CN104610766A - Efficient composite emulsion modifier - Google Patents
Efficient composite emulsion modifier Download PDFInfo
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- CN104610766A CN104610766A CN201410848307.7A CN201410848307A CN104610766A CN 104610766 A CN104610766 A CN 104610766A CN 201410848307 A CN201410848307 A CN 201410848307A CN 104610766 A CN104610766 A CN 104610766A
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- asphalt
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Abstract
The invention discloses a preparation method of an efficient composite emulsion modifier. Under the action of a preferred tasteless sulfur-contained cross-linking agent, a double bond of a polybutadiene segment of a composite polymer or methylene adjacent to the double bond is very active, can react with heteroatoms and active groups in asphalt so as to graft the asphalt onto the composite polymer to generate a polymer-asphalt graft. The graft acts as a surfactant between a polymer phase and an asphalt phase, so that surface tensions between the polymer and the asphalt as well as Gibbs free energy of a system are reduced, and better compatibility of the polymer and the asphalt is promoted. Therefore, a polymer-modified asphalt emulsion is promoted to form a more stable system.
Description
Technical field
The present invention is specifically related to a kind of high efficiency composition emulsion modifying agent.
Background technology
The emulsifying process of modified emulsifying asphalt is complicated, usually shorter emulsion stationary phase is formed with physical adsorption in " seed soap lye " between composition polymer and pitch, after displaying certain hour, due to the difference of the physical and chemical performance such as density of material, surface tension, easy generation physical layering, causes " ununiformity " of composition polymer modifying asphalt.In polymer modified asphalt, usually add linking agent and address this problem.But in emulsified bitumen, this research have not been reported.
The preparation of modified emulsifying asphalt mainly carries out modification and emulsification to pitch, according to modification different with the sequencing of emulsification can be divided into modifying asphalt emulsification, emulsification properties-correcting agent and the modification of asphalt emulsification mixed once, second heat hybrid system modified emulsifying asphalt three kinds of techniques.The emulsified bitumen performance comparison of three kinds of technique acquisitions is in table 1.
The emulsified bitumen performance comparison that table 1 three kinds of techniques obtain
| Preparation method | The emulsification of modifying asphalt | A cold mixing method | Second heat hybrid system |
| Homogeneity | Excellent | Shang Ke | Well |
| Road effect | Excellent | Poor | Well |
| Complexity | Difficult | Easily | Easily |
| Production cost | High | Low | Low |
Viewed from the evaluation result table, no matter second heat hybrid system is from which aspect, and effect is all relatively good.
(1) emulsification of modifying asphalt
The method of modifying asphalt emulsification is: first by dissolution with solvents or mechanical shearing effect, the properties-correcting agent of the high molecular polymer such as rubber, plastics class is made to be dispersed in pitch with tiny particulate homogenous, and form reticulated structure after being cross-linked in a variety of manners, cause asphalt performance to be improved greatly, thus produce modifying asphalt; And then carry out emulsification production modified emulsifying asphalt with the modifying asphalt finished product produced.
There is a following difficult problem in the technical elements that is emulsified in of modifying asphalt: during to asphalt modification, and the equipment that shearing force is very strong need be adopted to carry out, but when shearing force is too strong, shearing action can make the reticulated structure of formation destroy, and modified effect declines; The extremely difficult emulsification of modifying asphalt, the emulsifying agent requiring performance extremely excellent ability emulsification: during emulsification, modifying asphalt and the soap lye temperature difference are comparatively large, easily seethe with excitement, cause emulsification to be difficult to carry out; Finished product temperature after emulsification is higher, easily causes the emulsion breaking of harsh product; The density of modifying asphalt is large, and the pitch particle granularity after emulsification is comparatively large, poor storage stability.
(2) modification again after asphalt emulsification
1) heated bitumen is joined among mulser together with emulsifier aqueous solution, form common emulsified asphalt, and then with the high-speed stirring mixing by a certain percentage of properties-correcting agent emulsion, form modified emulsifying asphalt, i.e. a cold mixing method.
2) the same properties-correcting agent of the heated bitumen heated, emulsifier aqueous solution join in the middle of mulser together by required fixed proportion, carry out emulsification, form the emulsified bitumen of modification, i.e. second heat hybrid system.No matter second heat hybrid system is from which aspect, and effect is all relatively good.
Normal temperature bituminous liquids is primarily of compositions such as pitch, emulsifying agent, water, multiple polymers composite modifiers.On microcosmic, normal temperature pitch presents typical water-in-oil structure, is different from existing emulsified bitumen or modified emulsifying asphalt with oil-in-water structure.Ideal structure as shown in Figure 1.
Summary of the invention
Goal of the invention: in order to solve the deficiency of existing modified emulsifying asphalt technology, the invention provides a kind of high efficiency composition emulsion modifying agent.
Technical scheme: a kind of preparation method of high efficiency composition emulsion modifying agent, is characterized in that: comprise as follows:
(1) styrene-butadiene-styrene thermoplastic elastomer aqueous latex is prepared;
(2) in styrene-butadiene-styrene thermoplastic elastomer aqueous latex, add the blending emulsion of the self-crosslinking modified acrylate emulsion (FG-H1811) of ethylene-vinyl acetate water miscible liquid (FG-CP606W)/anti-strong acid of positively charged ion, and be optimized compound; When FG-CP606W/FG-H1811 blending ratio is 80/20, emulsion has optimum performance;
(3), in normal temperature pitch composite emulsion, the weight percent of styrene-butadiene-styrene thermoplastic elastomer aqueous latex is 6%-10%, FG-CP606W/FG-H1811 blending emulsion (80/20) is 8%-15%, and pitch is 55%-65%, and water is 25%-35%;
(4) composite good by above-mentioned mass ratio the CP606W/ H1811 of styrene-butadiene-styrene thermoplastic elastomer aqueous latex and optimization, and add wooden amine cation asphalt emulgent: 2%-3.5%, one piece is mixed with seed soap lye;
(5) heated bitumen is mixed by certain mass ratio containing sulfur crosslinking agent with tasteless: dosage of crosslinking agent is heated bitumen 0.3%-1.0%;
(6) step (4) and step (5) gained mixture are joined in mulser together, seed soap lye temperature controls at 50-60 DEG C, heated bitumen temperature controls at 135-150 DEG C, and the storage time controls more than 4 hours, final obtained high efficiency composition emulsion modifying agent.
In high efficiency composition emulsion modifying agent, styrene-butadiene-styrene thermoplastic elastomer aqueous latex: the part by weight=3-6:10-15 of blending emulsion.
Beneficial effect: the present invention is preferably tasteless containing under the effect of sulfur crosslinking agent; the double bond of the polyhutadiene section of composition polymer or the methylene radical at double bond ortho position very active; can react with the heteroatoms in pitch and active group; make pitch be grafted on composition polymer, generate polymkeric substance-pitch grafts.Grafts serves as tensio-active agent polymer phase is alternate with pitch, surface tension between reduction polymkeric substance and pitch and the Gibbs free energy of system, promote that polymkeric substance is compatible better with pitch, be conducive to polymer modification emulsified bitumen and form more stable system.
Linking agent has good effect to emulsified bitumen stability, and its three norms to normal temperature pitch residue produces and also can have an impact.
Affect emulsified modified asphalt performance factor a lot, important factor wherein comprises: heavy traffic asphaltum character, polymer modifiers kind and consumption, soap lye temperature, asphalt temperature, mechanical shearing, dosage of crosslinking agent and storage time etc.For the emulsified modified asphalt of upgrading, i.e. normal temperature bituminous liquids, the compound of different aqueous polymer dispersion is even more important.Different emulsifying process stablizes the chemical network formed and normal temperature asphalt performance has considerable influence, and wherein, dosage of crosslinking agent, soap lye temperature and storage time are the important factors affecting normal temperature pitch chemical network and performance.
Accompanying drawing explanation
Fig. 1 is normal temperature asphalt oil bag water structure schematic diagram;
Fig. 2 is the displaing micro picture that the present invention deposits the chemically crosslinked rock steady structure of non-chemically rock steady structure and interpolation linking agent after 5 days;
Fig. 3 is stable TEM morphological structure figure of the present invention;
Fig. 4 is the TEM morphological structure figure of instability of the present invention.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described.For those skilled in the art, under the premise without departing from the principles of the invention, can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Embodiment 1
A preparation method for high efficiency composition emulsion modifying agent, comprises as follows:
(1) styrene-butadiene-styrene thermoplastic elastomer aqueous latex is prepared;
(2) in styrene-butadiene-styrene thermoplastic elastomer aqueous latex, add the blending emulsion of the self-crosslinking modified acrylate emulsion (FG-H1811) of ethylene-vinyl acetate water miscible liquid (FG-CP606W)/anti-strong acid of positively charged ion, and be optimized compound; When FG-CP606W/FG-H1811 blending ratio is 80/20, emulsion has optimum performance; Wherein, styrene-butadiene-styrene thermoplastic elastomer aqueous latex: blending emulsion part by weight=1:3;
(3), in normal temperature pitch composite emulsion, the weight percent of styrene-butadiene-styrene thermoplastic elastomer aqueous latex is 5%, FG-CP606W/FG-H1811 blending emulsion (80/20) is 15%, and pitch is 55%, and water is 45%;
(4) composite good by above-mentioned mass ratio the CP606W/ H1811 of styrene-butadiene-styrene thermoplastic elastomer aqueous latex and optimization, and add wooden amine cation asphalt emulgent: 2%, one piece is mixed with seed soap lye;
(5) heated bitumen is mixed by certain mass ratio containing sulfur crosslinking agent with tasteless: dosage of crosslinking agent is heated bitumen 0.3%;
(6) step (4) and step (5) gained mixture are joined in mulser together, seed soap lye temperature controls at 50-60 DEG C, heated bitumen temperature controls at 135-150 DEG C, storage time controls more than 4 hours, final obtained high efficiency composition emulsion modifying agent, wherein styrene-butadiene-styrene thermoplastic elastomer aqueous latex: blending emulsion part by weight=1:3
Embodiment 2
A preparation method for high efficiency composition emulsion modifying agent, comprises as follows:
(1) styrene-butadiene-styrene thermoplastic elastomer aqueous latex is prepared;
(2) in styrene-butadiene-styrene thermoplastic elastomer aqueous latex, add the blending emulsion of the self-crosslinking modified acrylate emulsion (FG-H1811) of ethylene-vinyl acetate water miscible liquid (FG-CP606W)/anti-strong acid of positively charged ion, and be optimized compound; When FG-CP606W/FG-H1811 blending ratio is 80/20, emulsion has optimum performance; Wherein, styrene-butadiene-styrene thermoplastic elastomer aqueous latex: blending emulsion part by weight=2:3
(3), in normal temperature pitch composite emulsion, the weight percent of styrene-butadiene-styrene thermoplastic elastomer aqueous latex is 10%, FG-CP606W/FG-H1811 blending emulsion (80/20) is 15%, and pitch is 65%, and water is 35%;
(4) composite good by above-mentioned mass ratio the CP606W/ H1811 of styrene-butadiene-styrene thermoplastic elastomer aqueous latex and optimization, and add wooden amine cation asphalt emulgent: 3.5%, one piece is mixed with seed soap lye;
(5) heated bitumen is mixed by certain mass ratio containing sulfur crosslinking agent with tasteless: dosage of crosslinking agent is heated bitumen 1.0%;
(6) step (4) and step (5) gained mixture are joined together in mulser, seed soap lye temperature controls at 50-60 DEG C, and heated bitumen temperature controls at 135-150 DEG C, and the storage time controls more than 4 hours, final obtained high efficiency composition emulsion modifying agent,
Wherein styrene-butadiene-styrene thermoplastic elastomer aqueous latex: blending emulsion part by weight=1:3
embodiment 3
A preparation method for high efficiency composition emulsion modifying agent, comprises as follows:
(1) styrene-butadiene-styrene thermoplastic elastomer aqueous latex is prepared;
(2) in styrene-butadiene-styrene thermoplastic elastomer aqueous latex, add the blending emulsion of the self-crosslinking modified acrylate emulsion (FG-H1811) of ethylene-vinyl acetate water miscible liquid (FG-CP606W)/anti-strong acid of positively charged ion, and be optimized compound; When FG-CP606W/FG-H1811 blending ratio is 80/20, emulsion has optimum performance;
(3), in normal temperature pitch composite emulsion, the weight percent of styrene-butadiene-styrene thermoplastic elastomer aqueous latex is 7%, FG-CP606W/FG-H1811 blending emulsion (80/20) is 14%, and pitch is 58%, and water is 29%;
(4) composite good by above-mentioned mass ratio the CP606W/ H1811 of styrene-butadiene-styrene thermoplastic elastomer aqueous latex and optimization, and add wooden amine cation asphalt emulgent: 2.6%, one piece is mixed with seed soap lye;
(5) heated bitumen is mixed by certain mass ratio containing sulfur crosslinking agent with tasteless: dosage of crosslinking agent is heated bitumen 0.7%;
(6) step (4) and step (5) gained mixture are joined together in mulser, seed soap lye temperature controls at 54 DEG C, and heated bitumen temperature controls at 142 DEG C, and the storage time controls more than 4 hours, final obtained high efficiency composition emulsion modifying agent,
Wherein styrene-butadiene-styrene thermoplastic elastomer aqueous latex: blending emulsion part by weight=1:2
For the emulsified modified asphalt of upgrading, i.e. normal temperature bituminous liquids, the compound of different aqueous polymer dispersion is even more important.Table 2-8 is that the combination of different polymkeric substance is on the impact of the performance of normal temperature pitch.Result shows, only use the modification of a kind of styrene-butadiene-styrene thermoplastic elastomer water and milk sol, the softening temperature of pitch residue only reaches 60
oc, exceeds 5 than unmodified pitch
oc-10
oCleft and right.With styrene-butadiene-styrene thermoplastic elastomer and CP606W composite modified time, cohesive force need be improved, but low-temperature ductility decline many; And during CP606W/H1811 blending and modifying agent with styrene-butadiene-styrene thermoplastic elastomer+optimization, viscosifying power strong (raising more than 1 times more thermoplastic elastomer modified than styrene-butadiene-styrene), resistance to elevated temperatures good (raising 16 DEG C more thermoplastic elastomer modified than styrene-butadiene-styrene).
Table 1 composite emulsion is on the impact of normal temperature asphalt performance
Visible, when FG-CP606W/FG-H1811 blending and modifying agent of styrene-butadiene-styrene thermoplastic elastomer water and milk sol and optimization is composite modified, not only cohesive strength, softening temperature, kinetic viscosity increase substantially, and ductility is also better, reaches the requirement to emulsified bitumen height rigidity-toughness balanced, high combination property.
Table 2 composite emulsion is coated with the impact of film dynamic performance to normal temperature pitch
Table 2 is the test results obtained on UMT-2 micro tribology trier.Three kinds of samples are applied respectively to the load of 15mN, record sapphire pressure head to the depth of indentation of sample, thus can calculate the contact area of sapphire pressure head and sample.As can be seen from the table: the depth of indentation of sample styrene-butadiene-styrene thermoplastic elastomer (modifying asphalt) film is maximum, is out of shape maximum, and minimum with the film impression of three kinds of emulsion compounds, the most stable after pressurized; Taking second place of two kinds of emulsion compounds.Consistent with table 1.
Linking agent has good effect to emulsified bitumen stability, and its three norms to normal temperature pitch residue produces and also can have an impact.Affect emulsified modified asphalt performance factor a lot, important factor wherein comprises: heavy traffic asphaltum character, polymer modifiers kind and consumption, soap lye temperature, asphalt temperature, mechanical shearing, dosage of crosslinking agent and storage time etc.For the emulsified modified asphalt of upgrading, i.e. normal temperature bituminous liquids, the compound of different aqueous polymer dispersion is even more important.Different emulsifying process stablizes the chemical network formed and normal temperature asphalt performance has considerable influence, wherein, dosage of crosslinking agent, soap lye temperature and storage time are the important factors affecting normal temperature pitch chemical network and performance, if table 3 technique and form are below on shown in the impact of normal temperature asphalt performance.
Table 3 technique and form are on the impact of normal temperature asphalt performance
Note: emulsifying process I, II difference is that the former has done Optimization Work to dosage of crosslinking agent, soap lye temperature and storage time.
As seen from Table 3, emulsifying process I produces normal temperature pitch stable chemical network, and its cohesive strength, softening temperature and ductility are all better than (the corresponding emulsifying process II) of chemical network instability, and package stability is much better than the latter.
As shown in Figure 3,4, to be cross-linked by composition polymer and in the spacial framework formed because pitch is wrapped in, resultant of reaction is present between polymer phase and pitch phase interface, play Action of Surfactant, the Gibbs free energy of the polymer phase surface tension alternate with pitch and system can be reduced, prevent the cohesion of polymkeric substance, stop and be separated with composition polymer, thus the dispersion of stabilization of polymer in pitch.
Fig. 2 is the displaing micro picture of the chemically crosslinked rock steady structure depositing non-chemically rock steady structure and interpolation linking agent after 5 days.As seen from the figure, the normal temperature Bituminous stabilized of chemical network structure is good, but not chemically stable, produces agglomeration.
Claims (2)
1. a preparation method for high efficiency composition emulsion modifying agent, is characterized in that: comprise as follows:
(1) prepare styrene-butadiene-styrene thermoplastic elastomer aqueous latex: first add in organic solvent by solid thermoplastic rubber, be heated to 70 DEG C, and stir under the rotating speed of 300-400 rev/min; Next carries out emulsification, slowly add in this solution under low shearing speed 2500-3000 rev/min and be dissolved with tensio-active agent, the electrolytical aqueous solution, then rotating speed is transferred to high speed shear 7500-8000 rev/min of thermoplastic elastomer grain breakage to less than 1 micron, emulsification obtains emulsion form thermoplastic elastomer liquid, finally reclaim the organic solvent in aforesaid liquid, finally obtain rubber water-based latex bitumen properties-correcting agent;
(2) in styrene-butadiene-styrene thermoplastic elastomer aqueous latex, add the blending emulsion of the self-crosslinking modified acrylate emulsion (FG-H1811) of ethylene-vinyl acetate water miscible liquid (FG-CP606W)/anti-strong acid of positively charged ion, and be optimized compound; When FG-CP606W/FG-H1811 blending ratio is 80/20, emulsion has optimum performance;
(3), in normal temperature pitch composite emulsion, the weight percent of styrene-butadiene-styrene thermoplastic elastomer aqueous latex is 6%-10%, FG-CP606W/FG-H1811 blending emulsion (80/20) is 8%-15%, and pitch is 55%-65%, and water is 25%-35%;
(4) composite good by above-mentioned mass ratio the CP606W/ H1811 of styrene-butadiene-styrene thermoplastic elastomer aqueous latex and optimization, and add wooden amine cation asphalt emulgent: 2%-3.5%, one piece is mixed with seed soap lye;
(5) heated bitumen is mixed by certain mass ratio containing sulfur crosslinking agent with tasteless: dosage of crosslinking agent is heated bitumen 0.3%-1.0%;
(6) step (4) and step (5) gained mixture are joined in mulser together, seed soap lye temperature controls at 50-60 DEG C, heated bitumen temperature controls at 140-150 DEG C, and the storage time controls more than 4 hours, final obtained high efficiency composition emulsion modifying agent.
2. the preparation method of high efficiency composition emulsion modifying agent according to claim 1, is characterized in that: in high efficiency composition emulsion modifying agent, styrene-butadiene-styrene thermoplastic elastomer aqueous latex: the part by weight=3-6:10-15 of blending emulsion.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106590423A (en) * | 2016-12-22 | 2017-04-26 | 南通福伦利新材料有限公司 | Primary color compound waterproof factice and preparing method and construction technology thereof |
| CN115045154A (en) * | 2022-07-13 | 2022-09-13 | 华运通达(广东)道路科技有限公司 | Cold-mixed cold-paved ultrathin asphalt wearing layer and preparation method thereof |
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| CN101565533A (en) * | 2009-05-11 | 2009-10-28 | 山西省交通科学研究院 | Method for preparing color liquid SBS modified emulsion resin |
| US20100267865A1 (en) * | 2007-06-26 | 2010-10-21 | Petroleo Brasileiro S.A. - Petrobras | Compositions of controlled-breakage cationic asphalt microsurfacing emulsions |
| CN102010603A (en) * | 2010-10-27 | 2011-04-13 | 周乃承 | Rubber powder modified emulsified asphalt and preparation method thereof |
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2014
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100267865A1 (en) * | 2007-06-26 | 2010-10-21 | Petroleo Brasileiro S.A. - Petrobras | Compositions of controlled-breakage cationic asphalt microsurfacing emulsions |
| CN101565533A (en) * | 2009-05-11 | 2009-10-28 | 山西省交通科学研究院 | Method for preparing color liquid SBS modified emulsion resin |
| CN102010603A (en) * | 2010-10-27 | 2011-04-13 | 周乃承 | Rubber powder modified emulsified asphalt and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106590423A (en) * | 2016-12-22 | 2017-04-26 | 南通福伦利新材料有限公司 | Primary color compound waterproof factice and preparing method and construction technology thereof |
| CN106590423B (en) * | 2016-12-22 | 2019-04-19 | 南通福伦利新材料有限公司 | A kind of primary colors composite water-proof ointment and preparation method thereof and construction technology |
| CN115045154A (en) * | 2022-07-13 | 2022-09-13 | 华运通达(广东)道路科技有限公司 | Cold-mixed cold-paved ultrathin asphalt wearing layer and preparation method thereof |
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