CN1227296C - Polymer modified asphalt composition and preparing method thereof - Google Patents
Polymer modified asphalt composition and preparing method thereof Download PDFInfo
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- CN1227296C CN1227296C CN 02144954 CN02144954A CN1227296C CN 1227296 C CN1227296 C CN 1227296C CN 02144954 CN02144954 CN 02144954 CN 02144954 A CN02144954 A CN 02144954A CN 1227296 C CN1227296 C CN 1227296C
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Abstract
The present invention provides polymer modified road asphalt composition and a preparing method thereof. Thermoplastic rubber is ground and evenly dispersed into basic asphalt by the special equipment of high shearing or colloid milling, etc. in the temperature of 140 to 240 DEG C to prepare modified asphalt composition; then, composite additive accounting for 0.1% to 6%(m) of the total amount of asphalt is added to prepare a polymer modification road asphalt product. The present invention has simple production process; the polymer modification road asphalt product has good storage stability, superior high-low temperature performance, etc., and is suitable for building high-grade highways.
Description
Technical field
The present invention relates to a kind of polymer-modified asphalt compositions and preparation method thereof, relate in particular to polymer-modified asphalt compositions of a kind of stable storing and preparation method thereof.
Background technology
At present, along with the continuous increase of the volume of traffic, road speed and traffic loading, more and more higher to the specification of quality of high-grade highway.Improve though the mass ratio of existing heavy duty road asphalt has had largely in the past, can not adapt to some harsh climate condition and the requirement of the traffic loading of increase day by day fully, the phenomenon that early damage, maintenance in advance appear in the road surface happens occasionally.In order further to improve the bituminous quality, improve bituminous temperature sensibility and high and low temperature performance, polymer modified asphalt technology is arisen at the historic moment.
Really, polymer modified asphalt is compared with heavy duty road asphalt, no matter at aspects such as temperature sensibility and high and low temperature performances, still all is greatly increased at aspects such as abrasion resisting, antiskid and anti-water damages.But because high molecular polymer compares with pitch, exist bigger difference, cause the two to be difficult to dissolve each other and form stabilising system at aspects such as molecular weight, density and other physico-chemical properties.In the heating storage process, the two is very easily emanated and demixing phenomenon occurs, also is that stability in storage is relatively poor, and it is higher to show as the top polymer content, and the lower section bituminous is more.This ununiformity must have influence on the inconsistent or unstable of performance of modified bitumen, in case after being used to build the road, can cause bad influence to pavement quality.Therefore, the present mostly method that adopts the working-yard to produce modifying asphalt is paved the way with the aggregate mix after producing modifying asphalt immediately, this not only has relatively high expectations to production unit and production power, but also to comprise various raw-material transportation supervisors, therefore, production cost is higher.
In order to overcome the drawback that above-mentioned in-situ processing modifying asphalt exists, at present, the finished product asphaltum good in the plant produced stability in storage caused people's great attention.Once there were some document patent reports to attempt to improve storage Stability of Polymer Modified Asphalt with different methods.Wherein class methods are to reach the purpose of improving consistency by the basic asphalt of selecting to suit, just according to saturated branch, fragrant branch, colloid and bitum content in the basic asphalt, select fragrance to divide the content height and the few basic asphalt of asphalt content is used for producing modifying asphalt as far as possible, though having, this way idol proves effective, but exist significant limitation, in the middle of reality, be difficult to promote.Another kind of is to improve consistency by adding additive, be to adopt the way that adds mineral acid (especially phosphoric acid) as US5070123, but effect is unsatisfactory.In WO9845372, make linking agent with sulphur, reach the compatible purpose of polymkeric substance and pitch, but its disposable adding sulphur can not be too fast or too much, otherwise the asphalt-polymer component easily is condensed into colloid and flow difficulties, can't continue operation, and can only take the mode that repeatedly adds slowly, not only processing step is loaded down with trivial details, and course of processing length consuming time, therefore, treatment capacity is restricted.Chinese patent 99119742.9 discloses a kind of preparation method of polymer-asphalt composition, product stable more satisfactory, but its reaction promoter kind is single, need use compatilizer just can achieve the goal simultaneously.Owing to used the more compatilizer of specific content, restricted material choice, increased production cost.In addition, polymkeric substance and reaction promoter add successively, because polymkeric substance is not fully ground and evenly spreads in the pitch, have influenced the swelling of pitch to polymkeric substance, the rate of crosslinking that makes polymkeric substance itself is greater than polymkeric substance and bituminous rate of crosslinking, thereby influenced the homogeneity of modifying asphalt character.
Summary of the invention
The purpose of this invention is to provide and a kind ofly have that stability in storage, cost are low, the polymer denatured road pitch combination of character homogeneous, the invention provides simple, the easy to operate method for preparing polymer modified asphalt of a kind of technology simultaneously.
Polymer modified asphalt of the present invention comprises following component by weight:
(1) basic asphalt 84%～98.9%;
(2) polymkeric substance 1%～10%, is preferably 3%～6%;
(3) composite additive 0.1%～6%, is preferably 0.2%～3%.
Wherein basic asphalt can be residual oil, the straight-run pitch that crude distillation technology obtains, and also can be the various pitches such as blending pitch that the de-oiled asphalt that obtains of solvent deasphalting technology and mixing process make.Can make basic asphalt with a kind of pitch or above-mentioned two or more bituminous mixture.25 ℃ of penetration degrees of pressing the basic asphalt of GB/T4509 mensuration are (50～300) 1/10mm, are preferably (60～200) 1/10mm.The softening temperature of pressing the basic asphalt that GB/T4507 measures is (28～70) ℃, is preferably (35～58) ℃.
Used polymkeric substance is the thermoplastic elastomer class that contains the conjugated diolefine hydrocarbon structure, comprising: the similar with it high molecular polymer of diblock copolymer SB, triblock copolymer SBS and SIS and structure.Used polymkeric substance can be wherein a kind of polymkeric substance or two kinds of mixture of polymers, preferred SBS.
Used composite additive has comprised quininie dioxime derivative, the thiazole compound of sulfuration or crosslinked action and the inorganics composition that plays activation and promoter action.Wherein the quininie dioxime derivative can be paraquinonedioxime (QDM), thiazole compound can be dibenzothiazyl disulfide (MBTS) and/or 2-mercaptobenzothiazole (MBT), and other inorganics can be in zinc oxide, calcium oxide, carbon black, magnesium oxide, sulphur, calcium hydroxide, the lime carbonate etc. one or more.The paraquinonedioxime derivative accounts for 10%～60% in the composite additive, and thiazole compound accounts for 10%～20%, and other accounts for 30%～70%.
The preparation process of polymer modified asphalt of the present invention is as follows:
(1), prepares asphalt-polymer composition with basic asphalt and mixed with polymers.Mixing temperature is 140 ℃～240 ℃, is suitably 160 ℃～190 ℃, and mixing time is 10min～180min, and preferred 20min～80min grinds, evenly spreads to basic asphalt with high-shear or colloidal mill equipment with polymkeric substance and gets final product.
(2), asphalt-polymer composition and the composite additive that makes with (1) carries out the polymer modification road bitumen that crosslinking reaction prepares stable storing.Temperature of reaction can be identical or different with (1), is generally 140 ℃～240 ℃, is suitably 165 ℃～210 ℃.Temperature of reaction is preferably and is higher than 10～30 ℃ of (1) step mixing temperatures, can reduce the degree of aging of basic asphalt and polymkeric substance like this, and is simultaneously capable of reducing energy consumption.Reaction times is 10min～240min, is suitably 20min～180min.Reaction process can be with high shearing mixing emulsor, also available common whipping appts mixes and realizes, preferred common whipping appts is as paddle stirred reactor etc.
The dissimilar reaction promoter that the composite additive that polymer modified asphalt of the present invention uses selects for use several functions to emphasize particularly on different fields, particularly quininie dioxime derivative and thiazole compound are used, reached under the situation that does not have other compatilizer to exist, the crosslinking reaction fast and stable of polymkeric substance and basic asphalt carries out, product has satisfactory stability, has reduced product cost simultaneously.After the preparation method of polymer modified asphalt of the present invention adopts polymkeric substance at first fully to be distributed in the basic asphalt, add reaction promoter (composite additive) again, polymkeric substance can fully be ground to evenly spread in the pitch, and make pitch and polymkeric substance that a swelling process be arranged, polymkeric substance and the crosslinked favourable condition that provides of pitch are provided, have guaranteed the homogeneity of product property.Polymkeric substance adopts different temperature of reaction to cut down the consumption of energy with the mixing process and the cross-linking reaction process of basic asphalt, and the catabiosis that reduces asphaltic products. takes place; Mixing process adopts different alr modes with reaction process, can cut down the consumption of energy, and reduces facility investment, improves the treatment capacity of device.
Specific implementation method
To further specify the present invention by embodiment below.
The composite additive that each embodiment of table 1 uses is formed
| Embodiment | Composite additive is formed and weight percentage |
| Embodiment 1 | Paraquinonedioxime accounts for 35%, and dibenzothiazyl disulfide accounts for 20%, and zinc oxide accounts for 45% |
| Embodiment 2 | Paraquinonedioxime accounts for 40%, and dibenzothiazyl disulfide accounts for 15%, and calcium oxide accounts for 30%, and sulphur accounts for 15% |
| Embodiment 3 | Paraquinonedioxime accounts for 50%, and dibenzothiazyl disulfide accounts for 15%, and magnesium oxide accounts for 15%, and sulphur accounts for 15%, and carbon black accounts for 5% |
Embodiment 1
Basic asphalt is heated to molten state at 170 ℃, SBS (general petrochemical works, Yueyang produces the YH-791 type) is joined in the basic asphalt, wherein 25 of basic asphalt ℃ of penetration degrees are 148 1/10mm, softening temperature is 41.0 ℃, account for 96.2% (weight) of total amount, SBS accounts for 3% of total amount, under 170 ℃, with high shearing mixing emulsor (rotating speed: 3900r/min) mix 30min, add 0.8% composite additive afterwards, finish the character (the results are shown in Table 2) of test modifying asphalt behind the hybrid reaction 40min.
Embodiment 2
Basic asphalt is heated to 180 ℃ dissolves, (rotating speed: 3900r/min) SBS (general petrochemical works, Yueyang produces the YH-791 type) is joined in the basic asphalt that dissolves under stirring with high shearing mixing emulsor.Wherein 25 of basic asphalt ℃ of penetration degrees are 1331/10mm, and softening temperature is 42.2 ℃, account for 94% (weight) of modifying asphalt total amount, and SBS accounts for 5% of total amount.Under 180 ℃, mix 40min, use common paddle whipping appts (rotating speed 200r/min) afterwards instead, and the composite additive that will account for total amount 1% joins in the said mixture, keep finishing behind 200 ℃ of reaction 60min, and the character (the results are shown in Table 2) of test modifying asphalt.
Embodiment 3
Basic asphalt is heated to 180 ℃ dissolves, (rotating speed: 3900r/min) SBS is joined in the basic asphalt that dissolves under stirring with high shearing mixing emulsor.Wherein 25 of basic asphalt ℃ of penetration degrees are 111 1/10mm, and softening temperature is 43.9 ℃, account for 92.5% (weight) of modifying asphalt total amount, and SBS (general petrochemical works, Yueyang produces the YH-791 type) accounts for 6% of total amount.Under 180 ℃, shear-mixed 60min uses common paddle whipping appts (rotating speed 200r/min) then instead, and temperature is risen to the composite additive that 210 ℃ of addings account for total amount 1.5%, finish the character (the results are shown in Table 2) of test modifying asphalt behind the hybrid reaction 120min.
Comparative example
Condition is with embodiment 1, and just composite additive is replaced by single sulphur, and consumption is 1%, and along with the carrying out of reaction, sample forms colloidal gradually and can not continue operation, and this sample also can't carry out performance test because of losing flowability.
Table 2 embodiment and composition content and product property
| Embodiment | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| The SBS add-on, weight % composite additive, weight % | 3 0.8 | 5 1.0 | 6 1.5 |
| Penetration degree (25 ℃), the 1/10mm softening temperature, ℃ 5 ℃ of ductilities, the cm separation test (163 ℃, 48h) *Softening temperature is poor, ℃ recovery of elasticity (25 ℃), weight % viscosity (135 ℃), Pas penetrative index (PI) **Plastic zone, ℃ | 101 53.6 77 0.2 86.7 1.06 -0.5047 63.81 | 95 65.0 76 0.5 90.3 1.38 -0.4625 65.38 | 74 77.7 36 1.2 95.6 2.04 0.0836 71.49 |
*Stability in storage among the present invention (being consistency) is to estimate by upper and lower softening temperature difference behind the separation test of stipulating among the ASTMD5892-96.When softening temperature difference during, think that stability in storage is qualified less than 2.2 ℃.
*Obtain calculating and getting with PI=30/ (1+50A)-10 after the A by formula lgP=AT+K recurrence by the penetration degree under three temperature.
Claims (16)
1, a kind of polymer-modified asphalt compositions comprises following component by weight:
(1) basic asphalt 84%～98.9%;
(2) polymkeric substance 1%～10%;
(3) composite additive 0.1%～6%;
Wherein composite additive comprises quininie dioxime derivative and thiazole compound.
2, according to the described polymer-modified asphalt compositions of claim 1, it is characterized in that described polymer content is 3%～6%, composite additive content is 0.2%～3%.
3, according to the described polymer-modified asphalt compositions of claim 1, it is characterized in that the blending pitch that de-oiled asphalt that residual oil, straight-run pitch, solvent deasphalting technology that described basic asphalt is selected from crude distillation technology and obtains obtain or mixing process make, or above-mentioned two or more bituminous mixture.
4, according to claim 1 or 3 described polymer-modified asphalt compositions, it is characterized in that 25 ℃ of penetration degrees of described basic asphalt are 50～300 1/10mm, softening temperature is 28～70 ℃.
5,, it is characterized in that described polymkeric substance is the thermoplastic elastomer class that contains the conjugated diolefine hydrocarbon structure according to the described polymer-modified asphalt compositions of claim 1.
6,, it is characterized in that described polymkeric substance is SBS according to the described polymer-modified asphalt compositions of claim 5.
7,, it is characterized in that described composite additive also comprises one or more in inorganics zinc oxide, calcium oxide, carbon black, magnesium oxide, sulphur, calcium hydroxide and the lime carbonate according to the described polymer-modified asphalt compositions of claim 1.
8, according to the described polymer-modified asphalt compositions of claim 1, it is characterized in that described quininie dioxime derivative is a paraquinonedioxime, described thiazole compound is dibenzothiazyl disulfide and/or 2-mercaptobenzothiazole.
9, according to the described polymer-modified asphalt compositions of claim 7, it is characterized in that described composite additive comprises by weight: the quininie dioxime derivative accounts for 10%～60%, and thiazole compound accounts for 10%～20%, and other inorganics accounts for 30%～70%.
10, according to the preparation method of arbitrary polymer-modified asphalt compositions in the claim 1～9: it is characterized in that comprising following process:
(1), prepares asphalt-polymer composition with basic asphalt and mixed with polymers;
(2), the asphalt-polymer composition that makes with (1) and the polymer modification road bitumen of composite additive prepared in reaction stable storing.
11, according to the described preparation method of claim 10, it is characterized in that wherein the mixing temperature of step (1) is 140 ℃～240 ℃, mixing time is 10min～180min, uses equipment to be high-shear device or colloidal mill.
12, according to the described preparation method of claim 11, it is characterized in that described mixing temperature is 160 ℃～190 ℃, mixing time is 20min～80min.
13, according to the described preparation method of claim 10, it is characterized in that wherein the described temperature of reaction of step (2) is 140 ℃～240 ℃, the reaction times is 10min～240min.
14, according to the described preparation method of claim 13, it is characterized in that described temperature of reaction is 165 ℃～210 ℃, the reaction times is 20min～180min.
15,, it is characterized in that described temperature of reaction is higher than 10～30 ℃ of step (1) mixing temperatures according to the described preparation method of claim 13.
16,, it is characterized in that wherein the reaction process of step (2) adopts common whipping appts according to the described preparation method of claim 10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02144954 CN1227296C (en) | 2002-12-19 | 2002-12-19 | Polymer modified asphalt composition and preparing method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02144954 CN1227296C (en) | 2002-12-19 | 2002-12-19 | Polymer modified asphalt composition and preparing method thereof |
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| CN1508189A CN1508189A (en) | 2004-06-30 |
| CN1227296C true CN1227296C (en) | 2005-11-16 |
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| CN 02144954 Expired - Lifetime CN1227296C (en) | 2002-12-19 | 2002-12-19 | Polymer modified asphalt composition and preparing method thereof |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101608069B (en) * | 2008-06-19 | 2011-07-20 | 中国石油化工股份有限公司 | Composite modified bitumen and preparation method thereof |
| CN102051057B (en) * | 2009-10-27 | 2012-11-21 | 中国石油化工股份有限公司 | Styrene butadiene rubber modified asphalt and preparation method thereof |
| CN102453333B (en) * | 2010-10-15 | 2014-07-23 | 中国石油化工股份有限公司 | Preparation method of polymer modified asphalt |
| CN104556888B (en) * | 2013-10-22 | 2016-05-18 | 中国石油化工股份有限公司 | A kind of asphalt and preparation method thereof |
| CN110863518B (en) * | 2019-11-27 | 2021-07-23 | 荆门科顺新材料有限公司 | Anti-aging asphalt-based pre-paved waterproof coiled material and preparation method thereof |
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Granted publication date: 20051116 |