, makes bituminous composition.
Comparative Examples 7
Add in the pitch of preparation in the Comparative Examples 4 of 91 weight % in 150 ℃ reactor that aromatic content is 82% in the hydrocarbon, this hydrocarbon of 9 weight %, stirred then 1 hour, make bituminous composition.
Comparative Examples 8
Add in the pitch of preparation in the Comparative Examples 4 of 91 weight % in 150 ℃ reactor that aromatic content is 66% in the hydrocarbon, this hydrocarbon of 9 weight %, stirred then 1 hour, make bituminous composition.
Embodiment 1
In the Comparative Examples 1 of 99.5 weight %, add in the pitch of preparation 0.5 weight %, molecular-weight average is 150, the ethylene-methyl acrylate of 000g/mol stirred 2 hours down at 150 ℃ then, made according to bituminous composition of the present invention.
Embodiment 2
With pitch and the 0.5 weight % of preparation in the Comparative Examples 1 of 99.5 weight %, molecular-weight average is 200, the ethylene-propylene rubber(EPR) of 000g/mol mixes, and 150 ℃ of stirrings 2 hours down, makes according to bituminous composition of the present invention then.
Embodiment 3
With pitch and the 0.5 weight % of preparation in the Comparative Examples 1 of 99.5 weight %, molecular-weight average is 350, the ethane-acetic acid ethyenyl ester of 000g/mol mixes, and 150 ℃ of stirrings 2 hours down, makes according to bituminous composition of the present invention then.
Embodiment 4
In the Comparative Examples 1 of 99.6 weight %, add in the pitch of preparation 0.4 weight %, weight-average molecular weight is 1,000,000g/mol and styrene content are 23% styrene butadiene polymkeric substance, stir 1 hour in 180 ℃ reactor then, make according to bituminous composition of the present invention.
Embodiment 5
In the Comparative Examples 1 of 99.6 weight %, add in the pitch of preparation 0.4 weight %, weight-average molecular weight is 50,000g/mol and styrene content are 23% styrene butadiene polymkeric substance, in 180 ℃ reactor, stirred 1 hour then, make according to bituminous composition of the present invention.
Embodiment 6
With the pitch of preparation in the Comparative Examples 1 of 99.48 weight % and 0.4 weight %, weight-average molecular weight is 1,000,000g/mol and styrene content are 23% styrene butadiene mixed with polymers, in 180 ℃ reactor, stirred 1 hour, the free sulfur that further adds 0.02 weight % then stirred 30 minutes, and [3-(3 with the tetramethylolmethane base-four of 0.1 weight % then, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] mixed 1 hour, make according to bituminous composition of the present invention.
Embodiment 7
In the Comparative Examples 2 of 99 weight %, add in the pitch of preparation 1 weight %, weight-average molecular weight is 400,000g/mol and styrene content are 23% styrene butadiene polymkeric substance, stirred 1 hour down at 130 ℃ then, make according to bituminous composition of the present invention.
Embodiment 8
In the Comparative Examples 2 of 98.99 weight %, add in the pitch of preparation 1 weight %, weight-average molecular weight is 400,000g/mol and styrene content are 23% styrene butadiene polymkeric substance, and add 0.01% free sulfur, stirred 1 hour down at 140 ℃ then, make according to bituminous composition of the present invention.
Embodiment 9
With the pitch of preparation in the Comparative Examples 2 of 97 weight % and 2 weight %, weight-average molecular weight is 400,000g/mol and styrene content are 23% styrene butadiene mixed with polymers, stirred 1 hour, the free sulfur that further adds 1 weight %, stirred 1 hour down at 130 ℃ then, make according to bituminous composition of the present invention.
Embodiment 10
In the Comparative Examples 6 of 99.2 weight %, add in the pitch of preparation 0.8 weight %, weight-average molecular weight is 400,000g/mol and styrene content are 23% styrene butadiene polymkeric substance, stirred 1 hour down at 130 ℃ then, make according to bituminous composition of the present invention.
Embodiment 11
In the Comparative Examples 6 of 98 weight %, add in the pitch of preparation 2 weight %, weight-average molecular weight is 100, the isoprene copolymer of 000g/mol stirred 1 hour down at 120 ℃ then, made according to bituminous composition of the present invention.
Embodiment 12
In the Comparative Examples 6 of 99 weight %, add in the pitch of preparation 1 weight %, weight-average molecular weight is 700, the isoprene copolymer of 000g/mol stirred 1 hour down at 150 ℃ then, made according to bituminous composition of the present invention.
Embodiment 13
In the Comparative Examples 1 of 99.6 weight %, add in the pitch of preparation 0.3 weight %, weight-average molecular weight is 1,000,000g/mol and styrene content are 23% styrene butadiene polymkeric substance, stirred 1 hour down at 180 ℃, further add then 0.1 weight %, weight-average molecular weight is 300, the isoprene copolymer of 000g/mol makes according to bituminous composition of the present invention.
Embodiment 14
In the Comparative Examples 1 of 99.59 weight %, add in the pitch of preparation 0.4 weight %, weight-average molecular weight is 1,000,000g/mol and styrene content are 23% styrene butadiene polymkeric substance, stirred 1 hour down at 180 ℃, the phenylenediamine that further adds 0.01 weight % then is N-sec.-propyl-N '-diphenyl-para-phenylene diamine, mixed then 30 minutes, and made according to bituminous composition of the present invention.
Embodiment 15
In the Comparative Examples 1 of 99.58 weight %, add in the pitch of preparation 0.3 weight %, weight-average molecular weight is 1,000,000g/mol and styrene content are 23% styrene butadiene polymkeric substance, stirred 1 hour down at 180 ℃, further add then 0.1 weight %, weight-average molecular weight is 300, the isoprene copolymer of 000g/mol, adding 0.02 weight % phenylenediamine again is N-sec.-propyl-N '-diphenyl-para-phenylene diamine, mixed then 30 minutes, and made according to bituminous composition of the present invention.
Embodiment 16
In the pitch of the Comparative Examples 1 of 99 weight % with the speed of 0.5 weight % per hour add 0.8 weight % the latex form, weight-average molecular weight is 1,000,000g/mol and styrene content are 23% styrene butadiene polymkeric substance, afterwards, mixture was stirred 1 hour down at 200 ℃, add 0.1 weight %, weight-average molecular weight is 300, the isoprene copolymer of 000g/mol, and the phenylenediamine that further adds 0.1 weight % is N-sec.-propyl-N '-diphenyl-para-phenylene diamine, mixed then 30 minutes, and made according to bituminous composition of the present invention.
Embodiment 17
To 90 weight %, penetration degree is that the weight-average molecular weight that adds 8 weight % in 350 the pitch that is made by Chinese crude oil is 400,000g/mol and styrene content are 23% styrene butadiene polymkeric substance, stirred 2 hours down at 200 ℃, further add 1 weight %, weight-average molecular weight is 200, the isoprene copolymer of 000g/mol, add three (2 of the N-sec.-propyl-N '-diphenyl-para-phenylene diamine of 0.5 weight % and 0.5 weight % then, the 4-di-tert-butyl-phenyl) phosphite, mixed then 30 minutes, and made according to bituminous composition of the present invention.
Embodiment 18
In the pitch of the Comparative Examples 1 of 98 weight %, add 1.3 weight %'s, weight-average molecular weight is 400,000g/mol and styrene content are 23% styrene butadiene polymkeric substance, stirred 2 hours down at 180 ℃, with 0.3 weight %'s, weight-average molecular weight is 200, the isoprene copolymer of 000g/mol mixes, then further with N-sec.-propyl-N '-diphenyl-para-phenylene diamine of 0.1 weight %, 0.1 three (2 of weight %, the 4-di-tert-butyl-phenyl) phosphite, 0.1 the 2-methyl-4 of weight %, [3-(3 for the tetramethylolmethane base-four of 6-pair-[(sulfo-octyl group)-methyl] phenol and 0.1 weight %, the 5-di-tert-butyl-hydroxy phenyl) propionic ester], make according to bituminous composition of the present invention.
Embodiment 19
The aromatic content that adds 9 weight % in the Comparative Examples 4 of 90.5 weight % in the pitch of preparation is 82% hydrocarbon, stirred 1 hour down at 180 ℃, add 0.5 weight %, weight-average molecular weight is 1,000,000g/mol and styrene content are 23% styrene butadiene polymkeric substance, stirred then 1 hour, and made according to bituminous composition of the present invention.
Measured the performance of the bituminous composition of Comparative Examples 1-8 and embodiment 1-19, comprised before penetration degree, softening temperature and the film heating and the ductility after the heating.The result is as shown in table 2 below.
Table 2
| Penetration degree (25 ℃), dmm | Softening temperature, ℃ | Viscosity (60 ℃), pool | *PI | Before the Thin Film Oven Test TFOT, ductility (15 ℃), cm | Behind the Thin Film Oven Test TFOT, ductility (15 ℃), cm | |
| Comparative Examples 1 | 70 | 48.2 | 1908 | -1.61 | ＞150 | 71 |
| Comparative Examples 2 | 72 | 51.0 | 2599 | -0.3 | 12 | 5 |
| Comparative Examples 3 | 85 | 48.4 | 2385 | -0.4 | 137 | 13 |
| Comparative Examples 4 | 35 | 59.6 | - | - | 6 | 4 |
| Comparative Examples 5 | 70 | 50.3 | 2735 | -0.25 | 136 | 9 |
| Comparative Examples 6 | 72 | 49.0 | 2490 | -0.44 | 142 | 10 |
| Comparative Examples 7 | 73 | 49.2 | 2590 | -0.54 | 123 | 7 |
| Comparative Examples 8 | 75 | 48.8 | 2310 | -0.7 | 90 | 5 |
| Embodiment 1 | 74 | 49.1 | 2215 | -0.9 | ＞150 | ＞150 |
| Embodiment 2 | 75 | 49.3 | 2108 | -1.5 | ＞150 | 142 |
| Embodiment 3 | 78 | 48.8 | 2006 | -1.4 | ＞150 | 133 |
| Embodiment 4 | 69 | 48.7 | 2028 | -1.3 | ＞150 | ＞150 |
| Embodiment 5 | 69 | 48.6 | 1990 | -1.0 | ＞150 | 50 |
| Embodiment 6 | 70 | 49.0 | 2108 | -1.2 | ＞150 | 140 |
| Embodiment 7 | 70 | 51.5 | 2650 | -0.25 | ＞150 | 125 |
| Embodiment 8 | 69 | 51.8 | 2660 | -0.22 | ＞150 | 80 |
| Embodiment 9 | 67 | 52.4 | 2762 | -0.14 | ＞150 | 145 |
| Embodiment 10 | 72 | 49.0 | 2082 | -1.2 | ＞150 | ＞150 |
| Embodiment 11 | 73 | 48.6 | 2002 | -1.3 | ＞150 | ＞150 |
| Embodiment 12 | 69 | 49.4 | 2246 | -0.8 | ＞150 | ＞150 |
| Embodiment 13 | 73 | 48.8 | 1998 | -1.2 | ＞150 | ＞150 |
| Embodiment 14 | 72 | 49.0 | 2062 | -1.3 | ＞150 | ＞150 |
| Embodiment 15 | 73 | 48.9 | 2010 | -1.2 | ＞150 | ＞150 |
| Embodiment 16 | 71 | 49.0 | 2230 | -0.2 | ＞150 | ＞150 |
| Embodiment 17 | 78 | 72.1 | 4406 | 0.6 | ＞150 | ＞150 |
| Embodiment 18 | 70 | 49.9 | 2406 | -0.8 | ＞150 | ＞150 |
| Embodiment 19 | 72 | 49.5 | 2620 | -0.50 | ＞150 | ＞150 |
*PI (penetrative index): this index is to come evaluation temperature susceptibility by the penetration degree of measuring under 15 ℃, 25 ℃, 30 ℃.The increase of temperature sensitivity and above-mentioned numerical value index (numerical index) reduces (quality evalution is for excellent when the numerical value index is low) inversely proportionally.
PI=[20 (*) is (1-25A)]/(1+50A) (wherein, A is the slope that concerns between temperature and the penetration degree)
According to the penetration degree grade, the pitch that home and overseas is mainly used is divided into penetration degree and is the AP-5 pitch of 60-80 and the penetration degree AP-3 pitch as 80-100, and wherein, described penetration degree grade is to determine 25 ℃ hardness by measuring pitch.In the case, because the character of crude oil influences the bituminous quality strongly, therefore, the bituminous quality that is prepared by specific crude oil is restricted.For example, the pitch with low penetration degree has high viscosity, but poor ductility.On the contrary, the pitch with high penetration degree has low viscosity, but ductility is good.Therefore, the improvement by penetration degree fractionated bituminous quality by the crude oil preparation is restricted.
Yet, in the present invention, from table 2 apparently, use polymkeric substance and optionally used stablizer, therefore improved the PI of viscosity, softening temperature and representation temperature susceptibility, and simultaneously, the penetration degree grade of various types of crude oil has been remained on identical level.Especially, confirmed before the Thin Film Oven Test TFOT and the ductility after the test is obviously improved.Furtherly, compare with the composition that does not contain free sulfur, the softening temperature and the viscosity that contain the composition of free sulfur are improved, but ductility is not improved.And, can improve the bituminous quality though add ethane-acetic acid ethyenyl ester, the improvement effect of ductility then is lower than respectively or the effect when using styrene polymer and isoprene copolymer simultaneously.
And, when the composition that contains pitch and polymkeric substance mixes with suitable stabilizers, can improve ageing resistance, following Comparative Examples and embodiment can confirm this result.In order to estimate ageing resistance, composition at high temperature over a long time (120 ℃) is stored, and measures before storing then and the ductility after the character, particularly Thin Film Oven Test TFOT after storing.The result is as shown in table 3 below.
Table 3
Mixed polymkeric substance and stablizer in the pitch in embodiment 4,6,15 and 16, even at high temperature store 10 days, the change of ductility is not remarkable yet, therefore shows significantly improved resistance to deterioration and package stability.
According to The above results, can think that method of the present invention can make various types of bituminous quality be improved.Especially, confirmed greatly to have improved the adhesivity of estimating by measuring ductility (15 ℃, ASTM D113).Furtherly, except that ductility, the bituminous mechanical property be can also improve, penetration degree, softening temperature and PI comprised.
Claims (9)
1, a kind of method for preparing bituminous composition, this bituminous composition has improved mechanical property and ageing resistance, this method is included under 110-220 ℃, pitch or the bitumen component A of 90-99.9 weight % are mixed with one or more polymeric constituents B of 0.1-10 weight %, described pitch or pitch earth are 100-1 60 ℃ viscosity, 000,000 pool, 25 ℃ penetration degrees is 5-400dmm, and described dmm equals 1/10mm; It is 50 that described one or more polymeric constituents B is selected from by weight-average molecular weight, 000-2,000,000 and styrene content be the styrene polymer of 20-50 weight %, weight-average molecular weight is 50,000-1,000,000 and ethylene content be ethylene-methyl acrylate, ethylene-propylene rubber(EPR) or the ethane-acetic acid ethyenyl ester random copolymers of 40-99.7 weight %, and weight-average molecular weight is 50,000-1 is in the group that 000,000 isoprene copolymer is formed.
2, method according to claim 1, wherein, this method also comprises, except adding described pitch or bitumen component A and described polymeric constituent B, also adds one or more additives, described additive be selected from by:
A) based on the free sulfur of the 0.01-5 weight % of the amount of described pitch or bitumen component A;
B) based on the arene compound of the 1-10 weight % of the amount of described pitch or bitumen component A, aromatic content is 80 weight % or higher in the described arene compound; With
C) based on one or more stablizers of the 0.001-1 weight % of the amount of described pitch or bitumen component A, described stablizer is selected from N-(1, the 3-dimethylbutyl)-N '-diphenyl-para-phenylene diamine, three (2, the 4-di-tert-butyl-phenyl) phosphite, 2-methyl-4, two [(sulfo-octyl group)-methyl] phenol of 6-and tetramethylolmethane base-four [3-(3, the 5-di-tert-butyl-hydroxy phenyl)-propionic ester];
In the group of being formed.
3, method according to claim 1, wherein, described styrene polymer mixes with solid form or latex form.
4, method according to claim 3, wherein, when using the described styrene polymer of solid form, the styrene polymer of the described solid form of disposable adding predetermined amount; When using the described styrene polymer of latex form,, the styrene polymer of this latex form is added with the speed of 0.1-1.0 weight % per hour based on described bituminous amount.
5, method according to claim 2, wherein, when preparation contain described pitch or bitumen component A, a) during the bituminous composition of free sulfur and described polymeric constituent B, described pitch or bitumen component A and described polymkeric substance are 110-220 ℃ of adding, stirred 10 minutes to 10 hours, add a) free sulfur, and then mixed 0.5-10 hour.
6, method according to claim 2, wherein, when preparation contains described pitch or bitumen component A, b) during the bituminous composition of arene compound and described polymeric constituent B, described pitch or bitumen component A and b) arene compound is 110-220 ℃ of adding, stirred 0.5-10 hour, add described polymkeric substance, and then mixed 0.5-10 hour.
7, method according to claim 2, wherein, when preparation contains described pitch or bitumen component A, a) free sulfur, polymeric constituent B and c) during the bituminous composition of stablizer, described pitch, free sulfur and polymkeric substance are 110-220 ℃ of adding, stirred 0.5-10 hour, add stablizer, and then mixed 0.5-10 hour.
8, a kind of bituminous composition with improved mechanical property and ageing resistance, this bituminous composition contains the pitch of 90-99.9 weight % or one or more polymeric constituents B of bitumen component A and 0.1-10 weight %, described pitch or bitumen component A are 100-1 60 ℃ viscosity, 000,000 pool, 25 ℃ penetration degrees is 5-400dmm, and described dmm equals 1/10mm; It is 50 that described one or more polymeric constituents B is selected from by weight-average molecular weight, 000-2,000,000 and styrene content be the styrene polymer of 20-50 weight %, weight-average molecular weight is 50,000-1,000,000 and ethylene content be ethylene-methyl acrylate, ethylene-propylene rubber(EPR) or the ethane-acetic acid ethyenyl ester random copolymers of 40-99.7 weight %, and weight-average molecular weight is 50,000-1 is in the group that 000,000 isoprene copolymer is formed.
9, bituminous composition according to claim 8, wherein, this bituminous composition further contains one or more additives, described additive be selected from by:
A) based on the free sulfur of the 0.01-5 weight % of the amount of described pitch or bitumen component A;
B) based on the arene compound of the 1-10 weight % of the amount of described pitch or bitumen component A, aromatic content is 80 weight % or higher in the described arene compound; With
C) based on one or more stablizers of the 0.001-1 weight % of the amount of described pitch or bitumen component A, described stablizer is selected from by N-(1, the 3-dimethylbutyl)-N '-diphenyl-para-phenylene diamine, three (2, the 4-di-tert-butyl-phenyl) phosphite, 2-methyl-4, two [(sulfo-octyl group)-methyl] phenol of 6-and tetramethylolmethane base-four [3-(3, the 5-di-tert-butyl-hydroxy phenyl)-propionic ester];
In the group of being formed.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102505729A (en) * | 2011-12-19 | 2012-06-20 | 王景满 | Rainwater collection system extended from surface street |
| CN103044933A (en) * | 2011-10-17 | 2013-04-17 | 中国石油天然气股份有限公司 | Stabilizer composition for polymer modified asphalt |
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| KR101019827B1 (en) * | 2007-11-13 | 2011-03-04 | 에스케이에너지 주식회사 | Binder composition for color asphalt having improved mechanical property, anti-aging property, and crack resistance, and method for preparing the same |
| EP2166039A1 (en) * | 2008-09-19 | 2010-03-24 | Ceca S.A. | Preparation process of asphalt mixtures |
| KR101238116B1 (en) | 2010-10-26 | 2013-02-27 | 홍영근 | Modifying asphalt by in-situ polymerization of polyphenyleneoxide and the manufacturing method thereof |
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| US3900439A (en) * | 1974-05-24 | 1975-08-19 | Prod Res & Chem Corp | Method and composition for repairing asphalt pavement |
| US3985694A (en) * | 1974-08-29 | 1976-10-12 | Mobil Oil Corporation | Asphaltic compositions containing synthetic terpenic resin and an interpolymer of ethylene, vinyl acetate and an organic acid |
| US4130516A (en) * | 1976-04-12 | 1978-12-19 | Phillips Petroleum Company | High ductility asphalt |
| US5581225A (en) * | 1995-04-20 | 1996-12-03 | Littelfuse, Inc. | One-piece female blade fuse with housing |
| US5888289A (en) * | 1996-05-20 | 1999-03-30 | Shell Oil Company | Bitumen compositions and a process for their preparation |
| KR100267575B1 (en) * | 1998-04-08 | 2000-10-16 | 남창우 | Stabilized polymer modified asphalt composition, a method for preparing same and method for using same |
| KR20040058701A (en) * | 2002-12-27 | 2004-07-05 | 에쓰대시오일 주식회사 | Polymer-modified asphalt composition |
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| CN103044933A (en) * | 2011-10-17 | 2013-04-17 | 中国石油天然气股份有限公司 | Stabilizer composition for polymer modified asphalt |
| CN103044933B (en) * | 2011-10-17 | 2015-05-13 | 中国石油天然气股份有限公司 | Stabilizer composition for polymer modified asphalt |
| CN102505729A (en) * | 2011-12-19 | 2012-06-20 | 王景满 | Rainwater collection system extended from surface street |
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| KR20070105533A (en) | 2007-10-31 |
| KR101227739B1 (en) | 2013-01-29 |
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