阅读说明：本技术 一种固体温拌改性双效沥青改性剂及其制备方法 (Solid warm-mix modified double-effect asphalt modifier and preparation method thereof ) 是由 邹泰 冯勋红 董光彬 郝晓君 穆明浩 张哲� 陈秀秀 王盼 毕玉峰 耿立涛 刘占 于 2020-06-15 设计创作，主要内容包括：本发明提供了一种固体温拌改性双效沥青改性剂及其制备方法,主要由以下原料制备而成：MAH-g-POE、赖氨酸盐酸盐以及聚醚二醇单甲醚。所述固体温拌改性双效沥青改性剂同时兼备温拌与改性双重功效。具体地,其中包含聚醚链段具有非离子表面活性和润滑作用,可以降低沥青与集料石子间的表界面张力,提高沥青混合料的流动性,使沥青混合料远低于热拌温度下与矿料混拌均匀,实现温拌效果。其中包含POE链具有强韧性,可以有效改善沥青混合料的高温抗剪切能力和抗冲击阻滞能力,从而提高沥青改性料的高温抗车辙能力和低温耐屈挠能力；其中接枝的马来酸酰胺基团具有强极性,使沥青混合料与集料石子紧密包裹,混料更加均匀；实现改性效果,提升沥青混合料的路面使用性能。(The invention provides a solid warm-mix modified double-effect asphalt modifier and a preparation method thereof, and the modifier is mainly prepared from the following raw materials: MAH-g-POE, lysine hydrochloride, and polyether glycol monomethyl ether. The solid warm-mixing modified double-effect asphalt modifier has dual effects of warm mixing and modification. Specifically, the polyether chain segment contained in the asphalt mixture has nonionic surface activity and a lubricating effect, so that the surface interfacial tension between asphalt and aggregate stones can be reduced, the fluidity of the asphalt mixture is improved, the asphalt mixture is uniformly mixed with mineral aggregates at a temperature far lower than a hot-mixing temperature, and a warm-mixing effect is realized. The modified asphalt material comprises a POE chain which has obdurability and can effectively improve the high-temperature anti-shearing capability and the impact resistance retardation capability of the asphalt mixture, thereby improving the high-temperature anti-rutting capability and the low-temperature flex resistance capability of the asphalt modified material; the grafted maleic acid amide group has strong polarity, so that the asphalt mixture and aggregate stones are tightly wrapped, and the mixture is more uniform; the modification effect is realized, and the pavement service performance of the asphalt mixture is improved.)

1. The solid warm-mix modified double-effect asphalt modifier is characterized by being mainly prepared from the following raw materials: MAH-g-POE, lysine hydrochloride and polyether glycol monomethyl ether;

wherein the using molar ratio of the lysine hydrochloride to the polyether glycol monomethyl ether is (1.2-1.5) to 1; the polyether glycol monomethyl ether is one or a mixture of two of polyethylene glycol monomethyl ether and polypropylene glycol monomethyl ether in any proportion.

2. The solid warm-mix modified double-effect asphalt modifier of claim 1, wherein the melt index of MAH-g-POE is 10-30g/10min at 190 ℃ under the test condition of 2.16Kg, and the grafting ratio is 0.7-0.9%.

3. The solid warm-mix modified double-effect asphalt modifier as claimed in claim 1, wherein the molecular weight of the polyethylene glycol monomethyl ether is 200-550, and the hydroxyl value is 143-255 mgKOH/g.

4. The solid warm-mix modified double-effect asphalt modifier as claimed in claim 1, wherein the molecular weight of the polypropylene glycol monomethyl ether is 400-600, and the hydroxyl value is 100-150 mgKOH/g.

5. The preparation method of the solid warm-mix modified double-effect asphalt modifier as claimed in any one of claims 1 to 4, which is characterized by comprising the following steps:

step one, adding lysine hydrochloride and polyether glycol monomethyl ether into an anhydrous toluene solvent, stirring, carrying out an esterification reaction, and refluxing the reaction until no water is generated; then adding sodium bicarbonate solid, continuously stirring and reacting until no gas is discharged, and stopping the reaction; filtering and washing the reaction solution, and drying in vacuum to obtain polyether glycol monomethyl ether lysine ester;

step two, mixing 95-97 parts of MAH-g-POE and 3-5 parts of polyether glycol monomethyl ether lysine ester obtained in the step one in a high-speed mixer for 60min, wherein the mixing condition is that the temperature is 60 ℃ and the rotating speed is 500 rpm;

step three, extruding the material obtained after the mixing and stirring in the step two in an extruder, wherein the extrusion conditions are that the temperature is 180 ℃ and the rotating speed is 300 rpm; then drying and crushing at 80 ℃; and finally, screening the solid warm-mixed modified double-effect asphalt modifier with the grain size of 30-60 meshes.

Technical Field

The invention relates to the technical field of asphalt modification, in particular to a solid warm-mix modified double-effect asphalt modifier and a preparation method thereof.

Background

The traditional asphalt pavement construction method is a hot-mix asphalt mixture method, harmful gases can be released due to the mixing temperature in the mixing, transportation and construction processes, a large amount of energy can be consumed, and gases such as carbon dioxide and the like can be released. Therefore, in order to reduce the exhaust gas emission and reduce the energy consumption, people begin to develop energy-saving and environment-friendly warm-mix asphalt mixtures. The warm-mixed asphalt mixture is a technology which improves the construction workability of the asphalt mixture by reducing the viscosity of asphalt cement, so that asphalt can be mixed and constructed at a relatively low temperature, and meanwhile, the service performance of the warm-mixed asphalt mixture is not lower than that of the warm-mixed asphalt mixture.

In the application of road engineering, when the traditional warm-mixing agent is used for producing common asphalt mixture, only the warm-mixing function can be realized, but the improvement of the road performance of the asphalt mixture cannot be realized; in addition, when the warm mixing agent is used for producing the modified asphalt mixture, finished modified asphalt needs to be purchased in advance, so that the production cost is increased, and the hidden danger that the performance of the modified asphalt is decayed when the modified asphalt is stored to influence the pavement quality exists. Therefore, although the modification and warm mixing technologies of the asphalt mixture are developed more mature, no mature technology for integrating the functions of warm mixing and modification of the asphalt mixture is available at present.

Disclosure of Invention

Aiming at the problems in the prior art, the invention aims to provide an asphalt modifier with dual functions of warm mixing and modification, which can not only enable an asphalt mixture to be uniformly mixed at a temperature far lower than that of hot mixing, but also effectively improve the high-temperature anti-shearing capability and the impact resistance retardation capability of the asphalt mixture and improve the high-temperature anti-rutting capability and the low-temperature anti-flexing capability of the asphalt mixture. Meanwhile, the invention provides a preparation method thereof.

In order to achieve the purpose of the invention, the technical scheme provided by the invention is as follows:

the invention provides a solid warm-mix modified double-effect asphalt modifier which is mainly prepared from the following raw materials: MAH-g-POE, lysine hydrochloride and polyether glycol monomethyl ether; wherein the using molar ratio of the lysine hydrochloride to the polyether glycol monomethyl ether is (1.2-1.5) to 1; the polyether glycol monomethyl ether is one or a mixture of two of polyethylene glycol monomethyl ether and polypropylene glycol monomethyl ether in any proportion.

On the basis of the scheme, the MAH-g-POE is maleic anhydride grafted polyolefin elastomer, the melt index of the MAH-g-POE is 10-30g/10min under the test conditions of 190 ℃ and 2.16Kg, and the grafting rate is 0.7-0.9%. Under the performance, the adhesive property and compatibility when being combined with polar materials and non-polar materials can be effectively improved.

On the basis of the scheme, lysine hydrochloride is the only amino acid containing two amino groups, and the esterification reaction is carried out on the lysine hydrochloride and polyether glycol monomethyl ether to obtain the polyether glycol monomethyl ether lysine ester which has nonionic surface activity and can be used as a surfactant.

Based on the above scheme, the molecular weight of polyethylene glycol monomethyl ether is 200-600, which is recorded as MPEG200-600, and the hydroxyl value is 143-255 mgKOH/g. Under the performance, polyethylene glycol monomethyl ether is easy to perform esterification reaction with lysine hydrochloride.

On the basis of the scheme, the molecular weight of polypropylene glycol monomethyl ether is 400-600, and is marked as MPPG 400-600; the hydroxyl value is 100-150 mgKOH/g.

The invention provides a preparation method of a solid warm-mix modified double-effect asphalt modifier, which comprises the following steps:

step one, adding lysine hydrochloride and polyether glycol monomethyl ether into an anhydrous toluene solvent, stirring, carrying out an esterification reaction, and refluxing the reaction until no water is generated; then adding sodium bicarbonate solid, continuously stirring and reacting until no gas is discharged, and stopping the reaction; filtering and washing the reaction solution, and drying in vacuum to obtain polyether glycol monomethyl ether lysine ester;

step two, mixing MAH-g-POE and the polyether glycol monomethyl ether lysine ester obtained in the step one in a high-speed mixer for 60min, wherein the mixing condition is that the temperature is 60 ℃ and the rotating speed is 500 rpm;

step three, extruding the material obtained after the mixing and stirring in the step two in an extruder, wherein the extrusion conditions are that the temperature is 180 ℃ and the rotating speed is 300 rpm; then drying and crushing at 80 ℃; and finally, screening the solid warm-mixed modified double-effect asphalt modifier with the grain size of 30-60 meshes.

Wherein sodium bicarbonate is used as a neutralizer for neutralizing hydrochloric acid molecules in lysine hydrochloride in the reaction liquid, thereby improving the purity of the reaction product.

The synthetic reaction formula of the solid warm-mix modified double-effect asphalt modifier provided by the invention is shown in figure 1.

Specifically, lysine hydrochloride is the only amino acid compound containing two amino groups; the polyether glycol monomethyl ether has excellent lubricating property, moisture retention property and dispersing property; lysine hydrochloride and polyether glycol monomethyl ether are subjected to esterification reaction, and the polyether glycol monomethyl ether lysine ester obtained by the reaction has nonionic surface activity and can be used as a surfactant. MAH-g-POE is maleic anhydride grafted polyolefin elastomer, which introduces strong polar side group maleic anhydride on the main chain of nonpolar molecular polyolefin, can improve the adhesion and compatibility when combined with polar materials and nonpolar materials, and is used as a toughening agent and a compatilizer with excellent performance. And carrying out amidation reaction on the MAH-g-POE and polyether glycol monomethyl ether lysine ester in the extrusion process of an extruder to generate the graft copolymer of the weak polar elastomer molecular main chain grafted with the branched chain structure with comb-shaped nonionic surface activity.

As shown in figure 1, in the molecular structural formula of the solid warm-mix modified double-effect asphalt modifier prepared in the invention, POE (polyolefin elastomer) molecules have weaker polarity, and can be mutually soluble with an asphalt mixture in the production process. The POE chain has high toughness and is insensitive to temperature change, and the high-temperature shear resistance and impact resistance retardation of the asphalt mixture can be effectively improved, so that the high-temperature rutting resistance and the low-temperature flex resistance of the asphalt mixture are improved. The polyether chain segment has nonionic surface activity, can reduce the surface interfacial tension between nonpolar asphalt and aggregate stones, can play a role in lubrication, improves the fluidity of the asphalt mixture, and enables the asphalt mixture to be uniformly mixed with mineral aggregates at a temperature far lower than the hot-mixing temperature. The grafted maleic acid amide groups have strong polarity, can be uniformly distributed on the surface of the asphalt mixture, and are mutually compatible with the polar structure on the surface of the aggregate stones, so that the asphalt mixture and the aggregate stones are tightly wrapped, and the void ratio is reduced.

The technical scheme provided by the invention has the following beneficial effects:

1. the asphalt modifier provided by the invention has a warm-mixing effect, and the polyether chain segment contained in the asphalt modifier has nonionic surface activity and a lubricating effect, so that the surface interfacial tension between asphalt and aggregate stones can be reduced, the fluidity of an asphalt mixture is improved, and the asphalt mixture is uniformly mixed with mineral aggregates at a temperature far lower than a hot-mixing temperature.

2. The asphalt modifier provided by the invention has a modification effect, and the POE chain contained in the asphalt modifier has high toughness, so that the high-temperature shearing resistance and the impact resistance retardation of an asphalt mixture can be effectively improved, and the high-temperature rutting resistance and the low-temperature flexing resistance of the asphalt modifier are improved. The grafted maleic acid amide group has strong polarity, so that the asphalt mixture and aggregate stones are tightly wrapped, and the mixture is more uniform.

Therefore, the asphalt modifier with double effects of warm mixing and modification is provided, the warm mixing effect is realized, and the pavement service performance of the asphalt mixture can be effectively improved.

Drawings

FIG. 1 is a schematic diagram of a synthetic reaction formula of a medium-solid warm-mixing modified double-effect asphalt modifier.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the contents in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items. Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.