CN103788662B - Emulsified bitumen and its preparation method and application and waterproof paint and water-proof coating - Google Patents
Emulsified bitumen and its preparation method and application and waterproof paint and water-proof coating Download PDFInfo
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Abstract
The invention provides a kind of emulsified bitumen and its preparation method and application, with the total amount of this emulsified bitumen for benchmark, this emulsified bitumen contains the water of the polymer modified asphalt of 50-70 % by weight, at least one anionic emulsifier of 1.5-8 % by weight and 22-48.5 % by weight.The water-proof coating that present invention also offers a kind of waterproof paint and formed by this waterproof paint.Emulsified bitumen of the present invention is while having good preservation stability, and the waterproof paint prepared by emulsified bitumen of the present invention has higher solidification rate of set.Further, the water-proof coating formed by the waterproof paint containing emulsified bitumen of the present invention has high intensity.
Description
Technical field
The present invention relates to a kind of emulsified bitumen and its preparation method and application; The invention still further relates to a kind of waterproof paint containing described emulsified bitumen and the water-proof coating formed by described waterproof paint.
Background technology
The mixture that pitch is made up of the multiple macromolecular material of complex chemical composition, has good cohesiveness, resistance to deterioration and waterproof ability.Emulsified bitumen refers to an asphalt heating melting, under mechanical agitation power, and the emulsion formed in containing the aqueous solution of emulsifying agent with tiny microparticulate.Electrical according to used emulsifying agent, emulsified bitumen can be divided into cationic emulsified bitumen, anionic emulsified bitumen and non ionic emulsified bitumen etc.Emulsified bitumen may be used for the interlayer management of bituminous pavement, such as, can form the permeable layers of bituminous pavement, glutinous layer, road surface waterproof layer and slurry seal.Emulsified bitumen in water-proof material and sealing material field also tool have been widely used.
Anionic emulsified bitumen has excellent storage stability, can the feature of standing storage; During use, condensation can be cured by evaporation water wherein.Therefore, the solidification rate of set of anionic emulsified bitumen is slower.US3257231 discloses the solidification rate of set that can improve anionic emulsified bitumen by adding emulsion cracking promoter in anionic emulsified bitumen.But anionic emulsified bitumen disclosed in US3257231 is mainly used in the interlayer management of bituminous pavement, if for field of waterproof materials, then its solidification rate of set also needs further raising.
In addition, in field of waterproof materials and sealing material field, conventional asphalt waterproofing paint is generally by mixing bitumen emulsion and rubber latex with emulsifying agent and obtain, and wherein, bitumen emulsion is prepared by common matrix pitch emulsifying agent is carried out emulsification.During use, asphalt waterproofing paint is brushed to body surface, to be coated parch after carry out second time brushing, repeatedly brush successively.The construction process of this method is loaded down with trivial details, consuming time, and the undercapacity of the water-proof coating formed.
Summary of the invention
The coating formed after the object of the present invention is to provide a kind of condensation cure has the emulsified bitumen of excellent in strength, this emulsified bitumen also has good preservation stability simultaneously, the waterproof paint formed by this emulsified bitumen has very fast condensation cure speed, and the coating of formation has higher intensity.
A first aspect of the present invention provides a kind of emulsified bitumen, and with the total amount of this emulsified bitumen for benchmark, this emulsified bitumen contains the water of the polymer modified asphalt of 50-70 % by weight, at least one anionic emulsifier of 1.5-8 % by weight and 22-48.5 % by weight.
A second aspect of the present invention provides a kind of method preparing described emulsified bitumen, the method comprises: under the existence of the compatilizer contained or do not contain, described polymer modified asphalt, at least one anionic emulsifier and water are sent in emulsifier unit, under the existence of the stablizer contained or do not contain, carry out mixing and emulsification.
A third aspect of the present invention provides emulsified bitumen according to the present invention and is preparing the application in waterproof paint.
A fourth aspect of the present invention provides a kind of waterproof paint, and this waterproof paint comprises emulsified bitumen, at least one rubber latex and at least one accelerating chemicals, and wherein, described emulsified bitumen is emulsified bitumen provided by the invention.
A fifth aspect of the present invention provides a kind of water-proof coating, and this water-proof coating is formed by waterproof paint provided by the invention.
Emulsified bitumen according to the present invention is while having good preservation stability, and the waterproof paint prepared by emulsified bitumen of the present invention has higher solidification rate of set.Further, the water-proof coating formed by the waterproof paint containing emulsified bitumen of the present invention has higher intensity.
Embodiment
A first aspect of the present invention provides a kind of emulsified bitumen, this emulsified bitumen contains polymer modified asphalt, at least one anionic emulsifier and water, wherein, with the total amount of this emulsified bitumen for benchmark, the content of described polymer modified asphalt can be 50-70 % by weight, is preferably 60-70 % by weight; The total content of described anionic emulsifier can be 1.5-8 % by weight, is preferably 3-7 % by weight; The content of water can be 22-48.5 % by weight, is preferably 15-33 % by weight.
Emulsified bitumen according to the present invention contains polymer modified asphalt, and described polymer modified asphalt can be conventional various using matrix pitch as base-material in this area, adopts polymkeric substance to carry out modification and the pitch that obtains.
According to the present invention, the pitch (as coal tar pitch, petroleum pitch and rock asphalt) in the various sources that described matrix pitch can be commonly used for this area.Particularly, described matrix pitch can be the petroleum pitch of 40-100 for penetration degree, if be commercially available No. 50 heavy-duty road asphalts, No. 70 heavy-duty road asphalts, No. 90 heavy-duty road asphalts and No. 110 heavy-duty road asphalts.
In the present invention, penetration degree adopts the method specified in GB/T4509-2010 to measure.
Polymer modifiers in described polymer modified asphalt can carry out modification for various can be used in matrix pitch, thus prepares the polymer modifiers of polymer modified asphalt.Such as, described polymer modifiers can be selected from styrene-butadiene-styrene terpolymer and polyethylene.Preferably, described polymer modifiers is styrene-butadiene-styrene terpolymer.
According to the present invention, described styrene-butadiene-styrene terpolymer can for this area commonly use various can as the styrene-butadiene-styrene terpolymer of the polymer modifiers of matrix pitch.Preferably, with the total amount of described styrene-butadiene-styrene terpolymer for benchmark, the content of the structural unit formed by vinylbenzene is 20-40 % by weight, the content of the structural unit formed by divinyl is 60-80 % by weight, the emulsified bitumen formed thus, when for the formation of water-proof coating, can obtain higher strength of coating.
According to the present invention, in described polymer modified asphalt, the amount of polymer modifiers can be the routine selection of this area.Usually, with the total amount of described polymer modified asphalt for benchmark, the total content of described polymer modifiers can be 1.5-10 % by weight, is preferably 3-8 % by weight.
According to the present invention, described polymer modified asphalt can also contain at least one compatilizer.The present invention is not particularly limited for the kind of described compatilizer and content, can be that the routine of this area is selected.Usually, with the total amount of described polymer modified asphalt for benchmark, the content of described compatilizer can be 0.1-10 % by weight.The various materials that can improve consistency between matrix pitch and polymer modifiers that described compatilizer can be commonly used for this area, such as: described compatilizer can for the fragrant component of various richnesses (if aromaticity content is the richness virtue component of more than 70 % by weight) produced in oil refining process.Particularly, described compatilizer can be aromatic hydrocarbon oil.
According to the present invention, described anionic emulsifier for after conventional various in this area dissociate in water, can generate the emulsifying agent of hydrophobic nature negatively charged ion.Such as, described anionic emulsifier can be selected from carboxylic acid type anionic emulsifier, sulfonate type anionic emulsifier, phosphoric acid ester salt form anionic emulsifier and sulfate type anionic emulsifier.
Described carboxylic acid type anionic emulsifier can dissociate to form the emulsifying agent of carboxylic acid ion of hydrophobic in water, such as, can be that higher fatty acid salt is (as general formula R
1cOOM
1shown alkyl carboxylic acid salt form anionic emulsifier, wherein, R
1can be C
6-C
26straight or branched alkyl, M
1can be Na
+, K
+, NH
4 +, di-alcohol amido or Triethanolamine), be preferably stearate.
The specific examples of described carboxylic acid type anionic emulsifier can include but not limited to: potassium stearate, sodium stearate, ammonium stearate, stearic triethanolamine salt are (namely, the salt that stearic acid and trolamine are formed), the triethanolamine salt of potassium oleate, sodium oleate, ammonium oleate, oleic acid (namely, the salt that oleic acid and trolamine are formed), potassium laurate, sodium laurate, ammonium laurate and lauric triethanolamine salt (that is, lauric acid and trolamine are formed salt).
Described sulfonate type anionic emulsifier can dissociate to form the emulsifying agent of hydrophobic nature sulfonate ion in water, can be but be not limited to: alkylsulfonate (such as: general formula R
2-SO
3m
2shown alkylsulfonate, wherein, R
2for C
12-C
20straight or branched alkyl, M
2for the one in alkalimetal ion, described alkalimetal ion is preferably Na
+or K
+), alkylaryl sulphonate (such as: general formula R
3-Ar
1-SO
3m
3shown alkylaryl sulphonate, wherein, R
3for C
12-C
20straight or branched alkyl, M
3for the one in alkalimetal ion, Ar
1for phenyl or naphthyl, described alkalimetal ion is preferably Na
+or K
+), sulfonated α-olefin (such as: general formula R
4-SO
3m
4shown sulfonated α-olefin, wherein, R
4for C
12-C
20straight or branched thiazolinyl, M
4for the one in alkalimetal ion, described alkalimetal ion is preferably Na
+or K
+), alpha-sulfo monocarboxylate, lipid acid sulfoalkyl ester, sulphosuccinates (as sodium salt, sylvite or ammonium salt), sulfonated petro-leum (as sodium salt, sylvite or ammonium salt), sulfonated lignin (as sodium salt, sylvite or ammonium salt) and alkyl glyceryl ether sulfonate (as sodium salt, sylvite or ammonium salt).Preferably, described sulfonate type anionic emulsifier is alkylaryl sulphonate or sulfonated lignin.More preferably, described sulfonate type anionic emulsifier is alkylaryl sulphonate.
The specific examples of described sulfonate type anionic emulsifier includes but not limited to: sodium laurylsulfonate, sodium cetanesulfonate, Sodium dodecylbenzene sulfonate, cetyl benzenesulfonic acid sodium, dodecyl sodium naphthalene sulfonate, dodecyl sodium sulfonate base sodium succinate, sodium isethionate and sulfonated lignin.
Described phosphoric acid ester salt form anionic emulsifier can dissociate to form the emulsifying agent of phosphate of hydrophobic in water, such as can for but be not limited to: alkyl phosphate monoester salt and alkylphosphonic acid carboxylic acid dibasic acid esters salt.
The specific examples of described phosphoric acid ester salt form anionic emulsifier includes but not limited to: alkylphenol polyoxyethylene phosphoric acid ester, single dodecyl Tetraglycol 99 ortho-phosphoric acid ester monoethanolamine salt, two dodecyl Tetraglycol 99 ortho-phosphoric acid ester monoethanolamine salt and three (methylene phosphate) ammonium.
Described sulfate type anionic emulsifier can dissociate to form the emulsifying agent of sulfate ion of hydrophobic in water, can for but be not limited to: fatty alcohol sulphuric acid salt form emulsifying agent.
The specific examples of described sulfate type anionic emulsifier can include but not limited to: sodium lauryl sulphate, Sodium palmityl sulfate and sodium stearyl sulfate.
Preferably, described anionic emulsifier is be selected from one, two or three emulsifying agent in carboxylic acid type emulsifying agent, sulfonate type emulsifying agent and phosphoric acid ester salt form emulsifying agent.Described anionic emulsifier is preferably one or both and carboxylic acid type emulsifying agent in sulfonate type emulsifying agent and phosphoric acid ester salt form emulsifying agent.The weight ratio of one or both and carboxylic acid type emulsifying agent in sulfonate type emulsifying agent and phosphoric acid ester salt form emulsifying agent can be 0.025-0.7:1.
More preferably, described anionic emulsifier is preferably made up of at least one carboxylic acid type emulsifying agent, at least one sulfonate type emulsifying agent and at least one phosphoric acid ester salt form emulsifying agent, can improve the intensity of the coating formed by emulsified bitumen of the present invention so further.
Further preferably, described anionic emulsifier is made up of at least one carboxylic acid type emulsifying agent, at least one sulfonate type emulsifying agent and at least one phosphoric acid ester salt form emulsifying agent, and described carboxylic acid type emulsifying agent is selected from higher fatty acid salt; Described sulfonate type emulsifying agent is selected from alkylsulfonate and alkylaryl sulphonate; Described phosphoric acid ester salt form emulsifying agent is selected from alkyl phosphate salt and polyoxyethylene ether phosphate.
Still more preferably, described anionic emulsifier is made up of at least one carboxylic acid type emulsifying agent, at least one sulfonate type emulsifying agent and at least one phosphoric acid ester salt form emulsifying agent, and described carboxylic acid type emulsifying agent is selected from stearate (as stearic sodium salt, stearic sylvite and/or stearic ammonium salt); Described sulfonate type emulsifying agent is selected from alkylsulfonate and alkylaryl sulphonate (being preferably alkylaryl sulphonate); Described phosphoric acid ester salt form emulsifying agent is selected from alkyl phosphate salt and polyoxyethylene ether phosphate (being preferably polyoxyethylene ether phosphate).Coating containing the emulsified bitumen of this embodiment with good grounds can obtain good balance between stability in storage and condensation cure speed, and the coating formed has higher intensity.In this embodiment, described alkylaryl sulphonate is more preferably dodecylbenzene sulfonate, and described polyoxyethylene ether phosphate is more preferably thermally coupled distillation columns.
According to the present invention, when described anionic emulsifier is made up of at least one carboxylic acid type emulsifying agent, at least one sulfonate type emulsifying agent and at least one phosphoric acid ester salt form emulsifying agent, the relative content between three kinds of emulsifying agents can carry out appropriate selection according to the solidification rate of expection and strength of coating.Usually, the weight ratio of described carboxylic acid type emulsifying agent, sulfonate type emulsifying agent and phosphoric acid ester salt form emulsifying agent can be 1-4:1:0.1-1.Preferably, the weight ratio of described carboxylic acid type emulsifying agent, sulfonate type emulsifying agent and phosphoric acid ester salt form emulsifying agent is 1.5-3:1:0.1-0.5, the intensity of the final coating formed can be improved so further, and the coating containing this emulsified bitumen, while having better stability in storage, also has condensation cure speed faster.Further preferably, the weight ratio of described carboxylic acid type emulsifying agent, sulfonate type emulsifying agent and phosphoric acid ester salt form emulsifying agent is 1.5-3:1:0.1-0.4.Still more preferably, the weight ratio of described carboxylic acid type emulsifying agent, sulfonate type emulsifying agent and phosphoric acid ester salt form emulsifying agent is 15-3:1:01-03.
In the highly preferred embodiment of one of the present invention, described anionic emulsifier is made up of at least one carboxylic acid type emulsifying agent, at least one sulfonate type emulsifying agent and at least one phosphoric acid ester salt form emulsifying agent, and the weight ratio of described carboxylic acid type emulsifying agent, sulfonate type emulsifying agent and phosphoric acid ester salt form emulsifying agent is that 1.5-3:1:0.1-0.5(is preferably 1.5-3:1:0.1-0.4, is more preferably 1.5-3:1:0.1-0.3); Described carboxylic acid type emulsifying agent is selected from stearic acid salt form anionic emulsifier; Described sulfonate type emulsifying agent is selected from alkylsulfonate and alkylaryl sulphonate (be preferably selected from alkylaryl sulphonate, be more preferably sodium laurylsulfonate); Described phosphoric acid ester salt form emulsifying agent is selected from alkyl phosphate salt and polyoxyethylene ether phosphate (be preferably selected from polyoxyethylene ether phosphate, be more preferably thermally coupled distillation columns).
According to emulsified bitumen of the present invention, the various auxiliary agents that described emulsified bitumen can also be commonly used containing this area.Preferably, also at least one stablizer is contained according to emulsified bitumen of the present invention.
Various organic stabilizer and/or the inorganic stabilizers can improving the stability of emulsified bitumen that described stablizer can be commonly used for this area.The specific examples of described stablizer can be but be not limited to: ether of cellulose, polyvinyl alcohol, starch, sodium polyacrylate, sodium hydroxide, sodium carbonate and water glass.
The present invention is not particularly limited for the consumption of described stablizer, can be that the routine of this area is selected.Usually, with the total amount of described emulsified bitumen for benchmark, the content of described stablizer can be 0.1-5 % by weight, is preferably 0.2-2 % by weight.
A second aspect of the present invention provides a kind of method preparing described emulsified bitumen, the method comprises: described polymer modified asphalt, at least one anionic emulsifier and water are sent into respectively in emulsifier unit, under the existence of the stablizer contained or do not contain, carry out mixing and emulsification, thus obtain described emulsified bitumen.
According to method of the present invention, the various methods that described polymer modified asphalt can adopt this area conventional obtain.Such as, the preparation method of described polymer modified asphalt can comprise: under the existence of the compatilizer contained or do not contain, and is mixed by matrix pitch, obtain polymer modified asphalt with at least one polymer modifiers.The conventional various methods in this area can be adopted to be mixed with at least one polymer modifiers by described matrix pitch.Such as, at the temperature of 160-180 DEG C, matrix pitch can be mixed with polymer modifiers, thus obtain described polymer modified asphalt.From the further angle improving the consistency of matrix pitch and described polymer modifiers, matrix pitch preferably carried out with mixing of polymer modifiers under the existence of compatilizer.Such as: can first backward temperature be in the matrix pitch of 160-180 DEG C, add at least one compatilizer and at least one polymer modifiers, even through shear-mixed, thus obtain polymer modified asphalt.
According to method of the present invention, the kind of described matrix pitch, polymer modifiers, anionic emulsifier, stablizer and compatilizer, with described identical above, does not repeat them here.The consumption of described matrix pitch, polymer modifiers, anionic emulsifier, stablizer and compatilizer is as the criterion to make the content of each component in the emulsified bitumen of final preparation can meet previously described requirement.
According to method of the present invention, the various devices that can realize mixing and emulsification function that described emulsifier unit can be commonly used for this area, such as: colloidal mill emulsor.
According to method of the present invention, the condition that described polymer modified asphalt, at least one anionic emulsifier and water mix also emulsification is not particularly limited, as long as guarantee to prepare emulsified bitumen.Preferably, when being admitted in described emulsifier unit, the temperature of described polymer modified asphalt is 160-180 DEG C, and the temperature of described anionic emulsifier and water is 50-70 DEG C separately, and the pressure in described emulsifier unit is 0.2-0.4MPa.
According to method of the present invention, described emulsifying agent is preferably mixed with solution with water, then mixes with described polymer modified asphalt.
According to method of the present invention, from the angle of the stability of the emulsified bitumen of raising preparation further, preferably under the existence of at least one stablizer, by described polymer modified asphalt, at least one anionic emulsifier and water mixing also emulsification.According to method of the present invention, when preparing described emulsified bitumen under the existence of at least one stablizer, preferably described emulsifying agent and stablizer and water are mixed with the aqueous solution, then mix with described polymer modified asphalt.
According to method of the present invention, when preparing the aqueous solution containing emulsifying agent and optional stablizer, the pH value of the described aqueous solution is as the criterion can obtain the stable and transparent aqueous solution, usually, the pH value of the described aqueous solution is adjusted to alkalescence (such as: the pH value of the described aqueous solution is adjusted to 9-12).The various methods that this area can be adopted to commonly use, to regulate the pH value of the described aqueous solution, are not particularly limited, repeat no more herein.
The waterproof paint prepared by emulsified bitumen according to the present invention has suitable solidification rate, also has good preservation stability simultaneously; Further, the coating that the waterproof paint prepared by emulsified bitumen of the present invention is formed has excellent intensity.Therefore, emulsified bitumen according to the present invention is particularly useful for making waterproof paint.
Thus, a fourth aspect of the present invention provides a kind of emulsified bitumen according to the present invention and is preparing the application in waterproof paint.
A fifth aspect of the present invention provides a kind of waterproof paint, and this waterproof paint comprises emulsified bitumen, at least one rubber latex and at least one accelerating chemicals, and wherein, described emulsified bitumen is emulsified bitumen provided by the invention.According to waterproof paint of the present invention, when storing, accelerating chemicals being separated with emulsified bitumen and rubber latex and deposits.
Waterproof paint according to the present invention is that the emulsified bitumen that the application of the invention provides realizes waterproof paint rapid solidification, and make the coating of formation have high intensity, preparation method for other component in waterproof paint and waterproof paint is not particularly limited, and can be that the routine of this area is selected.
Such as, described rubber latex can be various rubber latexs conventional in waterproof paint, such as: Neoprene latex, styrene-butadiene latex and styrene-butadiene-styrene latex.The various materials that emulsified bitumen breakdown of emulsion can be made to solidify that described accelerating chemicals can be commonly used for this area.Usually, described accelerating chemicals can for being selected from one or more accelerating chemicalss in the complex inorganic salt catalyst of the inorganic salt of calcium, the inorganic salt of magnesium and ferro-aluminum.Preferably, described accelerating chemicals is the inorganic salt of calcium and/or the inorganic salt of magnesium.The present invention is not particularly limited for the using method of described accelerating chemicals, can be that the routine of this area is selected.Such as: described accelerating chemicals can be mixed with the aqueous solution use that concentration is 1-30 % by weight.
The consumption of described accelerating chemicals and rubber latex can be the routine selection of this area, and usually, in butt, relative to emulsified bitumen described in 100 weight parts, the consumption of described accelerating chemicals can be 5-30 weight part, is preferably 5-20 weight part; The consumption of described rubber latex can be 10-40 weight part, is preferably 10-30 weight part.The butt (or claiming evaporation residue content) of described emulsified bitumen adopts the method specified in T0651-1993 to measure; The method that the butt of described rubber latex can adopt this area conventional measures, and the solid content in the product information of the product that also can be available commercially calculates.In the embodiment of the present invention, the butt of rubber latex adopts the solid content that the product that is commercially available marks to calculate.
According to the present invention, described waterproof paint can adopt the ordinary method of this area prepare and use, such as: by being mixed with rubber latex by emulsified bitumen according to the present invention, during use, the mixture obtained can be sprayed to application site together with accelerating chemicals.
The coating formed by waterproof paint provided by the invention has higher intensity, is particularly suitable for the water-proof coating as using in various occasion.
Thus, a sixth aspect of the present invention provides a kind of water-proof coating, and wherein, described water-proof coating is formed by waterproof paint of the present invention.
Water-proof coating of the present invention is that the waterproof paint that the application of the invention provides obtains higher intensity, is not particularly limited for the method forming described water-proof coating.Such as, can use spray gun with double nozzles that waterproof paint prepared in accordance with the present invention and accelerating chemicals are sprayed to application site, after film-forming, form described water-proof coating.The present invention is not particularly limited for the condition of described solidification, can be that the routine of this area is selected, as long as can guarantee to make the waterproof paint spraying to application site solidify and form the coating with expection intensity.Preferably, the condition of described solidification comprises: temperature can be 10-50 DEG C, and the time can be 2-10 second.
The present invention is described in detail below in conjunction with embodiment and comparative example.
In following examples and comparative example, the method specified in GB/T16777-2008 is adopted to measure the setting time of coating; The method specified in T0651-1993 is adopted to measure the evaporation residue content of emulsified bitumen; Bituminous softening-point test (ring and ball method) method specified in T0606-2000 is adopted to measure the softening temperature of the evaporation residue of emulsified bitumen; The method specified in GB/T528-2009 is adopted to measure the tensile strength of water-proof coating; The method specified in T0655-1993 is adopted to measure the stability in storage of emulsified bitumen.
Embodiment 1-10 is for illustration of emulsified bitumen according to the present invention and its preparation method and application and waterproof paint and water-proof coating.
Embodiment 1
The compositing formula (by weight) of polymer modification emulsified bitumen:
Surplus is water
Wherein, matrix pitch is be purchased No. 70 heavy-duty road asphalts from Zhenghai refinery, and penetration degree is 68.1;
Polymer modifiers is that to be purchased from the trade mark of Yueyang petrochemical industry be the styrene-butadiene-styrene terpolymer of SBS1301, wherein, with the total amount of styrene-butadiene-styrene terpolymer for benchmark, the content of the structural unit formed by vinylbenzene is 30 % by weight, and the content of the structural unit formed by divinyl is 70 % by weight;
Compatilizer to be aromaticity content be 70 % by weight aromatic hydrocarbon oil (being purchased from Qilu Petrochemical);
Emulsifying agent is the compound emulsifying agent of Sodium dodecylbenzene sulfonate and ammonium stearate, and the two weight ratio is 1:3.
The preparation method of emulsified bitumen is:
The first step: polymer modified asphalt is provided
Matrix pitch is heated to 170 DEG C, then adds compatilizer, then add polymer modifiers, after stirring, through high speed shear after 3 hours, grow 1 hour, thus obtain polymer modified asphalt.
Second step: prepare emulsified bitumen
In the water of 60 DEG C, add emulsifying agent and water glass, then add NaOH, the pH value of regulator solution is 11.5, stirs, obtains emulsifier solution.
Emulsifier solution and polymer modified asphalt are respectively charged in Soap liquid pot and asphalt tank, pressurization of respectively hanging oneself is rear to be sent in colloidal mill emulsor, wherein, the temperature of polymer modified asphalt is 170 DEG C, the temperature of emulsifier solution is 60 DEG C, pressure in colloidal mill emulsor is remained 0.2-0.4MPa, carries out the shear-mixed of 10 seconds.The mixture obtained obtains according to emulsified bitumen of the present invention after pressurization cooling.Measure the evaporation residue content of the emulsified bitumen of preparation, the softening temperature of evaporation residue and the stability in storage of emulsified bitumen, result provides in Table 1.
The emulsified bitumen of preparation and polychloroprene latex (are purchased from upper seamount rubber Chemical Co., Ltd., model is CRL50EF, solid content is 50 % by weight) according to the composition mixing shown in table 1, the mixture obtained and magnesium salts accelerating chemicals (being the magnesium sulfate solution of 20 % by weight) (are purchased from Shanghai Zuo great coating equipment company limited according to the weight ratio (in butt) of 10:1 with two component Airless spraying rifle, model is NH-46-2-1) spray on flat board, drying 0.5 hour at the temperature of 20 DEG C, thus formation thickness is the water-proof coating of 2mm.Measure the tensile strength of the coating of breakdown of emulsion setting time and formation, result provides in Table 1.
Embodiment 2
The compositing formula (by weight) of polymer modification emulsified bitumen:
Surplus is water
Wherein, matrix pitch is be purchased No. 90 heavy-duty road asphalts from Jinan petrochemical industry, and penetration degree is 94.4;
Polymer modifiers is that to be purchased from the trade mark of Yueyang petrochemical industry be the styrene-butadiene-styrene terpolymer of SBS1401, wherein, with the total amount of styrene-butadiene-styrene terpolymer for benchmark, the content of the structural unit formed by vinylbenzene is 40 % by weight, and the content of the structural unit formed by divinyl is 60 % by weight;
Compatilizer to be aromaticity content be 75 % by weight aromatic hydrocarbon oil (being purchased from Yanshan Petrochemical);
Emulsifying agent is ammonium stearate.
The preparation method of emulsified bitumen is:
The first step: polymer modified asphalt is provided
Matrix pitch is heated to 175 DEG C, then adds compatilizer, then add polymer modifiers, after stirring, through high speed shear after 3 hours, grow 1 hour, thus obtain polymer modified asphalt.
Second step: prepare emulsified bitumen
In the water of 60 DEG C, add emulsifying agent and water glass, then add NaOH, the pH value of regulator solution is 11.5, stirs, obtains emulsifier solution.
Emulsifier solution and polymer modified asphalt are respectively charged in Soap liquid pot and asphalt tank, pressurization of respectively hanging oneself is rear to be sent in colloidal mill emulsor, wherein, the temperature of polymer modified asphalt is 170 DEG C, the temperature of emulsifier solution is 60 DEG C, pressure in colloidal mill emulsor is remained 0.2-0.4MPa, carries out the shear-mixed of 15 seconds.The mixture obtained obtains according to emulsified bitumen of the present invention after pressurization cooling.Measure the evaporation residue content of the emulsified bitumen of preparation, the softening temperature of evaporation residue and the stability in storage of emulsified bitumen, result provides in Table 1.
The emulsified bitumen of preparation and polychloroprene latex (are purchased from upper seamount rubber Chemical Co., Ltd., model is CRL50EF, solid content is 50 % by weight) according to the composition mixing shown in table 1, the mixture obtained and calcium salt accelerating chemicals (being the calcium chloride water of 10 % by weight) (are purchased from Shanghai Zuo great coating equipment company limited according to the weight ratio of 10:1 with two component Airless spraying rifle, model is NH-46-2-1) spray on flat board, drying 0.5 hour at the temperature of 20 DEG C, thus formation thickness is the water-proof coating of 2mm.Measure the tensile strength of the coating of breakdown of emulsion setting time and formation, result provides in Table 1.
Embodiment 3
The compositing formula (by weight) of polymer modification emulsified bitumen:
Surplus is water
Wherein, matrix pitch is for being purchased No. 50 heavy-duty road asphalts from Zhenghai, and penetration degree is 47.6;
Polymer modifiers is that to be purchased from the trade mark of Yueyang petrochemical industry be the styrene-butadiene-styrene terpolymer of SBS1301, wherein, with the total amount of styrene-butadiene-styrene terpolymer for benchmark, the content of the structural unit formed by vinylbenzene is 30 % by weight, and the content of the structural unit formed by divinyl is 70 % by weight;
Compatilizer to be aromaticity content be 75 % by weight aromatic hydrocarbon oil (being purchased from Qilu Petrochemical);
Emulsifying agent is Sodium dodecylbenzene sulfonate (being purchased from Chengdu Long Teng ground Chemical Co., Ltd., content >95 % by weight).
The preparation method of emulsified bitumen is:
The first step: polymer modified asphalt is provided
Matrix pitch is heated to 180 DEG C, then adds compatilizer, then add polymer modifiers, after stirring, through high speed shear after 2 hours, grow 30 minutes, thus obtain polymer modified asphalt.
Second step: prepare emulsified bitumen
In the water of 60 DEG C, add emulsifying agent and water glass, then add NaOH, the pH value of regulator solution is 11.5, stirs, obtains emulsifier solution.
Emulsifier solution and polymer modified asphalt are respectively charged in Soap liquid pot and asphalt tank, pressurization of respectively hanging oneself is rear to be sent in colloidal mill emulsor, wherein, the temperature of polymer modified asphalt is 180 DEG C, the temperature of emulsifier solution is 60 DEG C, pressure in colloidal mill emulsor is remained 0.2-0.4MPa, carries out the shear-mixed of 12 seconds.The mixture obtained obtains according to emulsified bitumen of the present invention after pressurization cooling.Measure the evaporation residue content of the emulsified bitumen of preparation, the softening temperature of evaporation residue and the stability in storage of emulsified bitumen, result provides in Table 1.
The emulsified bitumen of preparation and polychloroprene latex (are purchased from upper seamount rubber Chemical Co., Ltd., model is CRL50EF, solid content is 50 % by weight) according to the composition mixing shown in table 1, the mixture obtained and calcium salt accelerating chemicals (being the calcium chloride of 20 % by weight) (are purchased from Shanghai Zuo great coating equipment company limited according to the weight ratio of 5:1 with two component Airless spraying rifle, model is NH-46-2-1) spray on flat board, drying 0.5 hour at the temperature of 20 DEG C, thus formation thickness is the water-proof coating of 2mm.Measure the tensile strength of the coating of breakdown of emulsion setting time and formation, result provides in Table 1.
Embodiment 4
The compositing formula (by weight) of polymer modification emulsified bitumen:
Surplus is water
Wherein, matrix pitch is be purchased No. 70 heavy-duty road asphalts from Zhenghai refinery, and penetration degree is 68.1;
Polymer modifiers is that to be purchased from the trade mark of Yueyang petrochemical industry be the styrene-butadiene-styrene terpolymer of SBS1301, wherein, with the total amount of styrene-butadiene-styrene terpolymer for benchmark, the content of the structural unit formed by vinylbenzene is 30 % by weight, and the content of the structural unit formed by divinyl is 70 % by weight;
Compatilizer to be aromaticity content be 70 % by weight aromatic hydrocarbon oil (being purchased from Qilu Petrochemical);
Emulsifying agent is the compound emulsifying agent of carboxylic acid type emulsifying agent, sulfonate type emulsifying agent and phosphoric acid ester salt form emulsifying agent, wherein, the weight ratio of carboxylic acid type emulsifying agent, sulfonate type emulsifying agent and phosphoric acid ester salt form emulsifying agent is 1.5:1:0.3, carboxylic acid type emulsifying agent is sodium stearate, sulfonate type emulsifying agent is Sodium dodecylbenzene sulfonate, phosphoric acid ester salt form emulsifying agent is thermally coupled distillation columns (be purchased from Changzhou Chi Yuan Chemical Co., Ltd., the trade mark is 98).
The preparation method of emulsified bitumen is:
The first step: polymer modified asphalt is provided
Matrix pitch is heated to 175 DEG C, then adds compatilizer, then add SBS1301 properties-correcting agent, after stirring, through high speed shear after 2 hours, grow 30 minutes, thus obtain polymer modified asphalt.
Second step: prepare emulsified bitumen
In the water of 60 DEG C, add emulsifying agent and water glass, then add NaOH, the pH value of regulator solution is 11.5, stirs, obtains emulsifier solution.
Emulsifier solution and polymer modified asphalt are respectively charged in Soap liquid pot and asphalt tank, pressurization of respectively hanging oneself is rear to be sent in colloidal mill emulsor, wherein, the temperature of polymer modified asphalt is 180 DEG C, the temperature of emulsifier solution is 60 DEG C, pressure in colloidal mill emulsor is remained 0.3-0.4MPa, carries out the shear-mixed of 10 seconds.The mixture obtained obtains according to emulsified bitumen of the present invention after pressurization cooling.Measure the evaporation residue content of the emulsified bitumen of preparation, the softening temperature of evaporation residue and the stability in storage of emulsified bitumen, result provides in Table 1.
The emulsified bitumen of preparation and polychloroprene latex (are purchased from upper seamount rubber Chemical Co., Ltd., model is CRL50EF, solid content is 50 % by weight) according to the composition mixing shown in table 1, the mixture obtained and calcium salt accelerating chemicals (being the calcium chloride solution of 10 % by weight) (are purchased from Shanghai Zuo great coating equipment company limited according to the weight ratio of 10:1 with two component Airless spraying rifle, model is NH-46-2-1) spray on flat board, drying 0.5 hour at the temperature of 20 DEG C, thus formation thickness is the water-proof coating of 2mm.Measure the tensile strength of the coating of breakdown of emulsion setting time and formation, result provides in Table 1.
Embodiment 5
The method identical with embodiment 4 is adopted to prepare polymer modified asphalt, unlike, use the compound emulsifying agent that carboxylic acid type emulsifying agent, sulfonate type emulsifying agent and sulfate type emulsifying agent form, the weight ratio of three is 1.5:1:0.3.Carboxylate salt emulsifying agent is sodium stearate, and sulfonate emulsifier is Sodium dodecylbenzene sulfonate, and sulfate type emulsifying agent is sodium lauryl sulphate (being purchased from Shanghai Chemical Co., Ltd. of Hang Seng, content >=93 % by weight).
Embodiment 6
The method identical with embodiment 4 is adopted to prepare polymer modified asphalt, unlike, do not use carboxylic acid type emulsifying agent, and the weight ratio of sulfonate type emulsifying agent and phosphoric acid ester salt form emulsifying agent is 1:0.3.
Embodiment 7
The method identical with embodiment 4 is adopted to prepare polymer modified asphalt, unlike, do not use sulfonate type emulsifying agent, and the weight ratio of carboxylic acid type emulsifying agent and phosphoric acid ester salt form emulsifying agent is 1.5:1.
Embodiment 8
The method identical with embodiment 4 is adopted to prepare polymer modified asphalt, unlike, carboxylic acid type emulsifying agent is ammonium oleate, sulfonate type emulsifying agent is sodium lignosulfonate, phosphoric acid ester salt form emulsifying agent is thermally coupled distillation columns (be purchased from Changzhou Chi Yuan Chemical Co., Ltd., the trade mark is 98).
Embodiment 9
Adopting the method identical with embodiment 4 to prepare emulsified bitumen, is 1:1:1 unlike, carboxylic acid type emulsifying agent, weight ratio between sulfonate type emulsifying agent and phosphoric acid ester salt form emulsifying agent.
Embodiment 10
Polymer modification emulsified bitumen compositing formula (by weight):
Surplus is water
Wherein, matrix pitch is be purchased No. 70 heavy-duty road asphalts from Zhenghai refinery, and penetration degree is 68.1;
Polymer modifiers is that to be purchased from the trade mark of Yueyang petrochemical industry be the styrene-butadiene-styrene terpolymer of SBS1301, wherein, with the total amount of styrene-butadiene-styrene terpolymer for benchmark, the content of the structural unit formed by vinylbenzene is 30 % by weight, and the content of the structural unit formed by divinyl is 70 % by weight;
Compatilizer to be aromaticity content be 70 % by weight aromatic hydrocarbon oil (being purchased from Qilu Petrochemical);
Emulsifying agent is the compound emulsifying agent of carboxylic acid type emulsifying agent, sulfonate type emulsifying agent and phosphoric acid ester salt form emulsifying agent, wherein, carboxylic acid type emulsifying agent is ammonium stearate, sulfonate type emulsifying agent is Sodium dodecylbenzene sulfonate, phosphoric acid ester salt form emulsifying agent is that thermally coupled distillation columns (is purchased from Changzhou Chi Yuan Chemical Co., Ltd., the trade mark is 98), wherein, the weight ratio of carboxylic acid type emulsifying agent, sulfonate type emulsifying agent and phosphoric acid ester salt form emulsifying agent is 3:1:0.1.
The preparation method of emulsified bitumen is:
The first step: polymer modified asphalt is provided
Matrix pitch is heated to 175 DEG C, then adds compatilizer, then add polymer modifiers, after stirring, through high speed shear after 3 hours, grow 1 hour, thus obtain polymer modified asphalt.
Second step: prepare emulsified bitumen
In the water of 60 DEG C, add emulsifying agent and water glass, then add NaOH, the pH value of regulator solution is 11.5, stirs, obtains emulsifier solution.
Emulsifier solution and polymer modified asphalt are respectively charged in Soap liquid pot and asphalt tank, pressurization of respectively hanging oneself is rear to be sent in colloidal mill emulsor, wherein, the temperature of polymer modified asphalt is 170 DEG C, the temperature of emulsifier solution is 60 DEG C, pressure in colloidal mill emulsor is remained 0.1-0.4MPa, carries out the shear-mixed of 15 seconds.The mixture obtained obtains according to emulsified bitumen of the present invention after pressurization cooling.Measure the evaporation residue content of the emulsified bitumen of preparation, the softening temperature of evaporation residue and the stability in storage of emulsified bitumen, result provides in Table 1.
The emulsified bitumen of preparation and polychloroprene latex (are purchased from upper seamount rubber Chemical Co., Ltd., model is CRL50EF, solid content is 50 % by weight) according to the composition mixing shown in table 1, the mixture obtained and calcium salt accelerating chemicals (being the calcium chloride solution of 10 % by weight) (are purchased from Shanghai Zuo great coating equipment company limited according to the weight ratio (in butt) of 10:1 with two component Airless spraying rifle, model is NH-46-2-1) spray on cement board, drying 0.5 hour at the temperature of 20 DEG C, thus formation thickness is the water-proof coating of 2mm.Measure the tensile strength of the coating of breakdown of emulsion setting time and formation, result provides in Table 1.
Comparative example 1
The method identical with embodiment 4 is adopted to prepare emulsified bitumen, unlike, do not use polymer modifiers, and the content of matrix pitch is 68.0 % by weight, adopts following methods to prepare emulsified bitumen:
In the water of 55 DEG C, add emulsifying agent and water glass, then add NaOH, the pH value of regulator solution is 11.5, stirs, obtains emulsifier solution.
Emulsifier solution and matrix pitch are respectively charged in Soap liquid pot and asphalt tank.Wherein, the temperature of matrix pitch is 140 DEG C, and the temperature of emulsifier solution is 55 DEG C.Carry out the normal pressure emulsification pretreatment of 1.0 minutes through colloidal mill, after cooling, obtain product emulsified bitumen.Measure the evaporation residue content of emulsified bitumen of preparation, the softening temperature of evaporation residue and emulsified bitumen stability in storage, result provides in Table 1.
The emulsified bitumen of preparation and polychloroprene latex (are purchased from upper seamount rubber Chemical Co., Ltd., model is CRL50EF, solid content is 50 % by weight) according to the composition mixing shown in table 1, the mixture obtained and calcium salt accelerating chemicals (being the calcium chloride solution of 10 % by weight) (are purchased from Shanghai Zuo great coating equipment company limited according to the weight ratio of 10:1 with two component Airless spraying rifle, model is NH-46-2-1) spray on cement board, drying 0.5 hour at the temperature of 20 DEG C, thus formation thickness is the water-proof coating of 2mm.Measure the tensile strength of the coating of breakdown of emulsion setting time and formation, result provides in Table 1.
The result display of table 1, emulsified bitumen according to the present invention has good preservation stability and suitable breakdown of emulsion setting time.The water-proof coating that the waterproof paint adopting emulsified bitumen of the present invention to prepare is formed demonstrates higher tensile strength.
Table 1
Claims (14)
1. an emulsified bitumen, with the total amount of this emulsified bitumen for benchmark, this emulsified bitumen contains the polymer modified asphalt of 50-70 % by weight, the at least one anionic emulsifier of 1.5-8 % by weight, and the water of 22-48.5 % by weight, described anionic emulsifier is by least one carboxylic acid type emulsifying agent, at least one sulfonate type emulsifying agent and at least one phosphoric acid ester salt form emulsifying agent composition, by weight, the total amount of described carboxylic acid type emulsifying agent, the ratio of the total amount of described sulfonate type emulsifying agent and the total amount of described phosphoric acid ester salt form emulsifying agent is 1.5-3:1:0.1-0.5,
Described carboxylic acid type emulsifying agent is selected from higher fatty acid salt; Described sulfonate type emulsifying agent is selected from alkylsulfonate and alkylaryl sulphonate; Described phosphoric acid ester salt form emulsifying agent is selected from alkyl phosphate salt and polyoxyethylene phosphate salt;
With the total amount of described polymer modified asphalt for benchmark, the content of described polymer modifiers is 1.5-10 % by weight;
Described polymer modifiers is styrene-butadiene-styrene terpolymer.
2. emulsified bitumen according to claim 1, wherein, by weight, the ratio of the total amount of the total amount of described carboxylic acid type emulsifying agent, the total amount of described sulfonate type emulsifying agent and described phosphoric acid ester salt form emulsifying agent is 1.5-3:1:0.1-0.3.
3. emulsified bitumen according to claim 1, wherein, described carboxylic acid type emulsifying agent is selected from stearate.
4. emulsified bitumen according to claim 1, wherein, with the total amount of described polymer modified asphalt for benchmark, the content of described polymer modifiers is 3-8 % by weight.
5. emulsified bitumen according to claim 1, wherein, with the total amount of described styrene-butadiene-styrene terpolymer for benchmark, the content of the structural unit formed by vinylbenzene is 20-40 % by weight, and the content of the structural unit formed by divinyl is 60-80 % by weight.
6. emulsified bitumen according to claim 1, wherein, described polymer modified asphalt is also containing at least one compatilizer, and with the total amount of described polymer modified asphalt for benchmark, the content of described compatilizer is 0.1-10 % by weight.
7. the emulsified bitumen according to claim 1 or 6, wherein, described emulsified bitumen is also containing at least one stablizer, and with the total amount of this emulsified bitumen for benchmark, the content of described stablizer is 0.1-5 % by weight.
8. prepare the method for the emulsified bitumen in claim 1-7 described in any one for one kind, the method comprises: described polymer modified asphalt, at least one anionic emulsifier and water are sent in emulsifier unit, containing or not containing under the existence of stablizer, carrying out mixing and emulsification.
9. method according to claim 8, wherein, when being admitted in described emulsifier unit, the temperature of described polymer modified asphalt is 160-180 DEG C, the temperature of described anionic emulsifier and water is 50-70 DEG C separately, and the pressure in described emulsifier unit is 0.2-0.4MPa.
10. method according to claim 8 or claim 9, wherein, the preparation method of described polymer modified asphalt comprises: containing or not containing under the existence of compatilizer, matrix pitch is mixed with at least one polymer modifiers.
The application in waterproof paint prepared by emulsified bitumen in 11. claim 1-7 described in any one.
12. 1 kinds of waterproof paints, this waterproof paint comprises emulsified bitumen, at least one rubber latex and at least one accelerating chemicals in claim 1-7 described in any one.
13. waterproof paints according to claim 12, wherein, in butt, relative to emulsified bitumen described in 100 weight parts, the content of described rubber latex is 10-40 weight part, and the content of described accelerating chemicals is 5-30 weight part.
14. 1 kinds of water-proof coatings, this water-proof coating is formed by the waterproof paint described in claim 12 or 13.
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| CN104592768B (en) * | 2013-10-31 | 2018-12-07 | 中国石油化工股份有限公司 | A kind of anionic emulsified bitumen and preparation method thereof |
| CN104087170A (en) * | 2014-06-18 | 2014-10-08 | 蚌埠市光华金属制品有限公司 | Preparation method for non-ionic emulsified-asphalt waterproof coating |
| CN105273507A (en) * | 2014-07-12 | 2016-01-27 | 卢桂才 | Reactive waterproof coating |
| CN104140761A (en) * | 2014-08-06 | 2014-11-12 | 苏州卓越工程塑料有限公司 | Sprayed rapid hardening rubber asphalt water-proof material used in severe cold areas |
| CN106810814B (en) * | 2015-12-02 | 2020-04-10 | 中国石油化工股份有限公司 | Colored emulsified asphalt composition, preparation method and application thereof, waterproof coating and waterproof coating film |
| CN106118474B (en) * | 2016-07-04 | 2019-06-25 | 常州市钰霖防水科技有限公司 | The preparation method of modified emulsifying asphalt water-repellent paint |
| CN106479363A (en) * | 2016-11-09 | 2017-03-08 | 天津市京建建筑防水工程有限公司 | High polymer SBS modified pitch water-emulsifying type waterproof coatings |
| CN109456499B (en) * | 2017-10-20 | 2020-03-10 | 山东大学 | Amide bis-quaternary ammonium salt type sodium hydroxypropyl phosphate asphalt emulsifier and preparation method thereof |
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| CN111825855B (en) * | 2020-07-31 | 2022-09-09 | 上海缤德新材料科技有限公司 | High-viscosity emulsified asphalt for cold mixing and cold paving and preparation method thereof |
| CN113444452A (en) * | 2021-05-31 | 2021-09-28 | 大禹伟业(北京)国际科技有限公司 | Construction method of composite waterproof layer for building structural engineering |
| CN114163884A (en) * | 2021-12-10 | 2022-03-11 | 河南蓝翎环科防水材料有限公司 | Waterproof anti-slip coating special for outer wall and preparation method and application thereof |
| CN114213970A (en) * | 2021-12-21 | 2022-03-22 | 大禹伟业(北京)国际科技有限公司 | Preparation method of spraying quick-setting rubber asphalt waterproof coating for corrosion prevention, product and application thereof |
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| CN102234436B (en) * | 2010-04-23 | 2012-12-26 | 中国石油化工股份有限公司 | Frost resistant emulsified bitumen and preparation method thereof |
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| CN102504554A (en) * | 2011-11-14 | 2012-06-20 | 镇江金阳道路材料科技发展有限公司 | Anion slow-cracking asphalt emulsifying agent and preparation method thereof |
| CN102690601A (en) * | 2012-06-19 | 2012-09-26 | 唐山德生防水材料有限公司 | Low temperature resisting polymer modified emulsified asphalt waterproof coating |
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