High-stability epoxy modified emulsified asphalt and preparation method thereof

Abstract

The invention provides high-stability epoxy modified emulsified asphalt and a preparation method thereof. The modified emulsified asphalt is obtained by uniformly mixing emulsified asphalt and waterborne epoxy emulsion, the emulsified asphalt comprises a modified emulsifier, and the waterborne epoxy emulsion comprises a modified waterborne epoxy curing agent. The matrix asphalt in the modified emulsifier is used as an oleophylic end, the storage stability of the emulsified asphalt can be greatly improved, and a large number of ether bonds are connected into the modified emulsifier, so that the hydrophilicity of the emulsifier is improved, and the free energy of the asphalt and water is effectively reduced; the epoxy resin reacts with amido in the modified waterborne epoxy curing agent to form a three-position network structure, so that the high-temperature performance and cohesion strength of the cured emulsified asphalt can be greatly improved, and the service life of the emulsified asphalt is prolonged; the waterborne epoxy is used for modifying the emulsified asphalt, a three-dimensional network structure formed after epoxy groups are cured can greatly improve cohesion strength, high-temperature performance and adhesive performance of the emulsified asphalt, and then waterproof performance and durability of a functional layer are improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of asphalt pavement materials, and particularly relates to a high-stability epoxy modified emulsified asphalt and a preparation method thereof. BACKGROUND

[0002] With the increase of service life, various diseases such as potholes, cracks and ruts continuously appear in asphalt pavements of various grades of highways. As a preventive maintenance scheme, thin overlay is widely used in asphalt pavement protection due to its obvious treatment effect, simplicity, high efficiency and high cost performance. Thin overlay is usually divided into two categories: cold paving and hot paving. Cold paving technology uses matrix or modified emulsified asphalt as a binder, and is constructed by layer paving or mixing process. Compared with hot paving technology, cold paving technology does not require heating equipment and is more simple and efficient. The stability of emulsified asphalt during storage and mixing, and the adhesion between emulsified asphalt and stone after demulsification directly affect the implementation effect of the cold paving scheme.

[0003] At present, the emulsified asphalt used in the cold paving technology generally has poor long-term storage stability, requires high stone for mixing, and needs to be tested for matching before construction, otherwise problems such as rapid demulsification and inability to pave may occur. At the same time, emulsified asphalt forms adhesive strength by evaporation of water and demulsification, and factors such as temperature, wind speed, sunlight and demulsification rate of emulsifier affect the solidification rate.

[0004] Patent CN118126533A discloses a high-adhesion anti-skid thin-layer maintenance material and water-based organic silicon epoxy resin modified emulsified asphalt, which is composed of the following components in parts by weight: 100 parts of 70# cationic emulsified asphalt with a solid content of 60% to 65%, 2.5 to 15 parts of water-based organic silicon epoxy resin with a solid content of 55% to 65%, and 1.2 to 10 parts of water-soluble modified amine curing agent. The water-based organic silicon epoxy resin is prepared according to the following steps: 1) condensing bisphenol A epoxy resin with alkoxyl or hydroxyl siloxane to obtain SiOC bond connected organic silicon modified epoxy resin; and 2) reacting the organic silicon modified epoxy resin with carboxylated dextran to obtain. The adhesion performance, toughness and weather resistance of the binder are improved.

[0005] The patent CN114686013A provides a kind of water-based epoxy resin modified emulsified asphalt and its preparation method, water-based epoxy resin modified emulsified asphalt includes nonionic water-based epoxy resin emulsion, ethylene amine addition type curing agent, SBR butyl benzene latex, modified white carbon black, cationic emulsified asphalt, and the weight ratio is (2-6) :(2-6) :(2-5) :(4-8) :100;The modified white carbon black is prepared after white carbon black is modified with trimesic acid;The water-based epoxy resin emulsion includes the following components by mass fraction: emulsifier 10~25 parts, bisphenol A type epoxy resin 100 parts, water 75~90 parts.The water-based epoxy resin modified emulsified asphalt obtained according to the method in the application has excellent high-temperature performance and low-temperature performance. SUMMARY

[0006] To solve the technical problems of general performance, poor storage stability and difficult to control curing time of conventional emulsified asphalt in the prior art, the present application provides a high-stability epoxy modified emulsified asphalt and a preparation method thereof. The prepared modified emulsified asphalt has excellent mechanical properties, high storage stability, and controllable curing speed.

[0007] A high-stability epoxy modified emulsified asphalt is prepared by uniformly mixing emulsified asphalt and water-based epoxy emulsion.

[0008] The use ratio of the emulsified asphalt to the water-based epoxy emulsion is 80:20.

[0009] The emulsified asphalt is prepared by mixing base asphalt, water and modified emulsifier at high speed, and the ratio of base asphalt, water and modified emulsifier is 50:50:0.5.

[0010] The modified emulsifier includes the following raw materials by weight fraction: 100 parts of base asphalt, 5-6 parts of dehydrogenation catalyst, 40-50 parts of monopropylene acid ester containing hydrophilic group monomer, 50-60 parts of diacrylate containing hydrophilic group monomer, and 1-2 parts of raft catalyst.

[0011] The preparation process of the modified emulsifier is as follows: the dehydrogenation catalyst is added to the base asphalt, heated to 450-500℃, and after 3-4h of reaction under the condition of oxygen circulation, the catalyst is removed by filtration to obtain dehydrogenated asphalt; the obtained dehydrogenated asphalt is uniformly mixed with monopropylene acid ester containing hydrophilic group monomer and diacrylate containing hydrophilic group monomer, and then raft catalyst is added, heated to 80-90℃, and reacted for 4-5h to obtain the modified emulsifier.

[0012] The base pitch is a base pitch with a mark number > 50, such as any one of Jinling 70# base pitch, Shuanglong 70# base pitch, and Shuanglong 90# base pitch. High mark number base pitch has better high temperature resistance, so the emulsified pitch often uses high mark number base pitch as raw material, uses high mark number base pitch as modified raw material, improves the compatibility and storage stability of the pitch emulsifier and the pitch.

[0013] The monofunctional monomer with hydrophilic group is any one of ethylene glycol methacrylate and propylene glycol methacrylate; the difunctional monomer with hydrophilic group is any one of diethylene glycol methacrylate and dipropylene glycol methacrylate. The difunctional monomer and the monofunctional monomer are modified by free radical polymerization, the hydrophilic group with a low critical solution temperature is introduced into the base pitch to synthesize the emulsifier, and the emulsified pitch is highly stable with the base pitch and water at a low temperature. Once the critical solution temperature is exceeded, the emulsified pitch is quickly precipitated to control the demulsification speed of the emulsified pitch.

[0014] The dehydrogenation catalyst is any one of platinum and palladium. The base pitch treated by dehydrogenation has a higher unsaturation degree, can graft more hydrophilic monomers, increases the hydrophilicity of the pitch emulsifier, and improves the storage stability of the emulsified pitch.

[0015] The raft catalyst is any one of dithiocarbamic acid ester and xanthate.

[0016] The water-based epoxy emulsion is obtained by mixing the modified water-based epoxy curing agent, water, and epoxy resin at high speed, the modified water-based epoxy curing agent: water: epoxy resin = 1:1:1; the epoxy resin is bisphenol A epoxy resin.

[0017] The modified water-based epoxy curing agent comprises the following raw materials in parts by weight: 80-100 parts of aliphatic amine, 40-50 parts of bisphenol A epoxy resin, 50 parts of hydrophilic inert diluent, 50-60 parts of monofunctional epoxy diluent, 100-110 parts of hydrophilic group-containing epoxy diluent, and 60 parts of deionized water.

[0018] The preparation process of the modified water-based epoxy curing agent is as follows: the bisphenol A epoxy resin and the inert hydrophilic diluent are uniformly mixed and then added dropwise into the aliphatic amine, reacted for 4-5 h to obtain the aliphatic amine S1 grafted with the epoxy resin; the hydrophilic group-containing epoxy diluent is added dropwise into S1, reacted for 2-3 h to obtain the aliphatic amine S2 grafted with the hydrophilic group-containing epoxy diluent and the epoxy resin; the monofunctional epoxy diluent is added dropwise into S2, reacted for 2-3 h to obtain the aliphatic amine S3 capped with the hydrophilic group-containing epoxy diluent and the epoxy resin; S3 is subjected to distillation to remove the inert hydrophilic diluent, then deionized water is added and uniformly mixed to obtain the modified water-based epoxy curing agent.

[0019] The reaction temperature in the preparation process of the modified waterborne epoxy curing agent is 65-70℃. The dropping method is dropping through a separatory funnel at a speed of 2s / drop, and the required reaction time of 4-5h is the time required after the dropping is completed.

[0020] The modified waterborne epoxy curing agent contains hydrophilic groups and lipophilic groups in its structure, which can form a stable emulsion with epoxy resin. On the other hand, the amine groups in the waterborne epoxy curing agent react with the epoxy resin to form a three-dimensional network structure, which can greatly improve the high-temperature performance and cohesive strength of the cured emulsified asphalt, and prolong the service life of the emulsified asphalt.

[0021] The hydrophilic group-containing epoxy diluent is any one of polyethylene glycol diglycidyl ether or polypropylene glycol diglycidyl ether. By reacting with the fatty amine, the epoxy diluent with a hydrophilic group is connected to the fatty amine, which increases the compatibility of the curing agent with water and forms a stable emulsion.

[0022] The bisphenol A type epoxy is any one of E51, E44, or E20. The epoxy resin reacts with the fatty amine to connect the lipophilic end to the fatty amine, which increases the compatibility of the waterborne epoxy curing agent with the epoxy resin.

[0023] The inert hydrophilic diluent is one of propylene glycol methyl ether, dipropylene glycol methyl ether, or tripropylene glycol methyl ether. As an inert diluent, it can dilute the epoxy resin, increase the processability and workability of the epoxy resin, reduce the activity of the reaction, and reduce the risk of gelation.

[0024] The monofunctional epoxy diluent is one of epoxy diluent C12-14 alkyl glycidyl ether (AGE) or butyl glycidyl ether (BGE). The monofunctional diluent is used to cap the curing agent, reduce the activity of the curing agent, and adjust the reaction speed of the curing agent.

[0025] The fatty amine is any one of diethylene triamine, triethylene tetramine, or tetraethylene pentamine, or a mixture of two or more of them in any ratio.

[0026] Preferably, the fatty amine is any one of diethylene triamine or triethylene tetramine, or a mixture of two or more of them in any ratio.

[0027] Preferably, the fatty amine is a mixture of diethylene triamine and triethylene tetramine in a mass ratio of 1:(1-1.5). When the fatty amine is such a mixture, the cross-linking degree and stereoscopic degree of the three-dimensional structure obtained are more excellent.

[0028] The preparation method of the high-stability epoxy modified emulsified asphalt comprises the following steps: (1) adding water and a modified emulsifier into a reaction kettle, stirring uniformly, heating to 60 DEG C, pouring matrix asphalt heated to 160-170 DEG C into the reaction kettle, and shearing at a high speed of 1000-1200 rpm to obtain emulsified asphalt; (2) mixing a modified waterborne epoxy curing agent and an epoxy resin uniformly, slowly adding deionized water, and shearing at a high speed of 1000-1200 rpm for 20-30 min to obtain a waterborne epoxy emulsion; and (3) mixing the waterborne epoxy emulsion and the emulsified asphalt, stirring at a speed of 400 rpm for 2-3 min to obtain the high-stability epoxy modified emulsified asphalt.

[0029] The water used in the entire preparation process of the high-stability epoxy modified emulsified asphalt is industrial deionized water, and the grade is ≤4.

[0030] Compared with the prior art, the present application has the following advantages:

[0031] (1) The present application has excellent storage stability compared with the prior art. First, the matrix asphalt in the asphalt-based emulsifier has natural compatibility with the asphalt component in the emulsified asphalt, which can greatly improve the storage stability of the emulsified asphalt. At the same time, a large number of ether bonds are introduced into the asphalt-based emulsifier as the hydrophilic end, which increases the hydrophilicity of the emulsifier, effectively reduces the free energy of asphalt and water, and forms a stable emulsion.

[0032] (2) The present application controls the demulsification speed of the emulsified asphalt by the type of the hydrophilic group of the emulsifier. The critical solution temperature of the hydrophilic group is slightly higher than the storage temperature. At room temperature, the emulsified asphalt is stable and does not demulsify during storage, transportation, mixing, etc. When the emulsified asphalt is subjected to direct sunlight, heating, etc., the temperature exceeds the critical temperature, and the emulsion can be demulsified and quickly cured.

[0033] (3) The emulsified asphalt prepared by the present application has excellent construction stability. The non-ionic emulsion can effectively reduce the influence of environmental factors such as stone acid and alkalinity on the mixing stability of the emulsified asphalt, and effectively avoid the problems of mixing of ionic emulsified asphalt with acid and alkaline stone, rapid demulsification, etc.

[0034] (4) The three-dimensional network structure formed by the curing of the epoxy group in the waterborne epoxy modified emulsified asphalt can greatly improve the cohesive strength, high-temperature performance and bonding performance of the emulsified asphalt, and further improve the waterproofness and durability of the functional layer. DETAILED DESCRIPTION

[0035] The technical solutions of the present application will be clearly and completely described below in combination with the embodiments of the present application. Obviously, the described embodiments are only some of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative work fall within the protection scope of the present application.

[0036] The specific conditions not indicated in the following examples and comparative examples are carried out according to the conventional conditions. The base asphalt is commercially available from SK in Korea; the supported nickel catalyst, Pd / Pt / Ru / Rh-C / Al2O3, and copper-based catalyst are commercially available from XunKai Catalyst; ethylene glycol methacrylate, propylene glycol methacrylate, diethylene glycol methacrylate, and dipropylene glycol methacrylate are commercially available from Mertry Reagent; dithio carbamate is commercially available from XiDan Experiment; O-ethyl xanthate is commercially available from Shaanxi Liedu Pharmaceutical; bisphenol A epoxy resin E51 and E44 are commercially available from NanYa.

[0037] Example 1

[0038] Example 1 provides a high-stability epoxy-modified emulsified asphalt, and the raw materials include the following components: base asphalt, supported nickel catalyst, ethylene glycol methacrylate, diethylene glycol methacrylate, dithio carbamate, deionized water, diethylene triamine, epoxy resin E51, propylene glycol methyl ether, polyethylene glycol diglycidyl ether, and epoxy diluent AGE.

[0039] A high-stability epoxy-modified emulsified asphalt, and a preparation method of the asphalt emulsifier and the emulsified asphalt includes the following steps:

[0040] S1: 100 parts of base asphalt are added into a reaction kettle, 5 parts of supported nickel catalyst are added, heated to 450℃, oxygen is introduced, oxygen circulation is maintained, and reaction is carried out for 3h, and then the catalyst is removed by filtration to obtain dehydrogenated asphalt.

[0041] S2: 100 parts of dehydrogenated asphalt are added into a reaction kettle, 45 parts of ethylene glycol methacrylate and 55 parts of diethylene glycol methacrylate are uniformly mixed, 2 parts of dithio carbamate are added, heated to 80℃, and reaction is carried out for 4h to obtain an asphalt emulsifier.

[0042] S3: 50 parts of water and 0.5 parts of the asphalt emulsifier are uniformly stirred in a reaction kettle, heated to 60℃, 50 parts of base asphalt are heated to 160℃, poured into the reaction kettle, and high-speed shearing is carried out at 1150rpm to obtain a finished product emulsified asphalt.

[0043] A high-stability epoxy-modified emulsified asphalt, and a preparation method of the modified waterborne epoxy curing agent, the epoxy emulsion, and the modified emulsified asphalt includes the following steps:

[0044] S1 in the reaction kettle 90 parts of diethylene triamine, heated to 70℃, 45 parts of epoxy resin E51 and 50 parts of propylene glycol methyl ether mixed evenly, through the separatory funnel with 2s / drop speed drop into the reaction kettle, after the end of the drop, reaction 4h, get grafting epoxy fatty amine.

[0045] S2 through the separatory funnel into the reaction kettle of S4 115 parts of polyethylene glycol diglycidyl ether, drop rate of 2s / drop, maintain temperature 70℃, after the end of the drop, reaction 2h, get grafting hydrophilic group epoxy diluent and epoxy resin of fatty amine.

[0046] S3 through the separatory funnel into the reaction kettle of S5 55 parts of epoxy diluent AGE, drop rate of 2s / drop, maintain temperature 70℃, after the end of the drop, reaction 2h, get grafting hydrophilic group epoxy diluent and epoxy resin of fatty amine.

[0047] S4 through the distillation of S3 product to remove propylene glycol methyl ether, then add 76 parts of deionized water, mixed evenly to get the modified waterborne epoxy curing agent.

[0048] S5 50 parts of modified waterborne epoxy curing agent and 50 epoxy resin mixed evenly, slowly add 50 parts of deionized water, with 1150 rpm high speed shearing 30 min to get waterborne epoxy emulsion.

[0049] S6 80 parts of waterborne epoxy emulsion and 20 parts of emulsified asphalt mixed with 400 rpm, stirring 2-3 min to get modified emulsified asphalt.

[0050] Example 2

[0051] Example 2 provides a high stability epoxy modified emulsified asphalt, raw materials including the following components: base asphalt, Pd / Pt / Ru / Rh-C / Al2O3, methyl propylene glycol methacrylate, methyl propylene glycol methacrylate, O-ethyl xanthate ethyl, deionized water, triethylene tetramine, epoxy resin E44, propylene glycol methyl ether, polypropylene glycol diglycidyl ether, epoxy diluent BGE.

[0052] A high stability epoxy modified emulsified asphalt, wherein the preparation method of the asphalt emulsifier and the emulsified asphalt comprises the following steps:

[0053] S1 in the reaction kettle 100 parts of base asphalt, add 5 parts of Pd / Pt / Ru / Rh-C / Al2O3, heated to 450℃, oxygen is introduced, maintain oxygen circulation, reaction 3h, filter to remove the catalyst, get dehydrogenated asphalt.

[0054] S2 add 100 parts of dehydrogenated asphalt in the reaction kettle, add 40 parts of propylene glycol methacrylate and 60 parts of dipropylene glycol methacrylate, mix evenly, add 2 parts of O-ethyl xanthate, heat to 80℃, react for 4h, get asphalt emulsifier.

[0055] S3 add 50 parts of water and 0.5 parts of asphalt emulsifier in the reaction kettle, stir evenly, heat to 60℃, heat 50 parts of base asphalt to 160℃, pour into the reaction kettle, high speed shearing at 1150rpm, get finished product emulsified asphalt.

[0056] A high stability epoxy modified emulsified asphalt, wherein the preparation method of modified water-based epoxy curing agent, epoxy emulsion and modified emulsified asphalt comprises the following steps:

[0057] S1 add 100 parts of triethylene tetramine in the reaction kettle, heat to 70℃, mix 50 parts of epoxy resin E44 and 50 parts of propylene glycol methyl ether evenly, drop into the reaction kettle through the separatory funnel at the speed of 2s / drop, after the end of dropping, react for 4h, get grafting epoxy fatty amine.

[0058] S2 drop 110 parts of polypropylene glycol diglycidyl ether into the reaction kettle of S4 through the separatory funnel, the dropping speed is 2s / drop, maintain the temperature at 70℃, after the end of dropping, react for 2h, get grafting hydrophilic group epoxy diluent and epoxy resin fatty amine.

[0059] S3 drop 60 parts of epoxy diluent BGE into the reaction kettle of S5 through the separatory funnel, the dropping speed is 2s / drop, maintain the temperature at 70℃, after the end of dropping, react for 2h, get capped grafting hydrophilic group epoxy diluent and epoxy resin fatty amine.

[0060] S4 remove propylene glycol methyl ether by distillation for the finished product of S3, then add 80 parts of deionized water, mix evenly to get finished product modified water-based epoxy curing agent.

[0061] S5 mix 50 parts of modified water-based epoxy curing agent and 50 parts of epoxy resin evenly, slowly add 50 parts of deionized water, high speed shearing at 1150rpm for 30min to get water-based epoxy emulsion.

[0062] S6 mix 80 parts of water-based epoxy emulsion and 20 parts of emulsified asphalt at the speed of 400rpm, stir for 2-3min to get modified emulsified asphalt.

[0063] Example 3

[0064] Example 3 provides a high-stability epoxy-modified emulsified asphalt, the raw materials including the following components: base asphalt, copper catalyst, propylene glycol methacrylate, dipropylene glycol methacrylate, O-ethyl ethyl xanthate, deionized water, tetraethylenepentamine, epoxy resin E20, propylene glycol methyl ether, polypropylene glycol diglycidyl ether, and epoxy diluent PGE.

[0065] A high-stability epoxy-modified emulsified asphalt, wherein the preparation method of the asphalt emulsifier and the emulsified asphalt comprises the following steps:

[0066] S1: 100 parts of base asphalt are added to a reaction kettle, 6 parts of copper catalyst are added, heated to 450°C, oxygen is introduced, oxygen circulation is maintained, and reacted for 3h. The catalyst is removed by filtration to obtain dehydrogenated asphalt.

[0067] S2: 100 parts of dehydrogenated asphalt are added to a reaction kettle, 43 parts of propylene glycol methacrylate and 57 parts of dipropylene glycol methacrylate are uniformly mixed, 1 part of O-ethyl ethyl xanthate is added, heated to 80°C, and reacted for 4h to obtain an asphalt emulsifier.

[0068] S3: 50 parts of water and 0.5 parts of asphalt emulsifier are uniformly stirred in a reaction kettle, heated to 60°C, 50 parts of base asphalt is heated to 160°C, and then poured into the reaction kettle for high-speed shearing at 1150rpm to obtain a finished emulsified asphalt.

[0069] A high-stability epoxy-modified emulsified asphalt, wherein the preparation method of the modified waterborne epoxy curing agent, the epoxy emulsion, and the modified emulsified asphalt comprises the following steps:

[0070] S1: 80 parts of tetraethylenepentamine are added to a reaction kettle, heated to 70°C, 40 parts of epoxy resin E20 and 50 parts of propylene glycol methyl ether are uniformly mixed, and then added to the reaction kettle at a rate of 2s / drop through a separatory funnel. After the addition is completed, the reaction is carried out for 4h to obtain a grafted epoxy aliphatic amine.

[0071] S2: 100 parts of polypropylene glycol diglycidyl ether is added to the reaction kettle of S4 through a separatory funnel at a rate of 2s / drop, and the temperature is maintained at 70°C. After the addition is completed, the reaction is carried out for 2h to obtain a grafted hydrophilic group epoxy diluent and epoxy resin aliphatic amine.

[0072] S3: 50 parts of epoxy diluent PGE is added to the reaction kettle of S5 through a separatory funnel at a rate of 2s / drop, and the temperature is maintained at 70°C. After the addition is completed, the reaction is carried out for 2h to obtain a capped grafted hydrophilic group epoxy diluent and epoxy resin aliphatic amine.

[0073] S4: The finished product of S3 is subjected to distillation to remove propylene glycol methyl ether, and then 68 parts of deionized water is added and uniformly mixed to obtain a finished modified waterborne epoxy curing agent.

[0074] S5 50 parts of modified waterborne epoxy curing agent and 50 parts of epoxy resin were mixed uniformly, 50 parts of deionized water was slowly added, and high-speed shearing was carried out at 1150 rpm for 30 min to obtain a waterborne epoxy emulsion.

[0075] S6 80 parts of waterborne epoxy emulsion and 20 parts of emulsified asphalt were mixed at a speed of 400 rpm for 2-3 min to obtain modified emulsified asphalt.

[0076] Example 4

[0077] Example 4 provides a high-stability epoxy modified emulsified asphalt, and the raw materials include the following components: base asphalt, supported nickel catalyst, ethylene glycol methacrylate, diethylene glycol methacrylate, dithio carbamate, deionized water, diethylene triamine, epoxy resin E51, propylene glycol methyl ether, polyethylene glycol diglycidyl ether, and epoxy diluent AGE.

[0078] A high-stability epoxy modified emulsified asphalt, and a preparation method of the asphalt emulsifier and the emulsified asphalt includes the following steps:

[0079] S1 100 parts of base asphalt were added to a reaction kettle, 6 parts of supported nickel catalyst were added, heated to 450°C, oxygen was introduced, oxygen circulation was maintained, and reaction was carried out for 3 h. The catalyst was removed by filtration to obtain dehydrogenated asphalt.

[0080] S2 100 parts of dehydrogenated asphalt were added to a reaction kettle, 50 parts of ethylene glycol methacrylate and 50 parts of diethylene glycol methacrylate were mixed uniformly, 1 part of dithio carbamate was added, heated to 80°C, and reaction was carried out for 4 h to obtain an asphalt emulsifier.

[0081] S3 50 parts of water and 0.5 parts of asphalt emulsifier were stirred uniformly in a reaction kettle, heated to 60°C, 50 parts of base asphalt was heated to 160°C, poured into the reaction kettle, and high-speed shearing was carried out at 1150 rpm to obtain finished emulsified asphalt.

[0082] A high-stability epoxy modified emulsified asphalt, and a preparation method of the modified waterborne epoxy curing agent, the epoxy emulsion, and the modified emulsified asphalt includes the following steps:

[0083] S1 85 parts of diethylene triamine were added to a reaction kettle, heated to 70°C, 43 parts of epoxy resin E51 and 50 parts of propylene glycol methyl ether were mixed uniformly, and were added dropwise to the reaction kettle at a speed of 2 s / drop through a separatory funnel. After the addition was completed, reaction was carried out for 4 h to obtain a grafted epoxy aliphatic amine.

[0084] S2 added 113 parts of polyethylene glycol diglycidyl ether into the reactor of S4 through a separatory funnel, the dropping speed was 2s / drop, the temperature was maintained at 70℃, after the dropping was completed, the reaction was carried out for 2h, to obtain the grafting hydrophilic group epoxy diluent and the fatty amine of epoxy resin.

[0085] S3 added 53 parts of epoxy diluent AGE into the reactor of S5 through a separatory funnel, the dropping speed was 2s / drop, the temperature was maintained at 70℃, after the dropping was completed, the reaction was carried out for 2h, to obtain the capped grafting hydrophilic group epoxy diluent and the fatty amine of epoxy resin.

[0086] S4 removed the propylene glycol methyl ether from the product of S3 by distillation, then added 74 parts of deionized water, and mixed uniformly to obtain the modified waterborne epoxy curing agent.

[0087] S5 mixed 50 parts of the modified waterborne epoxy curing agent and 50 parts of epoxy resin uniformly, slowly added 50 parts of deionized water, and sheared at a high speed of 1150rpm for 30min to obtain the waterborne epoxy emulsion.

[0088] S6 mixed 80 parts of the waterborne epoxy emulsion and 20 parts of the emulsified asphalt at a speed of 400rpm, and stirred for 2-3min to obtain the modified emulsified asphalt.

[0089] Example 5

[0090] Example 5 provides a high-stability epoxy modified emulsified asphalt, the raw materials of which include the following components: base asphalt, supported nickel catalyst, ethylene glycol methacrylate, diethylene glycol methacrylate, dithio carbamate, deionized water, fatty amine (diethylene triamine, triethylene tetramine mass ratio 1:1), epoxy resin E51, propylene glycol methyl ether, polyethylene glycol diglycidyl ether, and epoxy diluent AGE.

[0091] A high-stability epoxy modified emulsified asphalt, and a preparation method of the emulsified asphalt, which comprises the following steps:

[0092] S1 added 100 parts of base asphalt into a reactor, added 5 parts of supported nickel catalyst, heated to 450℃, and circulated oxygen, and reacted for 3h, and then filtered to remove the catalyst to obtain dehydrogenated asphalt.

[0093] S2 added 100 parts of dehydrogenated asphalt into a reactor, added 45 parts of ethylene glycol methacrylate and 55 parts of diethylene glycol methacrylate, and mixed uniformly, added 2 parts of dithio carbamate, heated to 80℃, and reacted for 4h to obtain an asphalt emulsifier.

[0094] S3 in the reaction kettle is added 50 parts of water and 0.5 parts of asphalt emulsifier, stirring evenly, heated to 60℃, 50 parts of base asphalt is heated to 160℃, pour into the reaction kettle, with 1150 rpm high speed shearing, get finished product emulsified asphalt.

[0095] A high stability epoxy modified emulsified asphalt, wherein the preparation method of modified water-based epoxy curing agent, epoxy emulsion and modified emulsified asphalt comprises the following steps:

[0096] S1 in the reaction kettle is added 90 parts of fatty amine, heated to 70℃, 45 parts of epoxy resin E51 and 50 parts of propylene glycol methyl ether are mixed evenly, through the separatory funnel with 2s / drop speed drop into the reaction kettle, after the end of drop, reaction 4h, get grafting epoxy fatty amine.

[0097] S2 through the separatory funnel, 115 parts of polyethylene glycol diglycidyl ether is dropped into the reaction kettle of S4, the drop rate is 2s / drop, the temperature is maintained at 70℃, after the end of drop, reaction 2h, get grafting hydrophilic group epoxy diluent and epoxy resin of fatty amine.

[0098] S3 through the separatory funnel, 55 parts of epoxy diluent AGE is dropped into the reaction kettle of S5, the drop rate is 2s / drop, the temperature is maintained at 70℃, after the end of drop, reaction 2h, get capped grafting hydrophilic group epoxy diluent and epoxy resin of fatty amine.

[0099] S4 the finished product of S3 is removed by distillation, then 76 parts of deionized water is added, mixed evenly to get finished product modified water-based epoxy curing agent.

[0100] S5 50 parts of modified water-based epoxy curing agent and 50 parts of epoxy resin are mixed evenly, 50 parts of deionized water is slowly added, with 1150 rpm high speed shearing for 30 min to get water-based epoxy emulsion.

[0101] S6 80 parts of water-based epoxy emulsion and 20 parts of emulsified asphalt are mixed with 400 rpm speed, stirring for 2-3 min to get modified emulsified asphalt.

[0102] Example 6

[0103] Example 6 provides a kind of high stability epoxy modified emulsified asphalt, raw materials include the following components: base asphalt, supported nickel catalyst, ethylene glycol methacrylate, diethylene glycol methacrylate, dithio carbamate, deionized water, fatty amine (diethylene triamine, triethylene tetramine mass ratio 1:1.5), epoxy resin E51, propylene glycol methyl ether, polyethylene glycol diglycidyl ether, epoxy diluent AGE.

[0104] A high stability epoxy modified emulsified asphalt, wherein the preparation method of asphalt emulsifier and emulsified asphalt comprises the following steps:

[0105] S1 in the reaction kettle is added 100 parts of base pitch, 5 parts of nickel catalyst is added, heated to 450℃, oxygen is introduced, oxygen circulation is maintained, reaction for 3h, the catalyst is removed by filtration, dehydrogenated pitch is obtained.

[0106] S2 in the reaction kettle is added 100 parts of dehydrogenated pitch, 45 parts of ethylene glycol methacrylate and 55 parts of diethylene glycol methacrylate are mixed uniformly, 2 parts of dithio carbamate is added, heated to 80℃, reaction for 4h, pitch emulsifier is obtained.

[0107] S3 in the reaction kettle is added 50 parts of water and 0.5 parts of pitch emulsifier is stirred uniformly, heated to 60℃, 50 parts of base pitch is heated to 160℃, poured into the reaction kettle, high speed shearing at 1150rpm, the finished product emulsified pitch is obtained.

[0108] A high stability epoxy modified emulsified pitch, wherein the preparation method of the modified water-based epoxy curing agent, the epoxy emulsion and the modified emulsified pitch comprises the following steps:

[0109] S1 in the reaction kettle is added 90 parts of aliphatic amine, heated to 70℃, 45 parts of epoxy resin E51 and 50 parts of propylene glycol methyl ether are mixed uniformly, added into the reaction kettle through the separatory funnel at the speed of 2s / drop, after the addition is completed, reaction for 4h, the aliphatic amine grafted with epoxy is obtained.

[0110] S2 through the separatory funnel, 115 parts of polyethylene glycol diglycidyl ether is added into the reaction kettle of S4, the dropping speed is 2s / drop, the temperature is maintained at 70℃, after the addition is completed, reaction for 2h, the aliphatic amine grafted with hydrophilic group epoxy diluent and epoxy resin is obtained.

[0111] S3 through the separatory funnel, 55 parts of epoxy diluent AGE is added into the reaction kettle of S5, the dropping speed is 2s / drop, the temperature is maintained at 70℃, after the addition is completed, reaction for 2h, the aliphatic amine grafted with hydrophilic group epoxy diluent and epoxy resin is obtained.

[0112] S4 the finished product of S3 is distilled to remove propylene glycol methyl ether, then 76 parts of deionized water is added, mixed uniformly to obtain the finished product of modified water-based epoxy curing agent.

[0113] S5 50 parts of modified water-based epoxy curing agent and 50 parts of epoxy resin are mixed uniformly, 50 parts of deionized water is slowly added, high speed shearing at 1150rpm for 30min to obtain the water-based epoxy emulsion.

[0114] S6 80 parts of water-based epoxy emulsion and 20 parts of emulsified pitch are mixed at the speed of 400rpm, stirring for 2-3min to obtain the modified emulsified pitch.

[0115] Comparative example 1

[0116] Comparative Example 1 differs from Example 1 in that Comparative Example 1 uses a common non-ionic fast-setting asphalt emulsifier (Sichuan Zhongjin Li Hua).

[0117] Comparative Example 2

[0118] Comparative Example 2 differs from Example 1 in that Comparative Example 2 does not contain a diacrylic acid hydrophilic group-containing monomer.

[0119] Comparative Example 3

[0120] Comparative Example 3 differs from Example 1 in that Comparative Example 3 does not add an epoxy emulsion to the emulsified asphalt.

[0121] Comparative Example 4

[0122] Comparative Example 4 differs from Example 1 in that Comparative Example 4 uses a common fast-setting cationic emulsifier, the water-based epoxy curing agent is not grafted with a hydrophilic group-containing epoxy diluent, and acetic acid is added to ionize it.

[0123] Comparative Example 5

[0124] Comparative Example 5 differs from Example 1 in that Comparative Example 5 uses a common curing agent (593 curing agent).

[0125] Test Example:

[0126] The elongation at break, tensile strength refers to GB / T_1040.1-2018; the emulsified asphalt storage stability experiment refers to JTGE20-2011; the emulsified asphalt demulsification speed experiment refers to JTG E20-2011; and the emulsified asphalt mixing experiment refers to JTG E20-2011.

[0127] The specific test results are shown in Table 1:

[0128] Table 1

[0129]

[0130] Examples 1-6, on the one hand, use a modified base asphalt to prepare an asphalt emulsifier, which greatly improves the storage stability of the emulsified asphalt, and on the other hand, introduce a large number of ether bonds to the asphalt emulsifier, which enhances the hydrophilicity of the asphalt emulsifier and improves the storage stability of the emulsified asphalt.

[0131] Comparative Example 1, relative to Example 1, uses a common fast-setting non-ionic emulsifier, and the storage stability is significantly reduced, thereby causing the performance of the material to deteriorate.

[0132] Comparative Example 2 relative to Example 1, no hydrophilic group-containing diacrylic monomer is added in the asphalt emulsifier, which results in a higher critical temperature of the emulsified asphalt, a significant decrease in the demulsification speed of the emulsified asphalt, and a prolonged curing time.

[0133] Comparative Example 3 relative to Example 1, no epoxy emulsion is added, which results in a failure to form a three-dimensional network structure after demulsification of the emulsified asphalt due to the lack of epoxy groups, and a significant decrease in the cohesive strength, bonding strength, high-temperature performance, and waterproof durability of the material.

[0134] Comparative Example 4 relative to Example 1, the asphalt emulsifier is a fast-curing cationic emulsifier, and the waterborne epoxy curing agent is not grafted with a hydrophilic group-containing epoxy diluent, and acetic acid is added to ionize it, the demulsification rate of which is affected by the acid-base property of the stone, and the construction performance is unstable.

[0135] Comparative Example 5 relative to Example 1, a common epoxy curing agent is used, and the common epoxy curing agent (593 curing agent, Zhangjiagang Yuanbang Chemical Material Co., Ltd.) has no hydrophilic group, which cannot be made into an emulsion with epoxy resin, and thus the performance of the modified emulsified asphalt cannot be measured.

[0136] The matrix asphalt, epoxy resin, suitable critical solution temperature hydrophilic group, epoxy diluent, and the amount of each component used in the present application are controlled within the above ranges, which helps to achieve high storage stability of the emulsified asphalt, control the demulsification speed of the emulsified asphalt, improve the construction stability of the emulsified asphalt, improve the cohesive strength, high-temperature performance, and bonding strength of the emulsified asphalt, and further improve the waterproof and durability of the functional layer.

[0137] Although embodiments of the present application have been shown and described, it is to be understood that various modifications, substitutions, replacements, and changes can be made to these embodiments without departing from the principles and spirit of the present application, and the scope of the present application is defined by the appended claims and their equivalents.

Claims

1. A high stability epoxy modified emulsified asphalt, characterized by, The modified emulsified asphalt is obtained by uniformly mixing the emulsified asphalt and the water-based epoxy emulsion; The emulsified asphalt and the water-based epoxy emulsion are used in a ratio of 80:20; The emulsified asphalt is obtained by mixing base asphalt, water and modified emulsifier at high speed, and the base asphalt:water:modified emulsifier is 50:50:0.

5. The modified emulsifier comprises the following raw materials in parts by weight: 100 parts of base asphalt, 5-6 parts of dehydrogenation catalyst, 40-50 parts of single acrylate monomer containing a hydrophilic group, 50-60 parts of double acrylate monomer containing a hydrophilic group, and 1-2 parts of raft catalyst. The water-based epoxy emulsion is obtained by mixing a modified water-based epoxy curing agent, water and epoxy resin at high speed, and the modified water-based epoxy curing agent:water:epoxy resin is 1:1:

1. The modified water-based epoxy curing agent comprises the following raw materials in parts by weight: 80-100 parts of aliphatic amine, 40-50 parts of bisphenol A epoxy resin, 50 parts of hydrophilic inert diluent, 50-60 parts of monofunctional epoxy diluent, 100-110 parts of hydrophilic group-containing epoxy diluent, and 60 parts of deionized water.

2. The high stability epoxy modified emulsified asphalt according to claim 1, characterized by, The base asphalt is base asphalt with a label of >50; the single acrylate monomer containing a hydrophilic group is any one of ethylene glycol methacrylate and propylene glycol methacrylate; and the double acrylate monomer containing a hydrophilic group is any one of diethylene glycol methacrylate and dipropylene glycol methacrylate.

3. The high stability epoxy modified emulsified asphalt according to claim 1, characterized in that: The dehydrogenation catalyst is a rare metal catalyst; and the raft catalyst is any one of dithiocarbamate and xanthate.

4. The high stability epoxy modified emulsified asphalt according to claim 1, characterized by, The modified emulsifier is prepared as follows: the dehydrogenation catalyst is added to the base asphalt, heated to 450-500℃, and reacted for 3-4h under the condition of oxygen circulation, and then the catalyst is removed by filtration to obtain dehydrogenated asphalt; the single acrylate monomer containing a hydrophilic group and the double acrylate monomer containing a hydrophilic group are added to the obtained dehydrogenated asphalt and uniformly mixed, and then the raft catalyst is added, heated to 80-90℃, and reacted for 4-5h to obtain the modified emulsifier.

5. The high stability epoxy modified emulsified asphalt according to claim 1, characterized in that: The hydrophilic group-containing epoxy diluent is any one of polyethylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether; the inert hydrophilic diluent is one of propylene glycol methyl ether, dipropylene glycol methyl ether and tripropylene glycol methyl ether; the monofunctional epoxy diluent is one of epoxy diluent C12-14 alkyl glycidyl ether and butyl glycidyl ether; and the aliphatic amine is any one of diethylene triamine, triethylene tetramine and tetraethylene pentamine, or a mixture of two or more thereof in any ratio.

6. The high stability epoxy modified emulsified asphalt according to claim 5, characterized in that: The aliphatic amine is any one of diethylene triamine and triethylene tetramine, or a mixture of two or more thereof in any ratio.

7. The high stability epoxy modified emulsified asphalt according to claim 1, characterized by, The modified waterborne epoxy curing agent is prepared as follows: after mixing the epoxy resin and inert hydrophilic diluent uniformly, the mixture is added dropwise into the aliphatic amine, and reacted for 4-5 h to obtain the aliphatic amine S1 grafted with the epoxy resin; the hydrophilic group-containing epoxy diluent is added dropwise into S1, and reacted for 2-3 h to obtain the aliphatic amine S2 grafted with the hydrophilic group-containing epoxy diluent and the epoxy resin; the monofunctional epoxy diluent is added dropwise into S2, and reacted for 2-3 h to obtain the aliphatic amine S3 capped with the hydrophilic group-containing epoxy diluent and the epoxy resin; S3 is subjected to distillation to remove the inert hydrophilic diluent, and then deionized water is added and mixed uniformly to obtain the modified waterborne epoxy curing agent.

8. The high temperature, qualitative, epoxy-modified emulsified asphalt according to claim 7, characterized in that: The reaction temperature in the preparation process of the modified waterborne epoxy curing agent is 65-70℃.

9. The process for the preparation of high stability epoxy modified emulsified bitumen according to any one of claims 1 to 8, characterized in that, comprising the following steps: (1) adding water and a modified emulsifier into a reaction kettle, stirring uniformly, heating to 60℃, pouring the matrix asphalt heated to 160-170℃ into the reaction kettle, and shearing at a high speed of 1000-1200 rpm to obtain emulsified asphalt; (2) mixing the modified waterborne epoxy curing agent and the epoxy resin uniformly, slowly adding deionized water, and shearing at a high speed of 1000-1200 rpm for 20-30 min to obtain a waterborne epoxy emulsion; (3) mixing the waterborne epoxy emulsion and the emulsified asphalt, stirring at a speed of 400 rpm for 2-3 min to obtain the high-stability epoxy modified emulsified asphalt.

10. Use of a high-stability epoxy-modified emulsified asphalt in thin-layer overlays, characterized in that: The high-stability epoxy modified emulsified asphalt is the high-stability epoxy modified emulsified asphalt according to any one of claims 1-8 or obtained by the preparation method according to claim 9. The high-stability epoxy modified emulsified asphalt is the high-stability epoxy modified emulsified asphalt according to any one of claims 1-8 or obtained by the preparation method according to claim 9.

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