CN107619608B - Block copolymer modified asphalt emulsion and preparation method thereof - Google Patents
Block copolymer modified asphalt emulsion and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a block copolymer modified asphalt emulsion, which comprises a block copolymer shown in a formula 1: p is a block copolymer of the general formula A1-B-A2, A1 and A2 are styrene blocks, B is a butadiene block; wherein the weight ratio (S/B) of the styrene block (S) to the butadiene block (B) is from 20/80 to 40/60; the mass percentage of the 1,2 structure in the butadiene block is 25-50%; the molecular weight of P is 8-20 ten thousand. In addition, the invention also discloses a preparation method of the asphalt emulsion. In the invention, the asphalt emulsion containing the block copolymer of the formula 1 has the advantages of high solid content, enhanced stability and high production efficiency. Compared with the existing known asphalt emulsion, the asphalt emulsion has the advantages of increased storage stability and good emulsifying effect.
Description
Technical Field
The invention belongs to the technical field of asphalt emulsion, and particularly relates to asphalt emulsion modified by block copolymer.
Background
Asphalt is used for paving, roofing waterproofing and coating materials. However, pure asphalt has some disadvantages in terms of physical properties. Therefore, improvement thereof is required. Previously, diene polymer rubbers (e.g., styrene-butadiene rubber) and styrene-rubber block copolymers (e.g., styrene-butadiene-styrene and styrene-isoprene-styrene block copolymers) have been added to asphalt to improve the thermal and mechanical properties of the asphalt. However, these polymer modified asphalts generally require high temperature heating for melting, and have the disadvantages of not saving energy, and releasing harmful gases at high temperature to pollute the environment. Therefore, there is an increasing trend towards the use of emulsified bitumen. The emulsified asphalt is road building material with very low viscosity and good flowability at normal temperature formed by dispersing high temperature road asphalt into water by a mechanical stirring and chemical stabilizing method. The emulsified asphalt has the characteristics of energy conservation, wide application, convenient use and the like, and is mainly used for road paving and upgrading and maintaining roads. Compared with the traditional hot asphalt, the emulsified asphalt is safer, energy-saving and environment-friendly, avoids harmful emission, reduces environmental pollution, and reduces the risk of burning workers and the risk of open fire heating explosion.
However, after general emulsified asphalt construction, the inherent defects of low-temperature brittleness and high-temperature flowing exist, and the popularization of the application is restricted. Therefore, in the prior art, styrene-butadiene rubber (SBR), neoprene rubber, EVA emulsion and the like are mostly added into emulsified asphalt to improve the property of the emulsified asphalt, but the method only improves the high-temperature property of the modified asphalt but cannot obviously improve the low-temperature property of the modified asphalt; or only the low temperature of the modified asphalt is improved, but the high temperature performance of the modified asphalt cannot be obviously improved, and the performance requirement of modern traffic on the pavement cannot be met. There are also related technologies of using SBS emulsion (also called liquid SBS) to modify emulsified asphalt, for example, chinese patent published in 5.25.2005 (publication No. 1618862) discloses a method for preparing liquid SBS, and chinese patent published in 21.1.2009 (publication No. 101348598) discloses a method for preparing SBS emulsion, which are basically the same, i.e., solid SBS is dissolved in an organic solvent, and SBS emulsion is obtained by an emulsification method using a surfactant and water, and contains a lot of harmful solvents, even if the patent document published as CN101348598A adopts a negative pressure method to recover the organic solvent, the technical difficulty of demulsification and complete recovery of the organic solvent is high, SBS emulsion is easily caused, and emulsified asphalt is produced by using the SBS emulsion, the adopted surfactant is too much, so that the emulsified asphalt is unqualified, and the emulsified asphalt is difficult to produce at present.
However, the research on the emulsified SBS modified asphalt is always active, and the purpose of emulsifying the SBS modified asphalt is achieved through the optimization of the emulsifier and the improvement of the emulsifying equipment and the emulsifying process, particularly the reduction of the hot viscosity of the SBS modified asphalt. For example, a chinese patent "an SBS modified emulsified asphalt and its preparation method" (publication No. CN1793234A) published in 28.6.2006 discloses a method of using Sasobit (Sasobit) to reduce the viscosity of hot SBS modified asphalt and obtaining emulsified SBS modified asphalt by a proper emulsification means, and for example, a chinese patent "emulsified SBS modified asphalt and its processing method" (publication No. CN1664012A) published in 7.9.2005 discloses a method of obtaining emulsified SBS modified asphalt by an ultrasonic emulsification mechanism under proper emulsifier and emulsification process conditions.
However, the above patents have a disadvantage that they have a poor emulsifying effect on asphalt and are not easy to emulsify. In addition, the solid content of these bitumen emulsions is not high, which affects the production efficiency.
Disclosure of Invention
In order to solve the technical problems of poor emulsification effect and low solid content in the prior art, the invention provides the asphalt emulsion which is easy to emulsify and has high solid content. In addition, the invention also comprises a preparation method of the asphalt emulsion.
A block copolymer modified bituminous emulsion comprising a block copolymer of formula 1:
p is a block copolymer of the general formula A1-B-A2, A1 and A2 are styrene blocks, B is a butadiene block; wherein the weight ratio (S/B) of the styrene block (S) to the butadiene block (B) is from 20/80 to 40/60; the mass percentage of the 1,2 structure in the butadiene block is 25-50%; the molecular weight of P is 8-20 ten thousand.
In the invention, the asphalt emulsion containing the block copolymer of the formula 1 has the advantages of high solid content, enhanced stability and high production efficiency. Compared with the prior known asphalt emulsion, the asphalt emulsion has the advantages of increased storage stability and good emulsifying effect.
Preferably, the 1, 2-structure mass percentage content in the butadiene block is 30-45%.
The molecular weight of the block portion P is preferably from 10 to 18 ten thousand.
The weight ratio (S/B) of the styrene block (S) to the butadiene block (B) is from 25/75 to 35/65.
R1And R2Independently selected from C1-C4 alkyl.
In the block copolymer, R1And R2The groups selected are the same or different. Preferably, R1And R2Independently selected from methyl, ethyl, propyl, isopropyl, butyl or isobutyl.
Further preferably, R1And R2Are all methyl.
The inventors have found that more preferred block copolymers are: the molecular weight of P is 10-18 ten thousand; wherein the weight ratio (S/B) of the styrene block (S) to the butadiene block (B) is from 25/75 to 35/65; the mass percentage of the 1,2 structure in the butadiene block is 30-45%; r1And R2Are all methyl.
The block copolymer modified asphalt emulsion of the present invention further comprises asphalt, water and an emulsifier. That is, the block copolymer-modified asphalt emulsion comprises asphalt, water, an emulsifier, and the block copolymer.
The weight portion ratio of the asphalt, the water, the emulsifier and the block copolymer is 50-60: 40-50: 1-3: 2.0-8.0.
The bitumen component comprised in the bitumen emulsion may be a naturally occurring bitumen or a petroleum derived bitumen. In addition, the asphalt component may also be a mixture of petroleum asphalt obtained by cracking and various asphalt materials. Examples of the bitumen component include, but are not limited to, distilled or straight-run bitumens, blown bitumens, multigrade bitumens and the like and mixtures thereof.
Preferably, the asphalt component is an asphalt having a penetration at 25 ℃ of 24 to 400; preferred are bitumens having a penetration of from 60 to 300, more preferred are straight run or distilled bitumens having a penetration of from 110 to 250. For example, the preferred asphalt is SK-70, which is imported from Korea.
The bitumen emulsion of the present invention comprises water, which may be any type of clean water, but in order to minimise the reaction of minerals in the water with the emulsion system, demineralised water is preferably used.
In the present invention, one or more emulsifier systems may be added to the asphalt emulsion, and the emulsifier system may be a system comprising only one or more emulsifiers, a system comprising one or more emulsifiers in combination with a mineral acid, or a system comprising one or more emulsifiers in combination with a base. Depending on the type of emulsion (cationic, anionic or nonionic), the emulsifier may be chosen from: (a) if a cationic emulsion is used, a cationic emulsifier known to the person skilled in the art can be selected, for example from salts, amides and imidazolines of fatty amines or mixtures thereof, preferably quaternary ammonium cationic emulsifiers, such as cetyltrimethyl ammonium chloride, octadecyltrimethyl ammonium chloride, dodecyltrimethyl ammonium bromide, octadecyltrimethyl ammonium chloride, cetyltrimethylbenzyl ammonium chloride, dodecyldimethylbenzyl ammonium chloride. (b) If anionic emulsions, the usual anionic emulsifiers familiar to the person skilled in the art can be selected, such as fatty acid salts, abietic acid, lignosulphonates and the like or mixtures thereof, preferably oleic acid is used. (c) If a nonionic emulsifier is used, an aminocarboxylic acid or salt thereof, or other suitable nonionic emulsifier can be selected.
In the invention, the preparation method of the block copolymer comprises the following steps: the general formula is R2R1And (3) initiating the polymerization of the block monomer by amine lithium of the-N-Li, forming PLi (active lithium polymer) after the polymerization is finished, adding maleic anhydride for end capping reaction, and finally acidifying to obtain the lithium-ion battery. Wherein said R1And R2The structure of the compound is the same as that of the formula 1, the two can be the same or different, and the compound can be C1-C4 alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl and the like.
The block copolymer preparation reaction equation is exemplified as follows:
a) the method comprises the following steps Active amine lithium preparation (equation 1):
alkyllithium reagent (R) used in the preparation of lithium amines3Li) is preferably n-butyllithium or sec-butyllithium; (R)1)R2The mass ratio of the-NH to the butyl lithium substance is 1: 1.01-1.05, the reaction temperature is 10-40 ℃, and the reaction time is 20-30 min. The reaction is carried out in a polymerization kettle or a bull horn flask. The synthesized active amine lithium reagent is an active initiator in the polymerization process, and the general structural formula is (R)1)R2-N-Li。
b) The method comprises the following steps Polymerization: the polymerization temperature is 30-85 ℃, and the reaction time is 25-85 min;
b-1): initiation of polymerization to form the styrene block A1 (equation 2):
b-2): initiation of polymerization to form the styrene block A1-butadiene block B (equation 3):
b-3): initiation of polymerization to form the styrene block A1-butadiene block B-styrene block A2 (equation 4):
b) in the formula, the mass ratio of the styrene to the butadiene is 20-40: 60-80. Wherein, the weight of the added styrene in the b-1) and the b-3) is the same;
3): acid end capping reaction: capping with, for example, maleic anhydride (equation 5);
in the acid-capping reaction, the mass ratio of maleic anhydride to butyl lithium is 1: 1.01-1.05, the reaction temperature is 40-65 ℃, and the reaction time is 15-30 min.
4): acidification (equation 6):
after the end-capping reaction is finished, the polymer glue solution (polymerization reaction solution) is acidified under the condition of dilute acid (when the pH value is 5-6), the acidification temperature is 20-60 ℃, and the acidification time is 15-20 min.
The dilute acid is preferably an aqueous solution of hydrochloric acid, sulfuric acid or phosphoric acid; or a cyclohexane solution of hydrogen chloride; or carbon dioxide and water.
a) The solvents used in the processes of b), c) can be selected from aliphatic, cycloaliphatic, alkyl-substituted cycloaliphatic, aromatic and alkyl-substituted aromatic hydrocarbons, ethers and mixtures thereof. Specifically, suitable solvents include aliphatic hydrocarbons such as butane, pentane, hexane, and heptane; cycloaliphatic hydrocarbons such as cyclopentane, cyclohexane and cycloheptane; alkyl-substituted aliphatic hydrocarbons such as methylcyclohexane and methylcycloheptane; aromatic hydrocarbons, such as benzene; alkyl-substituted aromatic hydrocarbons such as toluene and xylene; ethers such as tetrahydrofuran, diethyl ether and dibutyl ether.
Preferably, the solvent for preparing the block copolymer is at least one of cyclopentane, cyclohexane and hexane.
Further preferably, the solvent for preparing the block copolymer is cyclohexane or a cyclohexane-hexane mixed solvent.
It is to be noted that the block copolymers according to the invention can be prepared by any other feasible method than the method according to the invention, which is given by way of reference only and is not limiting.
The preferred method of preparing the block copolymer of the present invention comprises the steps of:
step (1): preparation of active lithium amine:
(R1)R2dissolving-NH in solvent, adding alkyl lithium reagent in inert atmosphere, and reacting at 10-40 deg.C for 20-30min to obtain active lithium amide reagent; (R)1)R2-the molar ratio of-NH to alkyllithium is 1: 1.01 to 1.05;
step (2): polymerization:
step (2-1): dissolving styrene (S) in an inert atmosphere, adding the active amine lithium reagent prepared in the step (1), and polymerizing at the temperature of 30-85 ℃; carrying out polymerization reaction for 20-30 min;
step (2-2): after the polymerization in the step (2-1) is finished, adding butadiene (B); carrying out polymerization reaction for 20-30 min;
step (2-3): after the polymerization in the step (2-2) is finished, continuously adding styrene with the same weight as that in the step (2-1); carrying out polymerization reaction for 20-30 min;
and (3): acid end capping reaction:
after the polymerization in the step (2-3) is finished, adding maleic anhydride to carry out end capping reaction, wherein the end capping reaction temperature is 40-65 ℃; the mass ratio of the maleic anhydride to the lithium alkyl is 1: 1.01-1.05, the reaction temperature is 40-65 ℃, and the reaction time is 15-30 min;
and (4): acidification
And (3) after the treatment in the step (3) is finished, acidifying by olefine acid with the pH value of 5-6, and then washing and drying to obtain the block copolymer, wherein the acidification temperature is 20-60 ℃, and the acidification time is 15-20 min.
In the preferred preparation method, the solvent adopted in the step (1) and the step (2) is cyclohexane or a cyclohexane-hexane mixed solvent.
The asphalt emulsion of the present invention can be made using any method known in the art for making asphalt emulsions, for example, using a colloid mill or a high shear mixer.
The emulsions of the present invention may be prepared by mixing the asphalt component with an emulsifier solution comprising one or more emulsifier systems. The bitumen component (bitumen phase) is prepared by blending bitumen with the block copolymer composition of the present invention. Any known tank or vessel can be used for preparing the asphalt composition as long as the tank or vessel can be stirred and heated.
In preparing the bitumen emulsion, the bitumen may be heated to a temperature of from about 130 ℃ to about 190 ℃, preferably from about 160 ℃ to about 180 ℃. Once the bituminous component has reached the desired temperature, the block copolymer may be added while stirring to form a homogeneous mixture of bituminous component and block copolymer composition. The mode and form of addition of the block copolymer are not limited, and the form may be granular, chip-like or their forms, and the mode of addition may be a single addition or a divided addition.
The emulsifier solution may be prepared by simply adding one or more of the emulsifying system components (e.g., emulsifier and acid or emulsifier and base) to water and heating to dissolve it.
And then adding the asphalt component and the emulsifier solution into a colloid mill or a high-shear mixer or other mixing equipment separately or simultaneously, carrying out high-speed shearing dispersion to form asphalt emulsion, and cooling to obtain the asphalt emulsion. The shear rate is preferably 3000-3500 r/min.
The temperature of the bitumen component and emulsifier solution will vary depending on the type of bitumen in the emulsion, the percentage, and the type of emulsifier. The temperature at which the bitumen component is added is from about 120 ℃ to about 160 ℃, preferably from about 130 ℃ to about 150 ℃. The temperature at which the emulsifier solution is added to the mixture is generally from about 30 ℃ to about 70 ℃, preferably from about 40 ℃ to about 50 ℃.
Preferably, in the asphalt emulsion of the present invention, the mass content of the base asphalt is 55 to 60%, the content of the block copolymer is 2.5 to 4%, the content of water is 40 to 45%, and the content of the emulsifier is 1 to 3%. In addition, the asphalt emulsion of the present invention may further contain other additives such as a stabilizer in an appropriate amount.
A preferred preparation method of the block copolymer modified asphalt emulsion comprises the steps of heating asphalt to 160-180 ℃, adding the block copolymer, and stirring to obtain an asphalt phase; and cooling the asphalt phase to 130-150 ℃, adding an aqueous solution of an emulsifier, shearing and dispersing in a colloid mill or a high-shear mixer to form asphalt emulsion, and cooling to obtain the asphalt emulsion.
In the preparation method, the temperature of the aqueous solution of the emulsifier is 40-50 ℃; the shear rate is 3000-3500 r/min. The prepared asphalt emulsion has high solid content and high stability.
The emulsions prepared in accordance with the present invention are generally useful in all general applications of asphalt emulsions, including roofing coatings, roofing felts, rolled product interlayer adhesives, paving chip sealer adhesives, paving slurry sealer adhesives, recycled asphalt pavement additives, asphalt concrete adhesives, and the like.
The asphalt emulsion prepared by the block copolymer has the characteristics of easy emulsification and improved storage stability. Compared with the emulsion prepared by the existing polymer, such as YH-791H, the asphalt emulsion prepared by the block copolymer has the characteristics of easy emulsification and improved storage stability.
Detailed Description
The following examples were carried out in accordance with the operating methods described above:
the present invention will be described in more detail below by way of examples, but it should be noted that these examples are not intended to limit the present invention.
Example 1
Under the protection of nitrogen gas in a clean and dry 150ml two-hole ox horn bottle, 2.5g of dimethylamine is added into the other hole of the ox horn bottle by a syringe at room temperature of 10 ℃, then 112.2ml of 0.5mol/L n-butyl lithium is added, and the reaction is completed after 20min of oscillation, wherein the concentration of the dimethylamino lithium is 0.48 mol/L.
Example 2
Under the protection of nitrogen gas in a clean and dry 150ml two-hole ox horn bottle, 5.1g of diisopropylamine is added into the other hole of the ox horn bottle by a syringe at room temperature of 32 ℃, then 103ml of 0.5mol/L n-butyl lithium is added, the reaction is completed after shaking for 25min, and the concentration of the diisopropylamine lithium is 0.47 mol/L.
Example 3
Under the protection of nitrogen, 3.5L of hexane-cyclohexane mixed solution was added into a 5-liter polymerization kettleThe preparation and 54g of styrene (S) are started to stir, 0.48mol/L of dimethylamino lithium prepared in example 1 is added into the mixture for reaction for 25min at 30-85 ℃, 252g of butadiene (B) is added for polymerization for 25-30min, 54g of styrene is added for reaction for 25min, 10ml of tetrahydrofuran solution of 0.29g of maleic anhydride is added for end capping reaction at 40-65 ℃ for 20min, 1.5g of 2, 6-di-tert-butyl-p-methylphenol, 6ml of dilute hydrochloric acid sol of 0.5mol/L and 100ml of deionized water are added into the mixture, and the mixture is stirred for 15min at room temperature. Finally, the SBS glue solution synthesized is condensed by water vapor to remove the solvent, and then the product is dried, wherein the number average molecular weight of the product is 16 multiplied by 104The content of bound active carboxyl groups was 0.032 wt%, and the content of 1, 2-structures was 42.3%, wherein the content of 1, 2-structures means the content of vinyl groups in the butadiene block, which was measured by nuclear magnetic resonance (the same below).
Example 4
The preparation of a number average molecular weight of 16.2X 10 was carried out in the same manner as in example 3 except that the lithium diisopropylamide prepared in example 2 was added in place of the 0.48mol/L lithium dimethylamide solution4SBS with combined active carboxyl content of 0.035 wt% and 1, 2-structure content of 44.3%.
Example 5
The base bitumen SK-70 was heated to 180 ℃ and then 5% (based on the total weight of polymer and bitumen) of the polymer prepared in example 3 was added and stirred for 20 minutes to give a bitumen phase. Adding cetyl benzene trimethyl ammonium chloride as emulsifier at 70 deg.C into hot water, stirring until completely dissolved, and adjusting pH to 3 with hydrochloric acid to obtain water phase (soap solution). Slowly adding hot molten asphalt phase (160 ℃) into hot water phase to emulsify under high-speed shearing of more than 3000r/min, wherein the weight ratio of the asphalt phase to soap solution is 55: 45, and cooling to obtain the emulsified asphalt. Then, the evaporation residue test of emulsified asphalt (T0651-1993) was carried out according to the test method of JTJ 052-2000 "road engineering asphalt and asphalt mixture test protocol" to test the asphalt penetration (T0604-2000), ductility (T0605-1993), softening point (T0606-2000) and storage stability of the emulsion evaporation residue. Wherein the storage stability is regulated according to JTJ 052-2000 road engineering asphalt and asphalt mixture test procedures: the storage stability of the modified asphalt emulsion is characterized in that the modified asphalt emulsion is stored in a specified container and under specified conditions (generally room temperature) in a vertical direction, and after a specified time (1d or 5d) is reached, the change degree of the evaporation residue quality in the upper part and the lower part of the emulsion is respectively tested, and the stability capability of the asphalt emulsion in the storage process is judged according to the difference of percentage. In the present invention, the stability of the sample was examined by taking the sample to stand for 5 days.
Example 6
An emulsion asphalt was prepared in the same manner as in example 5, except that the polymer used in this example was the polymer prepared in example 4, but not the polymer prepared in example 3.
Comparative example 1
The procedure of example 5 was repeated except that YH-791 was added instead of the polymer prepared in example 3.
Comparative example 2
The same procedure as in example 5 was repeated except that Dow 2# was added instead of the polymer prepared in example 3.
The properties of the asphalt emulsions prepared in the above examples are shown in table 1 below.
TABLE 1 comparison of Properties of Polymer-modified emulsified bitumens
As is clear from Table 1, the properties of the emulsified asphalt to which the block copolymer of the present invention was added were improved in all cases.
Claims (6)
1. A block copolymer modified asphalt emulsion comprising asphalt, water, an emulsifier and a block copolymer of formula 1; wherein the weight ratio of asphalt, water, emulsifier and the block copolymer of the formula 1 is 50-60: 40-50: 1-3: 2.0-8.0;
a block copolymer of formula 1:
formula 1
P is a block copolymer of the general formula A1-B-A2, A1 and A2 are styrene blocks, B is a butadiene block; wherein the weight ratio (S/B) of the styrene block (S) to the butadiene block (B) is from 20/80 to 40/60; the mass percentage of the 1,2 structure in the butadiene block is 25% -50%; the molecular weight of P is 8-20 ten thousand;
R1and R2Independently selected from C1-C4 alkyl.
2. The block copolymer modified bituminous emulsion of claim 1, wherein the 1,2 mass% of the butadiene blocks is between 30% and 45%.
3. The block copolymer-modified asphalt emulsion according to claim 1, wherein the weight ratio (S/B) of the styrene block (S) to the butadiene block (B) is from 25/75 to 35/65.
4. The block copolymer modified bituminous emulsion of claim 1, wherein R1And R2Independently selected from methyl, ethyl, propyl, isopropyl, butyl or isobutyl.
5. The block copolymer modified bituminous emulsion of claim 1, wherein in formula 1 block copolymer, R1 and R2 are methyl groups; the feeding ratio of the styrene to the butadiene is 30/70 when preparing the block copolymer; the mass percentage of the 1,2 structure in the butadiene block is 42.3 percent; the number average molecular weight of the block copolymer of formula 1 is 16 ten thousand; active carboxyl content 0.032 wt%;
alternatively, R1 and R2 are isopropyl; the feeding ratio of the styrene to the butadiene is 30/70 when preparing the block copolymer; the mass percentage of the 1,2 structure in the butadiene block is 44.3 percent; the number average molecular weight of the block copolymer of formula 1 is 16.2 ten thousand; the content of active carboxyl is 0.035 wt%.
6. A method for preparing the block copolymer modified asphalt emulsion of any one of claims 1 to 5, wherein the asphalt is heated to 160 ℃ to 180 ℃ and then added with the block copolymer of formula 1 and stirred to obtain an asphalt phase; and cooling the asphalt phase to 130-150 ℃, adding an aqueous solution of an emulsifier, shearing and dispersing in a colloid mill or a high-shear mixer to form asphalt emulsion, and cooling to obtain the asphalt emulsion.
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| CN112898509B (en) * | 2021-03-04 | 2022-11-18 | 苏州科技大学 | Styrene-butyl acrylate in-situ copolymerization modified asphalt |
| CN115403935B (en) * | 2021-05-28 | 2024-04-12 | 中国石油化工股份有限公司 | Micro-block nitrile rubber modified asphalt emulsion and preparation method thereof |
| CN116285400B (en) * | 2023-03-23 | 2024-04-02 | 山东金衢设计咨询集团有限公司 | Porous carbon polymer/block copolymer modified asphalt, and preparation method and application thereof |
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| WO2001018122A1 (en) * | 1999-09-03 | 2001-03-15 | J.S.G. Enterprises, Inc. | Polymer-modified asphalt emulsion |
| CN105482477A (en) * | 2016-01-25 | 2016-04-13 | 西安公路研究院 | Super-adhesive composite modified emulsified asphalt and preparation method thereof |
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