WO2019129148A1 - 一种改性沥青及其制备方法 - Google Patents

一种改性沥青及其制备方法 Download PDF

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Publication number
WO2019129148A1
WO2019129148A1 PCT/CN2018/124387 CN2018124387W WO2019129148A1 WO 2019129148 A1 WO2019129148 A1 WO 2019129148A1 CN 2018124387 W CN2018124387 W CN 2018124387W WO 2019129148 A1 WO2019129148 A1 WO 2019129148A1
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Prior art keywords
parts
modified asphalt
asphalt
modifier
present
Prior art date
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Ceased
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PCT/CN2018/124387
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English (en)
French (fr)
Inventor
虞将苗
苏国城
莫广亮
陈富达
陈丽娟
卢健元
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Guangdong Gt-Tech Road Material Technology Co Ltd
South China University of Technology SCUT
Original Assignee
Guangdong Gt-Tech Road Material Technology Co Ltd
South China University of Technology SCUT
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Priority to US16/650,099 priority Critical patent/US11572445B2/en
Publication of WO2019129148A1 publication Critical patent/WO2019129148A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/005—Processes for mixing polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2395/00—Bituminous materials, e.g. asphalt, tar or pitch
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2453/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2555/00—Characteristics of bituminous mixtures
    • C08L2555/40—Mixtures based upon bitumen or asphalt containing functional additives
    • C08L2555/80—Macromolecular constituents
    • C08L2555/84—Polymers comprising styrene, e.g., polystyrene, styrene-diene copolymers or styrene-butadiene-styrene copolymers

Definitions

  • the invention belongs to the technical field of road building materials, and particularly relates to a modified asphalt and a preparation method thereof.
  • Asphalt is an indispensable bonding material for road construction and pavement maintenance engineering. With the rapid development of highway construction and maintenance work, the demand for asphalt is increasing year by year. At present, all countries in the world have been striving to advocate the development concept of “resource conservation and environmental friendliness”. All kinds of thin layer asphalt pavement structure systems echo the main development direction of highway construction and maintenance. In addition, China has proposed the construction of “sponge city”. "The plan, high-performance permeable asphalt pavement is the key link in the process of building a "sponge city.” In the road industry, the development of related concepts requires a higher performance and more durable asphalt binder system.
  • asphalt binder As a typical viscoelastic material, asphalt binder has strong engineering significance for the viscosity and elasticity of asphalt binder. At present, there are many high-viscosity modified asphalts on the market, and there are also high-elastic modified asphalt systems. However, due to the contradiction between the two indicators, it is very technically difficult to obtain high viscosity and high elasticity indexes in the same asphalt cement material. At the same time, asphalt binder with high viscosity and high elasticity is considered to be a major development direction of high performance asphalt. It is an extremely important bonding material for ultra-thin asphalt structure and permeable asphalt pavement system.
  • the present invention provides a modified asphalt prepared by including the following raw materials in parts by weight, 100 to 120 parts of a matrix pitch, 6 to 20 parts of a modifier, 3 to 9 parts of a compatibilizer, and sulfur. 0.15 to 0.25 parts, 0.4 to 0.6 parts of a non-amine anti-stripping agent and 0.2 to 0.4 parts of a coupling agent;
  • the modifier includes a styrene-butadiene-styrene block copolymer, a rubber, and a polyurethane.
  • the mass ratio of the styrene-butadiene-styrene block copolymer, rubber and polyurethane in the modifier is from 1 to 4:0.5 to 2:0.5 to 2.
  • the styrene-butadiene-styrene block copolymer has a star structure, and the styrene-butadiene-styrene block copolymer has a number average molecular weight of more than 200,000;
  • the rubber is a rubber powder, and the rubber powder has a particle diameter of 40 to 100 mesh;
  • the polyurethane has a number average molecular weight of more than 10,000.
  • the compatibilizer comprises one or more of an aromatic hydrocarbon, a linear alkane, and a cycloalkane.
  • the coupling agent is a silane coupling agent.
  • the invention also provides a preparation method of the modified asphalt according to the above technical solution, comprising the following steps:
  • the second mixture obtained in the step (3) is sequentially subjected to shearing, grinding and development to obtain a modified asphalt.
  • the temperature mixed in the step (1) is 160 to 180 °C.
  • the shearing speed in the step (2) and the step (4) is independently 7000 to 10000 r/min, and the shearing time is independently 30 to 50 min.
  • the time of swelling in the step (2) is 30 to 50 minutes.
  • the grinding speed in the step (4) is 10,000-14000 r/min, and the grinding time is 10-30 min.
  • the modified asphalt provided by the invention is prepared from the raw materials including the following parts by weight, the asphalt is 100-120 parts, the modifier is 6-20 parts, the compatibilizer is 3-9 parts, the sulfur is 0.15-0.25 parts, and the non-amine anti-
  • the exfoliating agent is 0.4 to 0.6 parts and the coupling agent is 0.2 to 0.4 parts; and the modifier includes a styrene-butadiene-styrene block copolymer, a rubber, and a polyurethane.
  • the modifier is mainly composed of a styrene-butadiene-styrene block copolymer, a rubber and a polyurethane, and is compatible with the matrix asphalt to form a spatial crosslinked structure, thereby improving the matrix pitch.
  • the mechanical properties; the addition of components such as compatibilizer, sulfur, coupling agent, etc., further promote the uniform dispersion of the modifier in the matrix asphalt, and provide conditions for the function of the modifier.
  • the above components are combined to obtain a modified asphalt having high viscosity and elasticity.
  • the results of the examples show that the modified asphalt provided by the invention can simultaneously satisfy: elastic recovery of ⁇ 98% at 25 °C, dynamic viscosity of 60 °C ⁇ 500,000 Pa ⁇ s, composite shear modulus of 60 °C ⁇ 10 kPa, G * /Sin ⁇
  • the critical temperature of 2.2 kPa is ⁇ 94 °C.
  • the invention provides a modified asphalt prepared by using the following raw materials by weight, the matrix pitch is 100-120 parts, the modifier is 6-20 parts, the compatibilizer is 3-9 parts, the sulfur is 0.15-0.25 parts, The non-amine anti-stripping agent is 0.4 to 0.6 parts and the coupling agent is 0.2 to 0.4 parts; and the modifier includes a styrene-butadiene-styrene block copolymer, a rubber, and a polyurethane.
  • the raw materials of the modified asphalt are all commercially available products well known to those skilled in the art unless otherwise specified.
  • the modified asphalt raw material provided by the present invention comprises, by weight, 100 to 120 parts, more preferably 105 to 115 parts, and still more preferably 108 to 112 parts by weight of the base asphalt.
  • the present invention does not make any special provisions for the specific model of the matrix asphalt, and it is well known to those skilled in the art.
  • the matrix pitch is preferably 50# asphalt, 70# asphalt or 90# asphalt.
  • the modified asphalt provided by the present invention includes 6 to 20 parts of a modifier, more preferably 8 to 18 parts, and still more preferably 12 to 18 parts, based on the parts by weight of the base pitch.
  • the invention utilizes a styrene-butadiene-styrene block copolymer, a rubber and a polyurethane to form a modifier, and can form a spatial crosslinked structure after being compatible with the matrix asphalt, and the base material is wrapped in the crosslinked structure to be modified. The overall viscosity and elasticity of the bitumen are improved.
  • the mass ratio of the styrene-butadiene-styrene block copolymer (hereinafter referred to as SBS), rubber and polyurethane in the modifier is from 1 to 4:0.5 to 2:0.5 to 2, More preferably, it is 1.5 to 3.5:1 to 1.8:0.8 to 1.5, and more preferably 1.8 to 3:1.2 to 1.5:1.0 to 1.2.
  • the SBS is preferably a star structure.
  • the number average molecular weight of the SBS is preferably more than 200,000, more preferably from 210,000 to 500,000, still more preferably from 250,000 to 450,000.
  • the rubber is preferably a rubber powder, and the rubber powder preferably has a particle diameter of 40 to 100 mesh, more preferably 60 to 100 mesh, and still more preferably 80 to 100 mesh.
  • the rubber powder preferably has a specific surface area of 2 m 2 /g or more, more preferably 3 to 14 m 2 /g, and still more preferably 5 to 10 m 2 /g.
  • the number average molecular weight of the polyurethane is preferably more than 10,000, more preferably from 10,000 to 500,000, still more preferably from 100,000 to 300,000.
  • the specific source of the SBS, the rubber powder and the polyurethane is not particularly limited in the present invention, so that the control of the above parameters can be achieved.
  • the present invention preferably provides the modifier with excellent viscosity and elasticity by defining the SBS structure and the number average molecular weight, the particle size and specific surface area of the rubber powder, and the number average molecular weight of the polyurethane.
  • the modified asphalt provided by the present invention comprises 3 to 9 parts, preferably 3.5 to 8 parts, more preferably 4 to 6 parts, based on the parts by weight of the base pitch.
  • the compatibilizing agent preferably includes one or more of an aromatic hydrocarbon, a linear alkane, and a cycloalkane, and further preferably a linear alkane.
  • the number of carbon atoms of the aromatic hydrocarbon, linear alkane and cycloalkane is preferably C7 to C14, and more preferably C8 to C12.
  • the compatibilizing agent when the compatibilizing agent is a mixture of several components, the present invention does not have any particular regulation on the amount ratio of each component in the mixture.
  • the present invention further defines the components and amounts of the compatibilizing agent to promote the mutual solubility of the modifier and the matrix asphalt, thereby facilitating better formation of the spatial crosslinked structure.
  • the modified asphalt provided by the present invention comprises 0.15 to 0.25 parts of sulfur, preferably 0.18 to 0.22 parts, more preferably 0.2 parts, based on the parts by weight of the base pitch.
  • the present invention has no particular requirement for the particle size of the sulfur, and it is well known to those skilled in the art.
  • the invention improves the storage stability of the modified asphalt by adding sulfur.
  • the modified asphalt provided by the present invention includes 0.4 to 0.6 parts of a non-amine anti-stripping agent, and more preferably 0.45 to 0.55 parts, based on the parts by weight of the base pitch.
  • the non-amine anti-stripping agent is preferably an XT-1 type asphalt anti-stripping agent and/or an XT-2 type asphalt anti-stripping agent, and further preferably an XT-1 type asphalt anti-stripping agent.
  • the non-amine anti-stripping agent can improve the adhesion of the matrix asphalt to the aggregate through physical adsorption and chemical action, thereby improving the water damage resistance of the modified asphalt.
  • the modified asphalt provided by the present invention comprises 0.2 to 0.4 parts, more preferably 0.25 to 0.35 parts, based on the parts by weight of the base pitch.
  • the coupling agent is preferably a silane coupling agent, and more preferably KH550 or KH560.
  • the invention utilizes a coupling agent to improve the bonding performance of the asphalt with the aggregate and the cement concrete aggregate, so that the modified asphalt has high bonding performance.
  • the modified asphalt of the invention can simultaneously satisfy: elastic recovery of ⁇ 98% at 25 °C, dynamic viscosity of 60 °C ⁇ 500,000 Pa ⁇ s, composite shear modulus of 60 °C ⁇ 10 kPa, critical temperature of G */ Sin ⁇ 2.2 kPa ⁇ 94 °C.
  • the invention also provides a preparation method of the modified asphalt according to the above technical solution, comprising the following steps:
  • the second mixture obtained in the step (3) is sequentially subjected to shearing, grinding and development to obtain a modified asphalt.
  • the present invention mixes the molten matrix asphalt with a modifier, a compatibilizer and a coupling agent to obtain a premix.
  • the modifier is preferably obtained by mixing a styrene-butadiene-styrene block copolymer, a rubber and a polyurethane at normal temperature.
  • the present invention has no particular requirement for the mixing order of the styrene-butadiene-styrene block copolymer, rubber and polyurethane.
  • the mixing according to the invention is preferably carried out under agitation to uniformly mix the styrene-butadiene-styrene block copolymer, the rubber and the polyurethane.
  • the present invention has no special requirements for the specific embodiment of the agitation, so that the components can be uniformly mixed.
  • the invention defines a mixing mode to obtain a modification effect with better viscoelasticity.
  • the present invention is not particularly limited in the manner of melting the matrix pitch.
  • the matrix asphalt preferably has a melting temperature of 160 to 200 ° C, more preferably 165 to 175 ° C, and the melting time is preferably 2. ⁇ 3h, further preferably 2.2 to 2.8h.
  • the temperature at which the molten matrix pitch is mixed with the modifier, the compatibilizing agent and the coupling agent is preferably from 160 to 200 ° C, more preferably from 165 to 175 ° C.
  • the mixing is preferably carried out under stirring.
  • the specific embodiment of the agitation of the present invention is not particularly limited, so that the components can be uniformly dispersed.
  • the mixing order of the molten matrix asphalt, the modifier, the compatibilizer and the coupling agent is not particularly limited in the present invention.
  • the present invention sequentially shears and swells the premix to obtain a first mixture.
  • the premix is sheared by the present invention, the residual heat of the premix is used to maintain the mixed system as a slurry state, and only the premix is required to be insulated.
  • the present invention has no particular requirements for the specific embodiment of the thermal insulation, and is well known to those skilled in the art.
  • the shearing speed is preferably 7,000 to 10,000 r/min, more preferably 8,000 to 9000 rpm
  • the shearing time is preferably 30 to 50 minutes, more preferably 35 to 48 minutes, still more preferably 40 to 45 minutes.
  • the specific embodiment of the shearing of the present invention is not particularly limited, and it is well known to those skilled in the art.
  • the sheared premix is swollen.
  • the swelling temperature is preferably 165 to 175 ° C, more preferably 170 ° C; the swelling time is preferably 30 to 50 min, more preferably 35 to 48 min, still more preferably 40 to 45 min.
  • the specific embodiment of the swelling of the present invention is not particularly limited, so that the control of the above parameters can be achieved.
  • the swelling of the present invention is accomplished in a swelling tank.
  • the invention sequentially shears and swells the premix, and utilizes strong shearing force and collision action to fully disperse the modifier in the matrix asphalt, and at the same time refine the particles of each component to form a stable mixture.
  • Dissolving system; and swelling provides favorable conditions for the modifier to form a spatial crosslinked structure with the matrix asphalt.
  • the present invention mixes the first mixture with a non-amine anti-stripping agent and sulfur to obtain a second mixture.
  • the temperature at which the first mixture is mixed with the non-amine anti-stripping agent and sulfur is preferably 170 to 180 ° C, and more preferably 172 to 178 ° C.
  • the mixing is preferably carried out under stirring. The present invention does not specifically stipulate the specific embodiment of the agitation, so as to achieve the purpose of uniform mixing of the components.
  • the second mixture is sequentially sheared and ground to obtain a modified asphalt.
  • the shear rate of the second mixture is preferably 7,000 to 10,000 r/min, further preferably 8,000 to 9000 rpm, and the shearing time of the second mixture is preferably 30 to 50 minutes, further preferably It is 35 to 48 minutes, more preferably 40 to 45 minutes.
  • the shearing specific embodiment of the second mixture of the present invention is not particularly limited, and it is well known to those skilled in the art.
  • the second mixture is sheared by the invention, and the non-amine anti-stripping agent and the sulfur are thoroughly mixed with the first mixture by using the strong force generated during shearing, thereby further improving the stability of the second mixture mixing system and improving the stability. Water damage resistance of matrix asphalt.
  • the second mixture of the sheared material is ground by the present invention to obtain a modified asphalt initial sample.
  • the polishing speed of the present invention is preferably 10,000 to 14,000 r/min, more preferably 12,000 rpm, and the polishing time is preferably 10 to 30 minutes, more preferably 15 to 28 minutes.
  • the grinding according to the invention is preferably carried out in a colloid mill.
  • the average particle diameter of the modifier in the modified asphalt initial sample is preferably ⁇ 4 ⁇ m, and more preferably 0.1 to 3 ⁇ m.
  • the initial sample of the modified asphalt is obtained, and the invention develops the initial sample of the modified asphalt, so that the modifier cross-links in the matrix asphalt, thereby forming a spatial network structure better, and ensuring the obtained modified asphalt. Sticky effect.
  • the modified asphalt is preferably transferred to a finished development tank for development.
  • the development temperature is preferably 170 to 190 ° C, more preferably 180 ° C, and the development time is preferably 24 to 48 h, and more preferably 36 to 48 h.
  • the invention develops the initial sample of the modified asphalt, and uses the high temperature effect to fully dissolve the modifier with the matrix asphalt to form a stable spatial crosslinked structure, thereby ensuring storage stability and viscoelasticity of the modified asphalt. .
  • modified asphalt provided by the present invention and its preparation method are described in detail below with reference to the examples, but they are not to be construed as limiting the scope of the invention.
  • Modifier 2 parts of SBS having a number average molecular weight of 300,000, 1 part of a rubber powder having a particle size of 80 mesh, and 1 part of a polyurethane having a number average molecular weight of 100,000; and being obtained by mixing at room temperature for 20 minutes.
  • Raw materials 110 parts of 50# matrix asphalt, 13 parts of modifier, 4 parts of sodium dodecylbenzenesulfonate, 0.2 parts of sulfur, 0.5 parts of XT-1 anti-stripping agent and 0.50 parts of KH;
  • the matrix asphalt was heated at 175 ° C for 2 h, then the modifier, sodium dodecylbenzene sulfonate and KH560 were added and stirred for 20 min to obtain a premix;
  • the shear rate was controlled to be 8000 r/min, and the premix after shearing was placed in a swelling tank and swollen at 175 ° C for 50 min to obtain a first mixture;
  • the second mixture was placed in a shearing pump, the shearing speed was controlled to 8000 r/min, and after shearing for 40 min, it was ground in a colloid mill for 30 min to obtain a modified asphalt initial sample; the average particle of the modifier in the initial sample The diameter is 1.5 ⁇ m.
  • the modified asphalt was transferred to the finished development tank, and was kept at 180 ° C for 36 h to obtain a modified asphalt.
  • the invention tests the performance and key indexes of the modified asphalt obtained in the present embodiment, and adopts the relevant test methods in the “Test Code for Highway Engineering Asphalt and Asphalt Mixture” (JTG E20-2011), and the results are shown in Table 1. Shown.
  • Modifier 1.8 parts of SBS having a number average molecular weight of 200,000, 1.2 parts of a rubber powder having a particle size of 100 mesh, and 1 part of a polyurethane having a number average molecular weight of 150,000; and mixing at room temperature for 15 minutes.
  • Raw materials 110 parts of 70# matrix asphalt, 16 parts of modifier, 4.5 parts of aromatic oil, 0.2 parts of sulfur, 0.5 parts of XT-1 anti-stripping agent, and KH5500.3 parts.
  • the base asphalt was heated at 170 ° C for 3 h, then the modifier, aromatic oil and KH550 were added and stirred for 15 min to obtain a premix;
  • the premixed material was placed in a shearing pump, the shearing speed was controlled to be 9000 r/min, and after shearing for 30 min, the sheared premix was placed in a swelling tank at 170 ° C for 30 min to obtain a first mixture;
  • the second mixture was placed in a shearing pump, the shearing speed was controlled to 9000 r/min, and after shearing for 30 min, it was ground in a colloid mill for 10 min to obtain a modified asphalt initial sample; the average particle of the modifier in the initial sample The diameter is 2.7 ⁇ m.
  • the modified asphalt was transferred to the finished development tank and incubated at 182 °C for 32 h to obtain a modified asphalt product.
  • the modifier was the same as in Example 1.
  • Raw materials 110 parts of 90# matrix pitch, 18 parts of modifier, 5 parts of aromatic oil, 0.2 parts of sulfur, 0.5 parts of XT-2 anti-stripping agent, and 0.3 parts of silane coupling agent.
  • the matrix asphalt was heated at 168 ° C for 2.5 h, then the modifier, aromatic oil and KH550 were added and stirred for 25 min to obtain a premix;
  • the premixed material is placed in a shear pump, the shear rate is controlled to be 8000r/min, and after shearing for 45 minutes, the sheared premix is placed in a swelling tank and swollen at 168 ° C for 40 min to obtain a first mixture. ;
  • the second mixture was placed in a shearing pump, the shearing speed was controlled at 8000 r/min, and after shearing for 35 minutes, it was ground in a colloid mill for 20 minutes to obtain a modified asphalt initial sample; the average particle of the modifier in the initial sample The diameter is 2.1 ⁇ m.
  • the modified asphalt was transferred to the finished development tank and incubated at 176 ° C for 24 h to obtain a modified asphalt.
  • the modified asphalt provided by the present invention has excellent elastic recovery performance, thermal stability, high temperature stability, adhesive property and storage stability, and the modified asphalt provided by the present invention is in terms of technical indicators. It can be simultaneously satisfied: 25°C elastic recovery ⁇ 98%, 60°C dynamic viscosity ⁇ 500,000Pa ⁇ s, 60°C composite shear modulus ⁇ 10kPa, and G */ Sin ⁇ 2.2kPa critical temperature ⁇ 94°C.

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Abstract

本发明提供的改性沥青由包括以下重量份的原料制备而成：沥青100～120份，改性剂6～20份，相容剂3～9份，硫磺0.15～0.25份，非胺类抗剥落剂0.4～0.6份和偶联剂0.2～0.4份；所述改性剂包括苯乙烯-丁二烯-苯乙烯嵌段共聚物、橡胶和聚氨酯。本发明提供的改性沥青可同时满足：25℃弹性恢复≥98％，60℃动力粘度≥50万Pa·s，60℃复合剪切模量≥10kPa，G*/Sin≥2.2kPa的临界温度≥94℃。

Description

一种改性沥青及其制备方法
本申请要求于2017年12月28日提交中国专利局、申请号为CN201711461130.5、发明名称为“一种改性沥青及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明属于道路建材技术领域，具体涉及一种改性沥青及其制备方法。
背景技术
沥青是道路建设和路面养护工程必不可少的一种粘结材料，而且随着公路建设和养护工作的飞速发展，沥青的需求量还在逐年增长。目前，世界各国一直致力倡导“资源节约和环境友好”发展理念，各类薄层沥青路面结构体系则作为公路建设和养护的主要发展方向与此理念相呼应；另外，我国提出了建设“海绵城市”的规划，高性能透水式沥青路面是构建“海绵城市”过程中的关键环节。在道路行业中，相关理念的发展均需要性能更高、更加耐久的沥青胶结料体系。
沥青胶结料作为典型的粘弹性材料，沥青胶结料的粘性和弹性指标均有很强的工程实施意义。目前市面上有较多的高粘改性沥青，也有高弹改性沥青体系。但由于该两项指标存在一定的矛盾，要在同一种沥青胶结材料中同时获得高粘度和高弹性指标则具有很大的技术难度。而同时具有高粘高弹双特性的沥青胶结料则被认为是目前高性能沥青的一个主要的发展方向，是超薄沥青结构体系和透水沥青铺装体系的极为重要的粘结材料。
发明内容
本发明的目的在于提供一种改性沥青，本发明提供的改性沥青具有较高的粘弹性能。
为实现以上目的，本发明提供了一种改性沥青，由包括以下重量份的原料制备而成，基质沥青100～120份，改性剂6～20份，相容剂3～9份， 硫磺0.15～0.25份，非胺类抗剥落剂0.4～0.6份和偶联剂0.2～0.4份；所述改性剂包括苯乙烯-丁二烯-苯乙烯嵌段共聚物、橡胶和聚氨酯。
优选地，所述改性剂中苯乙烯-丁二烯-苯乙烯嵌段共聚物、橡胶和聚氨酯的质量比为1～4：0.5～2：0.5～2。
优选地，所述苯乙烯-丁二烯-苯乙烯嵌段共聚物为星型结构，所述苯乙烯-丁二烯-苯乙烯嵌段共聚物的数均分子量大于20万；
所述橡胶为橡胶粉，所述橡胶粉的粒径为40～100目；
所述聚氨酯的数均分子量大于1万。
优选地，所述相容剂包括芳香烃、直链烷烃和环烷烃中的一种或几种。
优选地，所述偶联剂为硅烷偶联剂。
本发明还提供了上述技术方案所述改性沥青的制备方法，包括如下步骤：
(1)将熔化的基质沥青与改性剂、相容剂和偶联剂混合，得到预混料；
(2)将所述步骤(1)得到的预混料依次进行剪切和溶胀，得到第一混合料；
(3)将所述步骤(2)得到的第一混合料与非胺类抗剥落剂和硫磺混合，得到第二混合料；
(4)对所述步骤(3)得到的第二混合料依次进行剪切、研磨和发育，得到改性沥青。
优选地，所述步骤(1)中混合的温度为160～180℃。
优选地，所述步骤(2)和步骤(4)中剪切的速度独立地为7000～10000r/min，剪切的时间独立地为30～50min。
优选地，所述步骤(2)中溶胀的时间为30～50min。
优选地，所述步骤(4)中研磨的速度为10000-14000r/min，研磨的时间为10～30min。
本发明提供的改性沥青由包括以下重量份的原料制备而成，沥青100～120份，改性剂6～20份，相容剂3～9份，硫磺0.15～0.25份，非胺类抗剥落剂0.4～0.6份和偶联剂0.2～0.4份；所述改性剂包括苯乙烯-丁二烯- 苯乙烯嵌段共聚物、橡胶和聚氨酯。在本发明中，所述改性剂以苯乙烯-丁二烯-苯乙烯嵌段共聚物、橡胶和聚氨酯为主要成分，与基质沥青相溶后能形成空间交联结构，进而提高了基质沥青的力学性能；而相容剂、硫磺、偶联剂等组分的添加，进一步促进改性剂在基质沥青中的均匀分散，为改性剂作用的发挥提供条件。上述各组分配合作用，得到了粘性和弹性较高的改性沥青。实施例结果表明，本发明提供的改性沥青可同时满足：25℃弹性恢复≥98％，60℃动力粘度≥50万Pa·s，60℃复合剪切模量≥10kPa，G */Sin≥2.2kPa的临界温度≥94℃。
具体实施方式
本发明提供了一种改性沥青，由包括以下重量份的原料制备而成，基质沥青100～120份，改性剂6～20份，相容剂3～9份，硫磺0.15～0.25份，非胺类抗剥落剂0.4～0.6份和偶联剂0.2～0.4份；所述改性剂包括苯乙烯-丁二烯-苯乙烯嵌段共聚物、橡胶和聚氨酯。
在本发明中，所述改性沥青的原料除特殊说明外，均为本领域技术人员熟知的市售产品。
本发明提供的改性沥青原料以重量份计，包括基质沥青100～120份，进一步优选为105～115份，更优选为108～112份。本发明对所述基质沥青的具体型号不做任何特殊规定，采用本领域技术人员熟知的即可。在本发明中，所述基质沥青优选为50#沥青、70#沥青或90#沥青。
以所述重量份的基质沥青为基准，本发明提供的改性沥青包括改性剂6～20份，进一步优选为8～18份，更优选为12～18份。本发明利用苯乙烯-丁二烯-苯乙烯嵌段共聚物、橡胶和聚氨酯形成改性剂，与基质沥青相溶后能形成空间交联结构，将基料包裹在交联结构内，使改性沥青的整体粘度和弹性得到提升。在本发明中，所述改性剂中苯乙烯-丁二烯-苯乙烯嵌段共聚物(以下用SBS表示)、橡胶和聚氨酯的质量比为1～4：0.5～2：0.5～2，进一步优选为1.5～3.5：1～1.8：0.8～1.5，更优选为1.8～3：1.2～1.5：1.0～1.2。
在本发明中，所述SBS优选为星型结构。在本发明中，所述SBS的数均分子量优选大于20万，进一步优选为21～50万，更优选为25～45万。 在本发明中，所述橡胶优选为橡胶粉，所述橡胶粉的粒径优选为40～100目，进一步优选为60～100目，更优选为80～100目。在本发明中，所述橡胶粉的比表面积优选为2m 2/g以上，进一步优选为3～14m 2/g，更优选为5～10m 2/g。在本发明中，所述聚氨酯的数均分子量优选为大于1万，进一步优选为1万～50万，更优选为10万～30万。本发明对所述SBS、橡胶粉和聚氨酯的具体来源不做任何特殊限定，以能实现上述参数的控制即可。本发明优选通过对SBS结构和数均分子量，橡胶粉的粒径和比表面积、聚氨酯的数均分子量各参数的限定，使改性剂具有优异的粘度和弹性。
以所述重量份的基质沥青为基准，本发明提供的改性沥青包括相容剂3～9份，优选为3.5～8份，进一步优选为4～6份。在本发明中，所述相容剂优选包括芳香烃、直链烷烃和环烷烃中的一种或几种，进一步优选为直链烷烃。在本发明中，所述芳香烃、直链烷烃和环烷烃的碳原子个数独立地优选为C7～C14，进一步优选为C8～C12。在本发明中，当所述相容剂为几种组分的混合物时，本发明对所述混合物中各组分的用量配比没有任何特殊规定。本发明进一步对相容剂的组分和用量进行上述限定，以促进改性剂与基质沥青的互溶，便于更好的形成空间交联结构。
以所述重量份的基质沥青为基准，本发明提供的改性沥青包括硫磺0.15～0.25份，优选为0.18～0.22份，更优选为0.2份。本发明对所述硫磺的粒径没有特殊要求，采用本领域技术人员熟知的即可。本发明通过添加硫磺提高改性沥青的储存稳定性。
以所述重量份的基质沥青为基准，本发明提供的改性沥青包括非胺类抗剥落剂0.4～0.6份，进一步优选为0.45～0.55份。在本发明中，所述非胺类抗剥落剂优选为XT-1型沥青抗剥落剂和/或XT-2型沥青抗剥落剂，进一步优选为XT-1型沥青抗剥落剂。在本发明中，所述非胺类抗剥落剂能通过物理吸附和化学作用，提高基质沥青与集料的粘附性，进而提高改性沥青的抗水损害性。
以所述重量份的基质沥青为基准，本发明提供的改性沥青包括偶联剂 0.2～0.4份，进一步优选为0.25～0.35份。在本发明中，所述偶联剂优选为硅烷偶联剂，进一步优选为KH550或KH560。本发明利用偶联剂提高沥青与集料、水泥混凝土集料的粘结性能，使改性沥青具有较高的粘结性能。
本发明所述改性沥青可同时满足：25℃弹性恢复≥98％，60℃动力粘度≥50万Pa·s，60℃复合剪切模量≥10kPa，G */Sin≥2.2kPa的临界温度≥94℃。
本发明还提供了上述技术方案所述改性沥青的制备方法，包括如下步骤：
(1)将熔化的基质沥青与改性剂、相容剂和偶联剂混合，得到预混料；
(2)将所述步骤(1)得到的预混料依次进行剪切和溶胀，得到第一混合料；
(3)将所述步骤(2)得到的第一混合料与非胺类抗剥落剂和硫磺混合，得到第二混合料；
(4)对所述步骤(3)得到的第二混合料依次进行剪切、研磨和发育，得到改性沥青。
本发明将熔化的基质沥青与改性剂、相容剂和偶联剂混合，得到预混料。在本发明中，所述改性剂优选通过将苯乙烯-丁二烯-苯乙烯嵌段共聚物、橡胶与聚氨酯在常温下混合得到。本发明对所述苯乙烯-丁二烯-苯乙烯嵌段共聚物、橡胶和聚氨酯的混合顺序没有特殊要求。本发明所述混合优选在搅拌条件下完成，以使苯乙烯-丁二烯-苯乙烯嵌段共聚物、橡胶和聚氨酯均匀混合。本发明对所述搅拌的具体实施方式没有特殊要求，以能实现各组分均匀混合即可。本发明通过对混合方式的限定，以得到粘弹性较好的改性效果。
本发明对所述基质沥青的熔化方式没有任何特殊限定，在本发明中，所述基质沥青的熔化温度优选为160～200℃，进一步优选为165～175℃，所述熔化的时间优选为2～3h，进一步优选为2.2～2.8h。在本发明中，所述熔化的基质沥青与改性剂、相容剂和偶联剂混合的温度优选为 160～200℃，进一步优选为165～175℃。在本发明中，所述混合优选在搅拌条件下进行。本发明对所述搅拌的具体实施方式没有特殊限定，以能实现各组分均匀分散即可。本发明对所述熔化的基质沥青、改性剂、相容剂和偶联剂的混合顺序不做特殊限定。
得到预混料后，本发明将所述预混料依次进行剪切和溶胀，得到第一混合料。本发明对所述预混料进行剪切时，利用预混料的余热保持混合体系为浆料状态，仅需对预混料进行保温。本发明对所述保温的具体实施方案没有特殊要求，采用本领域技术人员熟知的即可。在本发明中，所述剪切的速度优选为7000～10000r/min，进一步优选为8000～9000r/min；所述剪切的时间优选为30～50min，进一步优选为35～48min，更优选为40～45min。本发明对所述剪切的具体实施方式不做任何特殊限定，采用本领域技术人员熟知的即可。
对预混料进行剪切后，将所述剪切后的预混料进行溶胀。在本发明中，所述溶胀的温度优选为165～175℃，进一步优选为170℃；所述溶胀的时间优选为30～50min，进一步优选为35～48min，更优选为40～45min。本发明对所述溶胀的具体实施方式没有特殊限制，以能实现上述参数的控制即可。本发明所述溶胀在溶胀罐中完成。
本发明对预混料依次进行剪切和溶胀，利用强大的剪切力和碰撞作用，使改性剂在基质沥青中充分分散，同时还能细化各组分的颗粒，进而形成稳定的混溶体系；而溶胀则为改性剂与基质沥青形成空间交联结构提供了有利条件。
得到第一混合料后，本发明将所述第一混合料与非胺类抗剥落剂和硫磺混合，得到第二混合料。在本发明中，所述第一混合料与非胺类抗剥落剂和硫磺混合的温度优选为170～180℃，进一步优选为172～178℃。在本发明中，所述混合优选在搅拌条件下完成。本发明对所述搅拌的具体实施方式没有特殊规定，以能实现各组分均匀混合的目的即可。
得到第二混合料后，本发明将所述第二混合料依次进行剪切和研磨，得到改性沥青。本发明对第二混合料进行剪切时，无需对第二混合料进行 额外加热，利用第二混合料的余热保持混合体系为浆料状态。在本发明中，所述第二混合料的剪切速度优选为7000～10000r/min，进一步优选为8000～9000r/min；所述第二混合料的剪切时间优选为30～50min，进一步优选为35～48min，更优选为40～45min。本发明对所述第二混合料的剪切具体实施方式不做任何特殊限定，采用本领域技术人员熟知的即可。本发明对第二混合料进行剪切，利用剪切时产生的强大作用力使非胺类抗剥落剂、硫磺与第一混合料充分混合，进一步提高第二混合料混合体系的稳定性，改善基质沥青的抗水损害性能。
对第二混合料进行剪切后，本发明对所述剪切后的第二混合料进行研磨，得到改性沥青初样。对剪切后的第二混合料进行研磨，一方面可进一步细化初样中改性剂的平均粒径，另一方面，还能使得改性剂的空间交联结构更充分，改性剂在基质沥青中更加稳定，降低过早出现离析的风险。本发明所述研磨的速度优选为10000～14000r/min，进一步优选为12000r/min，所述研磨的时间优选为10～30min，进一步优选为15～28min。本发明所述研磨优选在胶体磨中完成。在本发明中，所述改性沥青初样中改性剂的平均粒径优选为＜4μm，进一步优选为0.1～3μm。
得到改性沥青初样，本发明对所述改性沥青初样进行发育，使得改性剂在基质沥青中发生交联反应，从而更好地形成空间网状结构，确保得到的改性沥青的粘弹效果。本发明优选将改性沥青初样转移至成品发育罐中，进行发育。在本发明中，所述发育的温度优选为170～190℃，进一步优选为180℃，发育的时间优选为24～48h，进一步优选为36～48h。本发明对所述改性沥青初样进行发育，利用高温作用，使改性剂与基质沥青充分相溶后，形成稳定的空间交联结构，从而确保改性沥青的储存稳定性和粘弹性能。
为了进一步说明本发明，下面结合实施例对本发明提供的改性沥青及其制备方法进行详细地描述，但不能将它们理解为对本发明保护范围的限定。
实施例1
以重量份计：
改性剂：数均分子量为30万的SBS 2份，粒径为80目的橡胶粉1份和数均分子量为10万的聚氨酯1份；常温下，混合20min得到。
原料：50#基质沥青110份，改性剂13份，十二烷基苯磺酸钠4份，硫磺0.2份，XT-1型抗剥落剂0.5份和KH5600.3份；
将基质沥青在175℃下加热2h，然后加入改性剂、十二烷基苯磺酸钠以及KH560，搅拌20min，得到预混料；
将预混物料放在剪切泵中剪切50min后，控制剪切速度为8000r/min，剪切后的预混料置于溶胀罐中，在175℃下溶胀50min，得到第一混合料；
向第一混合料中加入XT-1型抗剥落剂和硫磺，在175℃下搅拌25min，得到第二混合料；
将第二混合料置于剪切泵中，控制剪切速度为8000r/min，剪切40min后，放入胶体磨中研磨30min，得到改性沥青初样；初样中改性剂的平均粒径为1.5μm。
将改性沥青初样转移至成品发育罐中，在180℃保温发育36h，得到改性沥青。
本发明对本实施例得到的改性沥青的性能和关键指标进行了测试，测试时采用《公路工程沥青及沥青混合料试验规》(JTG E20-2011)中的相关测试方法，结果显示如表1所示。
实施例2
改性剂：数均分子量为20万的SBS1.8份，粒径为100目的橡胶粉1.2份，数均分子量为15万的聚氨酯1份；常温下混合15min得到。
原料：70#基质沥青110份，改性剂16份，芳烃油4.5份，硫磺0.2份，XT-1型抗剥落剂0.5份，KH5500.3份。
将基质沥青在170℃下加热3h，然后加入改性剂、芳烃油以及KH550，搅拌15min，得到预混料；
将预混物料放在剪切泵中，控制剪切速度为9000r/min，剪切30min后，将剪切后的预混料置于170℃的溶胀罐中溶胀30min，得到第一混合料；
向第一混合料中加入XT-1型抗剥落剂和硫磺，在170℃下搅拌15min，得到第二混合料；
将第二混合料置于剪切泵中，控制剪切速度为9000r/min，剪切30min后，放入胶体磨中研磨10min，得到改性沥青初样；初样中改性剂的平均粒径为2.7μm。
将改性沥青初样转移至成品发育罐中，在182℃保温发育32h，得到改性沥青成品。
对本实施例得到的改性沥青的性能和关键指标进行了测试，结果显示如表1所示。
实施例3
改性剂同实施例1。
原料：90#基质沥青110份，改性剂18份，芳烃油5份，硫磺0.2份，XT-2型抗剥落剂0.5份，硅烷偶联剂0.3份。
将基质沥青在168℃下加热2.5h，然后加入改性剂、芳烃油以及KH550，搅拌25min，得到预混料；
预混物料放在剪切泵中，控制剪切速度为8000r/min，剪切45min后，将剪切后的预混料置于溶胀罐中，在168℃下溶胀40min，得到第一混合料；
第一混合料中加入XT-2型抗剥落剂和硫磺，在168℃下搅拌20min，得到第二混合料；
将第二混合料置于剪切泵中，控制剪切速度位8000r/min，剪切35min后，放入胶体磨中研磨20min，得到改性沥青初样；初样中改性剂的平均粒径为2.1μm。
将改性沥青初样转移至成品发育罐中，在176℃下保温发育24h，得到改性沥青。
对本实施例得到的改性沥青的性能和关键指标进行了测试，结果显示如表1所示。
表1实施案1～3改性沥青性能试验结果
Figure PCTCN2018124387-appb-000001
Figure PCTCN2018124387-appb-000002
根据表1数据可知，本发明提供的改性沥青具有优异的弹性恢复性能、热稳定性、高温稳定性、粘结性能和存储稳定性，从技术指标方面来看，本发明提供的改性沥青可同时满足：25℃弹性恢复≥98％，60℃动力粘度≥50万Pa·s，60℃复合剪切模量≥10kPa，G */Sin≥2.2kPa的临界温度≥94℃。
以上实施例的说明只是用于帮助理解本发明的方法及其核心思想。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。对这些实施例的多种修改对本领域的专业技术人员来说是显而易见的，本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下在其它实施例中实现。因此，本发明将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。

Claims (10)

  1. 一种改性沥青，由包括以下重量份的原料制备而成：
    基质沥青100～120份，改性剂6～20份，相容剂3～9份，硫磺0.15～0.25份，非胺类抗剥落剂0.4～0.6份和偶联剂0.2～0.4份；
    所述改性剂包括苯乙烯-丁二烯-苯乙烯嵌段共聚物、橡胶和聚氨酯。
  2. 如权利要求1所述的改性沥青，其特征在于，所述改性剂中苯乙烯-丁二烯-苯乙烯嵌段共聚物、橡胶和聚氨酯的质量比为1～4：0.5～2：0.5～2。
  3. 如权利要求1或2所述的改性沥青，其特征在于，所述苯乙烯-丁二烯-苯乙烯嵌段共聚物为星型结构，所述苯乙烯-丁二烯-苯乙烯嵌段共聚物的数均分子量大于20万；
    所述橡胶为橡胶粉，所述橡胶粉的粒径为40～100目；
    所述聚氨酯的数均分子量大于1万。
  4. 如权利要求1所述的改性沥青，其特征在于，所述相容剂包括芳香烃、直链烷烃和环烷烃中的一种或几种。
  5. 如权利要求1所述的改性沥青，其特征在于，所述偶联剂为硅烷偶联剂。
  6. 权利要求1～5任一所述改性沥青的制备方法，包括如下步骤：
    (1)将熔化的基质沥青与改性剂、相容剂和偶联剂混合，得到预混料；
    (2)将所述步骤(1)得到的预混料依次进行剪切和溶胀，得到第一混合料；
    (3)将所述步骤(2)得到的第一混合料与非胺类抗剥落剂和硫磺混合，得到第二混合料；
    (4)对所述步骤(3)得到的第二混合料依次进行剪切、研磨和发育，得到改性沥青。
  7. 如权利要求6所述的制备方法，其特征在于，所述步骤(1)中混 合的温度为160～180℃。
  8. 如权利要求6所述的制备方法，其特征在于，所述步骤(2)和步骤(4)中剪切的速度独立地为7000～10000r/min，剪切的时间独立地为30～50min。
  9. 如权利要求6或8所述的制备方法，其特征在于，所述步骤(2)中溶胀的时间为30～50min。
  10. 如权利要求6或8所述的制备方法，其特征在于，所述步骤(4)中研磨的速度为10000～14000r/min，研磨的时间为10～30min。
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