CN105384948A - Dication and dianion type asphalt emulsifier and preparation method thereof - Google Patents
Dication and dianion type asphalt emulsifier and preparation method thereof Download PDFInfo
- Publication number
- CN105384948A CN105384948A CN201510969040.1A CN201510969040A CN105384948A CN 105384948 A CN105384948 A CN 105384948A CN 201510969040 A CN201510969040 A CN 201510969040A CN 105384948 A CN105384948 A CN 105384948A
- Authority
- CN
- China
- Prior art keywords
- dication
- asphalt emulsifier
- mol
- type asphalt
- anion type
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
- C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
- C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
- C07C227/08—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid by reaction of ammonia or amines with acids containing functional groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/27—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/36—Compounds containing oxirane rings with hydrocarbon radicals, substituted by nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2395/00—Bituminous materials, e.g. asphalt, tar or pitch
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Civil Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
The invention discloses a dication and dianion type asphalt emulsifier, and belongs to the field of fine chemical engineering. The emulsifier is prepared from octadecylamine, an alcohol solvent, acrylic acid, small-carbon-number tertiary amine, industrial hydrochloric acid, epoxy chloropropane and sodium chloroacetate at the molar ratio of 1 mol:(4.00-9.00) mol: (1.00-1.06) mol: (1.02-1.10) mol: (1.02-1.10) mol: (1.02-1.08) mol: (1.01-1.08) mol. The asphalt emulsifier is prepared from the synthetic raw materials which are easy to obtain and is low in production cost, simple in process, free of high-temperature reactions and capable of emulsifying asphalt of different models; prepared emulsified asphalt is fine, uniform, good in storage stability and suitable for spreading of chip seal coat oil or prime coat oil or tack coat oil of highways; the asphalt emulsifier has the characteristics of a quick-breaking asphalt emulsifier.
Description
Technical field
The present invention relates to a kind of dication dual anion type asphalt emulsifier and preparation method thereof, belong to technical field of fine.
Background technology
Emulsified bitumen especially cationic emulsified bitumen, owing to having energy-conserving and environment-protective, can improve execution conditions, and can effectively reduce many excellent application characteristics such as pitch overaging, and is widely used in Road construction and pavement preservation.
The most critical factor affecting emulsified bitumen pavement performance is exactly asphalt emulsifier, and current domestic and international cationic asphalt emulsifier principal item has organic amine, quaternary ammonium salt, imidazolines, amides etc., and wherein quaternary ammonium salt emulsifying agent is most widely used general.Along with the application of cationic emulsified bitumen, the kind of asphalt emulsifier is also enriched gradually.
US Patent No. P4338136 is with C
12-18long carbon chain lipid acid and diethylenetriamine react under certain condition prepares asphalt emulsifier.The shortcoming of the method is that the asphalt emulsifier prepared is expensive, and when constructing for slurry seal, the breakdown of emulsion time is long, and molding time is slow, and the open to traffic time is long.Chinese patent CN1096714 utilizes refinery by-product naphthenic acid and alkenyl polyamine to react, and prepares asphalt emulsifier.The shortcoming of the method is that the raw material supply of emulsifying agent is subject to severely restricts, is unfavorable for applying.Chinese patent CN1861721A relates to a kind of rosin cation asphalt emulgent.This emulsifying agent is reacted by rosin and alkenyl polyamine, obtains rosin intermediate, then, with dissimilar quaternary ammonium salt intermediate condensation, and the rosin cation asphalt emulgent of obtained excellent property.The shortcoming of this method is that reactions steps is loaded down with trivial details, needs pyroreaction.Chinese patent CN101712625A relates to a kind of method for synthesizing amphoteric slow-breaking quick-setting asphalt emulsifier, adopts oleic acid and polyamines to react and generates polyamide-polyamino, then add Mono Chloro Acetic Acid generation halogenating reaction, obtained asphalt emulsifier.The shortcoming of the method needs pyroreaction when being preparation.Chinese patent CN101745340A relates to a kind of cation asphalt emulgent preparation method, and host is obtained by reacting intermediate by mixed organic acid and organic amine, then carry out quaterisation obtain, assistant agent is nonionogenic tenside and modified additive.The shortcoming of the method is that preparation process is loaded down with trivial details, and cost is higher, needs pyroreaction.
Although asphalt emulsifier kind starts to enrich, due to the difference of asphalt source and refining process, cause pitch to form and differ, a kind of emulsifying agent is more difficult can all have good emulsifying effect to various pitch; And the less stable of emulsified bitumen; In addition, although above-mentioned prior art discloses multiple cationic asphalt emulsifier and preparation method thereof, its raw materials cost preparing emulsifying agent is higher, and source is restricted, and needs pyroreaction during preparation, higher to productive experiment equipment requirements.
The asphalt emulsifier of the new structure how cost of development is cheap, emulsifying effectiveness is good, especially applicable different model pitch, the asphalt emulsifier splitting type cationic emulsified bitumen soon that even for the preparation of exquisiteness, stability in storage is good are problems faced in this area.
Summary of the invention
For the deficiencies in the prior art, the object of the present invention is to provide dication dual anion type asphalt emulsifier that a kind of production cost is low, technique simply, does not need pyroreaction and preparation method thereof.
For achieving the above object, the present invention adopts following technical scheme:
The invention provides a kind of dication dual anion type asphalt emulsifier, it is characterized in that, the molecular structure of described dication dual anion type asphalt emulsifier is:
Wherein, R=methyl (-CH
3), ethyl (-C
2h
5), ethanol based (-C
2h
4oH).
Preferably, dication dual anion type asphalt emulsifier of the present invention, is prepared from by the raw material of following mol ratio:
Stearylamine: alcoholic solvent: vinylformic acid: low carbon number tertiary amine: technical hydrochloric acid: epoxy chloropropane: sodium chloroacetate=1mol:(4.00-9.00) mol:(1.00-1.06) mol:(1.02-1.10) mol:(1.02-1.10) mol:(1.02-1.08) mol:(1.01-1.08) mol;
Described alcoholic solvent is ethanol, methyl alcohol or Virahol;
Described low carbon number tertiary amine is trimethylamine aqueous solution, triethylamine or trolamine.
Stearylamine is used in dication dual anion type asphalt emulsifier synthesis of the present invention, described emulsifying agent hydrophobic grouping is octadecyl, adopt the alkyl of different carbon atoms can affect the HLB value (equilibrium value of hydrophilic group oleophilic group) of structure emulsifying agent described in the application, emulsifier hlb value of the present invention is 8-18, and tensio-active agent is due to aligning and have and reduce the effect of interfacial tension on oil-water interface, so it hydrophilicly answers proper equilibrium with oleophylic ability.If hydrophilic or oleophylic ability is excessive, then tensio-active agent will be soluble in the aqueous phase completely or in oil phase, seldom be present on interface, is difficult to reach the effect reducing interfacial tension.By testing the alkyl (as used amino dodecane, tetradecy lamine etc. in synthesis material) of different carbon atoms, emulsifying agent of the present invention has better asphalt emulsifier HLB value.
In addition, the emulsifying agent that the hydrophobic grouping of different carbon chain lengths and hydrophilic radical are formed, its CMC (micelle-forming concentration) is also often different, CMC can be used as the surface-active one tolerance of tensio-active agent, and CMC is less, shows that the concentration that this tensio-active agent is formed needed for micella is lower, the concentration reaching surperficial saturated adsorption is lower, emulsifying agent CMC value of the present invention is less, has good emulsifying effectiveness, belong to and split type asphalt emulsifier soon pitch.
Present invention also offers the preparation method of this dication dual anion type asphalt emulsifier, comprise the following steps:
(1) preparation or acquisition octadecyl amido propionic acid;
(2) intermediate is prepared: low carbon number tertiary amine, add concentrated hydrochloric acid, add epoxy chloropropane gradually again, be obtained by reacting epoxypropyl tri alkyl ammomium chloride hydrochloride intermediate, shown in I, intermediate described in formula I is added 60-80 DEG C of reaction in octadecyl amido propionic acid, intermediate shown in obtained formula II;
(3) add sodium chloroacetate solution in the reaction solution obtained to step (2), 60-80 DEG C of stirring reaction obtains dication dual anion type asphalt emulsifier.
Described low carbon number tertiary amine is Trimethylamine 99, triethylamine or trolamine.
It should be noted that, the reaction preparing octadecyl amido propionic acid belongs to prior art, as ten thousand is loyal and righteous, the synthesis and characteries of the novel cation asphalt emulsifier " characterize " (Master's thesis) is disclosed to be reacted by stearylamine and vinylformic acid and generates octadecyl amido propionic acid Series of Asphalt emulsifying agent, and this content is introduced the application in the lump.
Preferably, the preparation method of this dication dual anion type asphalt emulsifier, comprises the following steps:
(1) join in reaction vessel by stearylamine, add alcoholic solvent, heated and stirred is dissolved, then adds vinylformic acid, at 60-80 DEG C of stirring reaction 2-4h;
(2) in another reactor, low carbon number tertiary amine is added, add technical hydrochloric acid gradually, add epoxy chloropropane gradually again, 30-70 DEG C of stirring reaction 2h, obtain reaction intermediate, the reaction intermediate of preparation is added drop-wise in above-mentioned steps (1) synthetic product, 60-80 DEG C of stirring reaction 2-4h;
(3) in the reaction solution of step (2), adding mass concentration is the 25-35% sodium chloroacetate aqueous solution, at 60-80 DEG C of stirring reaction 2-7h, obtains dication dual anion type asphalt emulsifier;
Preferably, in step (1), (2) and (3), the mol ratio of stearylamine, alcoholic solvent, vinylformic acid, low carbon number tertiary amine, technical hydrochloric acid, epoxy chloropropane, sodium chloroacetate is 1:(4.00-9.00): (1.00-1.06): (1.02-1.10): (1.02-1.10): (1.02-1.08): (1.01-1.08), the substrate of different mol ratio, its product structure generated can produce huge difference.Through many experiments checking with analyze, the yield of the dication dual anion type asphalt emulsifier that each raw material of above-mentioned molar ratio makes the present invention prepare and best performance;
In step (1), described alcoholic solvent is ethanol, methyl alcohol or Virahol;
In step (2), described low carbon number tertiary amine is trimethylamine aqueous solution, triethylamine or trolamine;
In step (3), sodium chloroacetate reacts obtained by Mono Chloro Acetic Acid and sodium hydroxide.
Preferably, in step (1), temperature of reaction is 65-75 DEG C;
Preferably, in step (2), temperature of reaction is 65-75 DEG C;
Preferably, in step (3), temperature of reaction is 65-75 DEG C.
In addition, the present invention also provides the dication dual anion type asphalt emulsifier of described preparation preparing the application in emulsified bitumen.
Preferably, described application method is: dication dual anion type asphalt emulsifier is mixed with the aqueous solution that mass concentration is 1.0-3.0%, with salt acid for adjusting pH value to 2-3, is heated to 65 DEG C, obtained soap lye; Pitch and emulsifying agent soap lye are prepared cationic emulsified bitumen by colloidal mill emulsification.
Preferably, described application method is: dication dual anion type asphalt emulsifier is mixed with the aqueous solution that mass concentration is 1.0-3.0%, by sodium hydroxide adjust ph to 10-11, is heated to 65 DEG C, obtained soap lye; Pitch and emulsifying agent soap lye are prepared anionic emulsified bitumen by colloidal mill emulsification.
The present invention has following beneficial effect relative to prior art:
(1) raw material that the raw material stearylamine of dication dual anion type asphalt emulsifier of the present invention is used relative to current cationic asphalt emulsifier is cheap, wide material sources, and asphalt emulsifier production cost is low.
(2) preparation method's technique of dication dual anion type asphalt emulsifier of the present invention simply, not needs pyroreaction.
(3) the dication dual anion type asphalt emulsifier prepared of the present invention can the pitch of the multiple different model of emulsification, the emulsified bitumen of preparation is evenly fine and smooth, stability in storage is good, is applicable to the spread of road metal sealing, priming oil or sticking layer oil, has the characteristic splitting asphalt emulsifier soon.Obtained emulsified bitumen properties all can meet the cationic emulsified bitumen standard (JTJ052-2000) that Chinese transportation portion works out.
(4) in raw material of the present invention by adding vinylformic acid, low carbon number tertiary amine, epoxy chloropropane and sodium chloroacetate, the asphalt emulsification agent molecule prepared is made to have dication dual anion type, enhance the charge density of asphalt emulsification agent molecule, improve the wetting ability of asphalt emulsification agent molecule.Not only increase the emulsifying property of asphalt emulsifier like this, and improve the use properties of emulsified bitumen.
(5) in asphalt emulsifier molecular structure of the present invention, there is anionic group and cation group simultaneously, both sexes asphalt emulsifier is applicable to different environment, present the feature of cationic surfactant in an acidic solution, in basic solution, present the feature of aniorfic surfactant.
Embodiment
The present invention is further illustrated in conjunction with the embodiments, should be noted that following explanation is only to explain the present invention, not limiting its content.
Raw material used in the embodiment of the present invention, reagent are conventional chemical product, all buy by market and obtain.
Embodiment 1
(1) preparation of dication dual anion type asphalt emulsifier:
1) add 269.5g stearylamine in the reactor, 260g Virahol, heated and stirred is dissolved.Then 73.5g vinylformic acid is dripped, 70 DEG C of stirring reaction 2h.
2) add 193.1g33% trimethylamine aqueous solution in the reactor, add 131.2g30% technical hydrochloric acid gradually, then add 97.1g epoxy chloropropane gradually, 30-70 DEG C of stirring reaction 2h, obtains reaction intermediate A.The reaction intermediate A of preparation is added drop-wise to above-mentioned steps 1) in synthetic product, 70 DEG C of stirring reaction 2h.
3) be dissolved in 80.0g water by 41.2g sodium hydroxide and obtain aqueous sodium hydroxide solution, 97.3g Mono Chloro Acetic Acid is dissolved in 180.0g water and obtains the Mono Chloro Acetic Acid aqueous solution; Aqueous sodium hydroxide solution is added drop-wise in the Mono Chloro Acetic Acid aqueous solution and obtains the sodium chloroacetate aqueous solution.The sodium chloroacetate aqueous solution of preparation is added drop-wise to above-mentioned steps 2) in synthetic product, 70 DEG C of stirring reaction 4h.Obtain dication dual anion type asphalt emulsifier, give over to emulsified bitumen test.
Synthetic product carries out FTIR detection after recrystallization separating-purifying, and result is as follows: 3349cm
-1for the stretching vibration absorption peak of O-H, 2920cm
-1and 2849cm
-1be respectively asymmetric stretching vibration and the symmetrical stretching vibration absorption peak of methylene radical, 1648cm
-1for C=O stretching vibration absorption peak in carboxylic acid, 1534cm
-1for C=O stretching vibration absorption peak in carboxylate salt, 1472cm
-1for methylene radical scissoring vibration absorption peak, 1382cm
-1for methyl symmetric curvature vibration absorption peak, 1237cm
-1for C-N stretching vibration absorption peak, 1064cm
-1for C-OH stretching vibration absorption peak, 926cm
-1for the wagging vibration absorption peak of O-H in carboxylic acid, 717cm
-1for methylene radical rocking vibration absorption peak.
Reaction equation is as follows:
(2) preparation of emulsified bitumen:
Get AH-90# pitch 300g, be heated to 125 DEG C, asphalt emulsifier prepared by 12.5g the present embodiment is joined in 200g water, by technical hydrochloric acid adjust ph to 2-3, be heated to 65 DEG C, obtained soap lye.Pitch and emulsifying agent soap lye are prepared cationic emulsified bitumen by colloidal mill emulsification.
(3) emulsified bitumen Performance Detection:
The cationic emulsified bitumen standard (JTJ052-2000) that obtained emulsified bitumen is worked out by Chinese transportation portion detects, result is as follows: emulsified bitumen prepared by the present embodiment is even, fine and smooth, asphalt content is 60%, on sieve, residual content is 0.01%, wrap area with mineral aggregate and be greater than 2/3, stability in storage (5d) is 3.6%; In de-emulsification speed test, adopt category-B material, Mixable time is 11 seconds.Employing is mixed and stirred material and is mixed and stirred, and Mixable time is 3 seconds.Show that bitumen emulsion prepared by this emulsifying agent is for split type cationic emulsified bitumen soon, properties all can meet the requirement of JTJ052-2000 standard.
Embodiment 2
(1) preparation of dication dual anion type asphalt emulsifier:
1) add 269.5g stearylamine in the reactor, 260g Virahol, heated and stirred is dissolved.Then 73.5g vinylformic acid is dripped, 65 DEG C of stirring reaction 3h.
2) add 109.1g triethylamine in the reactor, add 131.2g30% technical hydrochloric acid gradually, then add 97.1g epoxy chloropropane gradually, 30-70 DEG C of stirring reaction 2h, obtains reaction intermediate B.The reaction intermediate B of preparation is added drop-wise to above-mentioned steps 1) in synthetic product, 65 DEG C of stirring reaction 3h.
3) be dissolved in 80.0g water by 41.2g sodium hydroxide and obtain aqueous sodium hydroxide solution, 97.3g Mono Chloro Acetic Acid is dissolved in 180.0g water and obtains the Mono Chloro Acetic Acid aqueous solution; Aqueous sodium hydroxide solution is added drop-wise in the Mono Chloro Acetic Acid aqueous solution and obtains the sodium chloroacetate aqueous solution.The sodium chloroacetate aqueous solution of preparation is added drop-wise to above-mentioned steps 2) in synthetic product, 75 DEG C of stirring reaction 3h.Obtain dication dual anion type asphalt emulsifier, give over to emulsified bitumen test.
Synthetic product carries out FTIR detection after recrystallization separating-purifying, and result is as follows: 3346cm
-1for the stretching vibration absorption peak of O-H, 2920cm
-1and 2846cm
-1be respectively asymmetric stretching vibration and the symmetrical stretching vibration absorption peak of methylene radical, 1653cm
-1for C=O stretching vibration absorption peak in carboxylic acid, 1532cm
-1for C=O stretching vibration absorption peak in carboxylate salt, 1475cm
-1for methylene radical scissoring vibration absorption peak, 1385cm
-1for methyl symmetric curvature vibration absorption peak, 1239cm
-1for C-N stretching vibration absorption peak, 1063cm
-1for C-OH stretching vibration absorption peak, 927cm
-1for the wagging vibration absorption peak of O-H in carboxylic acid, 723cm
-1for methylene radical rocking vibration absorption peak.
Reaction equation is as follows:
(2) preparation of emulsified bitumen:
Get AH-70# pitch 300g, be heated to 125 DEG C, asphalt emulsifier prepared by 12.5g the present embodiment is joined in 200g water, by technical hydrochloric acid adjust ph to 2-3, be heated to 65 DEG C, obtained soap lye.Pitch and emulsifying agent soap lye are prepared cationic emulsified bitumen by colloidal mill emulsification.
(3) emulsified bitumen Performance Detection:
Detection method is with embodiment 1, and detected result is: emulsified bitumen is even, fine and smooth, and asphalt content is 58%, and on sieve, residual content is 0.02%, wraps area be greater than 2/3 with mineral aggregate, and stability in storage (5d) is 4.4%; In de-emulsification speed test, adopt category-B material, Mixable time is 25 seconds.Employing is mixed and stirred material and is mixed and stirred, and Mixable time is 3 seconds.Show that bitumen emulsion prepared by this emulsifying agent is for split type cationic emulsified bitumen soon, properties all can meet the requirement of JTJ052-2000 standard.
(4) preparation of emulsified bitumen:
Get AH-90# pitch 300g, be heated to 125 DEG C, asphalt emulsifier prepared by 12.5g the present embodiment is joined in 200g water, by sodium hydroxide adjust ph to 10-11, be heated to 65 DEG C, obtained soap lye.Pitch and emulsifying agent soap lye are prepared anionic emulsified bitumen by colloidal mill emulsification.
(5) emulsified bitumen Performance Detection:
Detection method is with embodiment 1, and detected result is: emulsified bitumen is even, fine and smooth, and asphalt content is 59%, and on sieve, residual content is 0.03%, wraps area be greater than 2/3 with mineral aggregate, and stability in storage (5d) is 4.1%; In de-emulsification speed test, adopt category-B material, Mixable time is 16 seconds.Employing is mixed and stirred material and is mixed and stirred, and Mixable time is 5 seconds.Show that bitumen emulsion prepared by this emulsifying agent is for split type anionic emulsified bitumen soon.
Embodiment 3
(1) preparation of dication dual anion type asphalt emulsifier:
1) add 269.5g stearylamine in the reactor, 260g Virahol, heated and stirred is dissolved.Then 73.5g vinylformic acid is dripped, 70 DEG C of stirring reaction 2h.
2) add 189.6g85% trolamine in the reactor, add 131.2g30% technical hydrochloric acid gradually, then add 97.1g epoxy chloropropane gradually, 30-70 DEG C of stirring reaction 2h, obtains reaction intermediate C.The reaction intermediate C of preparation is added drop-wise to above-mentioned steps 1) in synthetic product, 70 DEG C of stirring reaction 2h.
3) be dissolved in 80.0g water by 41.2g sodium hydroxide and obtain aqueous sodium hydroxide solution, 97.3g Mono Chloro Acetic Acid is dissolved in 180.0g water and obtains the Mono Chloro Acetic Acid aqueous solution; Aqueous sodium hydroxide solution is added drop-wise in the Mono Chloro Acetic Acid aqueous solution and obtains the sodium chloroacetate aqueous solution.The sodium chloroacetate aqueous solution of preparation is added drop-wise to above-mentioned steps 2) in synthetic product, 65 DEG C of stirring reaction 6h.Obtain dication dual anion type asphalt emulsifier, give over to emulsified bitumen test.
Synthetic product carries out FTIR detection after recrystallization separating-purifying, and result is as follows: 3393cm
-1for the stretching vibration absorption peak of O-H, 2921cm
-1and 2846cm
-1be respectively asymmetric stretching vibration and the symmetrical stretching vibration absorption peak of methylene radical, 1736cm
-1for C=O stretching vibration absorption peak in carboxylic acid, 1596cm
-1for C=O stretching vibration absorption peak in carboxylate salt, 1462cm
-1for methylene radical scissoring vibration absorption peak, 1396cm
-1for methyl symmetric curvature vibration absorption peak, 1253cm
-1and 1208cm
-1for C-N stretching vibration absorption peak, 1073cm
-1for C-OH stretching vibration absorption peak, 912cm
-1for the wagging vibration absorption peak of O-H in carboxylic acid, 720cm
-1for methylene radical rocking vibration absorption peak.
Reaction equation is as follows:
(2) preparation of emulsified bitumen:
Get A-100# pitch 300g, be heated to 125 DEG C, asphalt emulsifier prepared by 12.5g the present embodiment is joined in 200g water, by technical hydrochloric acid adjust ph to 2-3, be heated to 65 DEG C, obtained soap lye.Pitch and emulsifying agent soap lye are prepared cationic emulsified bitumen by colloidal mill emulsification.
(3) emulsified bitumen Performance Detection:
Detection method is with embodiment 1, and detected result is: emulsified bitumen is even, fine and smooth, and asphalt content is 60%, and on sieve, residual content is 0.02%, wraps area be greater than 2/3 with mineral aggregate, and stability in storage (5d) is 4.8%; In de-emulsification speed test, adopt category-B material, Mixable time is 4 seconds.Employing is mixed and stirred material and is mixed and stirred, and Mixable time is 2 seconds.Show that bitumen emulsion prepared by this emulsifying agent is for split type cationic emulsified bitumen soon, properties all can meet the requirement of JTJ052-2000 standard.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; one of ordinary skill in the art should be understood that; on the basis of technical scheme of the present invention, those skilled in the art do not need to pay various amendment or distortion that creative work can make still within protection scope of the present invention.
Claims (10)
1. a dication dual anion type asphalt emulsifier, is characterized in that, the molecular structure of described dication dual anion type asphalt emulsifier is:
Wherein, R=methyl (-CH
3), ethyl (-C
2h
5), ethanol based (-C
2h
4oH).
2. dication dual anion type asphalt emulsifier according to claim 1, is characterized in that, be prepared from by the raw material of following mol ratio:
Stearylamine: alcoholic solvent: vinylformic acid: low carbon number tertiary amine: technical hydrochloric acid: epoxy chloropropane: sodium chloroacetate=1mol:(4.00-9.00) mol:(1.00-1.06) mol:(1.02-1.10) mol:(1.02-1.10) mol:(1.02-1.08) mol:(1.01-1.08) mol;
Described alcoholic solvent is ethanol, methyl alcohol or Virahol;
Described low carbon number tertiary amine is trimethylamine aqueous solution, triethylamine or trolamine.
3. the preparation method of dication dual anion type asphalt emulsifier according to claim 1, comprises the following steps:
(1) preparation or acquisition octadecyl amido propionic acid;
(2) intermediate is prepared: low carbon number tertiary amine, add concentrated hydrochloric acid, add epoxy chloropropane gradually again, be obtained by reacting epoxypropyl tri alkyl ammomium chloride hydrochloride intermediate, shown in I, intermediate described in formula I is added 60-80 DEG C of reaction in octadecyl amido propionic acid, intermediate shown in obtained formula II;
(3) add sodium chloroacetate solution in the reaction solution obtained to step (2), 60-80 DEG C of stirring reaction obtains dication dual anion type asphalt emulsifier;
Described low carbon number tertiary amine is trimethylamine aqueous solution, triethylamine or trolamine.
4. the preparation method of dication dual anion type asphalt emulsifier described in claim 3, is characterized in that, comprise the following steps:
(1) join in reaction vessel by stearylamine, add alcoholic solvent, heated and stirred is dissolved, then adds vinylformic acid, at 60-80 DEG C of stirring reaction 2-4h;
(2) in another reactor, low carbon number tertiary amine is added, add technical hydrochloric acid gradually, add epoxy chloropropane gradually again, 30-70 DEG C of stirring reaction 2h, obtain reaction intermediate, the reaction intermediate of preparation is added drop-wise in above-mentioned steps (1) synthetic product, 60-80 DEG C of stirring reaction 2-4h;
(3) in the reaction solution of step (2), adding mass concentration is the 25-35% sodium chloroacetate aqueous solution, at 60-80 DEG C of stirring reaction 2-7h, obtains dication dual anion type asphalt emulsifier.
5. the preparation method of dication dual anion type asphalt emulsifier according to claim 4, it is characterized in that, in step (1), (2) and (3), the mol ratio of stearylamine, alcoholic solvent, vinylformic acid, low carbon number tertiary amine, technical hydrochloric acid, epoxy chloropropane, sodium chloroacetate is 1:(4.00-9.00): (1.00-1.06): (1.02-1.10): (1.02-1.10): (1.02-1.08): (1.01-1.08).
6. the preparation method of dication dual anion type asphalt emulsifier according to claim 5, it is characterized in that, in step (1), described alcoholic solvent is ethanol, methyl alcohol or Virahol.
7. the preparation method of dication dual anion type asphalt emulsifier according to claim 5, it is characterized in that, in step (2), described low carbon number tertiary amine is trimethylamine aqueous solution, triethylamine or trolamine.
8. the preparation method of dication dual anion type asphalt emulsifier according to claim 5, is characterized in that, in step (3), sodium chloroacetate reacts obtained by Mono Chloro Acetic Acid and sodium hydroxide.
9. described in claim 1, dication dual anion type asphalt emulsifier is preparing the application in emulsified bitumen.
10. apply according to claim 9, it is characterized in that, described application method is: dication dual anion type asphalt emulsifier is mixed with the aqueous solution that mass concentration is 1.0-3.0%, with salt acid for adjusting pH value to 2-3, be heated to 65 DEG C, obtained soap lye, prepares cationic emulsified bitumen by pitch and emulsifying agent soap lye by colloidal mill emulsification; Or, dication dual anion type asphalt emulsifier is mixed with the aqueous solution that mass concentration is 1.0-3.0%, by sodium hydroxide adjust ph to 10-11, is heated to 65 DEG C, obtained soap lye, prepares anionic emulsified bitumen by pitch and emulsifying agent soap lye by colloidal mill emulsification.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510969040.1A CN105384948B (en) | 2015-12-21 | 2015-12-21 | A kind of dication dual anion type asphalt emulsifier and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510969040.1A CN105384948B (en) | 2015-12-21 | 2015-12-21 | A kind of dication dual anion type asphalt emulsifier and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105384948A true CN105384948A (en) | 2016-03-09 |
| CN105384948B CN105384948B (en) | 2017-10-24 |
Family
ID=55417758
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510969040.1A Expired - Fee Related CN105384948B (en) | 2015-12-21 | 2015-12-21 | A kind of dication dual anion type asphalt emulsifier and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105384948B (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105860092A (en) * | 2016-06-22 | 2016-08-17 | 山东大学 | Lignin diamine cationic asphalt emulsifier and preparation method thereof |
| CN105885060A (en) * | 2016-06-22 | 2016-08-24 | 山东大学 | Lignin polyamine quaternary ammonium salt cationic asphalt emulsifier and preparation method thereof |
| CN105968382A (en) * | 2016-06-22 | 2016-09-28 | 山东大学 | Lignin polyamine cation rapid-cracking type asphalt emulsifier and preparation method thereof |
| CN106008996A (en) * | 2016-06-22 | 2016-10-12 | 山东大学 | Lignin polyamine cation type asphalt emulsifier as well as preparation method and application thereof |
| CN106084250A (en) * | 2016-06-22 | 2016-11-09 | 山东大学 | A kind of lignin cyclammonium cationoid type asphalt emulsifier and preparation method thereof |
| CN106831478A (en) * | 2017-01-23 | 2017-06-13 | 山东大学 | Asphalt emulsifier of type or slow breaking and preparation method thereof is split in a kind of polycation teritary amide class |
| CN106905943A (en) * | 2017-02-28 | 2017-06-30 | 陕西延长石油(集团)有限责任公司研究院 | A kind of preparation method of amphion molecule deposition film oil-displacing agent used for tertiary oil recovery |
| CN107056637A (en) * | 2017-01-23 | 2017-08-18 | 山东大学 | A kind of dication teritary amide type asphalt emulsifier and preparation method thereof |
| CN107056639A (en) * | 2017-01-23 | 2017-08-18 | 山东大学 | A kind of dication single anion teritary amide type asphalt emulsifier and preparation method thereof |
| CN107383391A (en) * | 2017-04-13 | 2017-11-24 | 山东大学 | A kind of secondary amide double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier and preparation method thereof |
| CN108047269A (en) * | 2018-01-05 | 2018-05-18 | 山东大学 | A kind of quaternary Hydroxypropyl phosphate ester sodium splits type asphalt emulsifier and preparation method thereof soon |
| CN108041035A (en) * | 2017-12-12 | 2018-05-18 | 中海油天津化工研究设计院有限公司 | A kind of dication epoxy type fungicide and preparation method thereof |
| CN108752223A (en) * | 2018-05-16 | 2018-11-06 | 南京林业大学 | Cation acrylic epoxy monoesters emulsifier and preparation method thereof |
| CN112138603A (en) * | 2020-09-11 | 2020-12-29 | 塔里木大学 | Preparation method of double-ended single-tail surfactant |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1563196A (en) * | 2004-04-06 | 2005-01-12 | 株洲时代新材料科技股份有限公司 | Dedicated asphalt emulsion and preparation method |
| CN1772759A (en) * | 2004-11-11 | 2006-05-17 | 气体产品与化学公司 | N,n-dialkyl polyhydroxy alkylamines |
| CN103980147A (en) * | 2014-05-23 | 2014-08-13 | 山东大学 | Method for preparing amphoteric betaine asphalt emulsifier |
| CN104151179A (en) * | 2014-08-07 | 2014-11-19 | 山东大学 | Dication asphalt emulsifier and preparation method thereof |
-
2015
- 2015-12-21 CN CN201510969040.1A patent/CN105384948B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1563196A (en) * | 2004-04-06 | 2005-01-12 | 株洲时代新材料科技股份有限公司 | Dedicated asphalt emulsion and preparation method |
| CN1772759A (en) * | 2004-11-11 | 2006-05-17 | 气体产品与化学公司 | N,n-dialkyl polyhydroxy alkylamines |
| CN103980147A (en) * | 2014-05-23 | 2014-08-13 | 山东大学 | Method for preparing amphoteric betaine asphalt emulsifier |
| CN104151179A (en) * | 2014-08-07 | 2014-11-19 | 山东大学 | Dication asphalt emulsifier and preparation method thereof |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106084250B (en) * | 2016-06-22 | 2018-06-12 | 山东大学 | A kind of lignin cyclammonium cationoid type asphalt emulsifier and preparation method thereof |
| CN105968382A (en) * | 2016-06-22 | 2016-09-28 | 山东大学 | Lignin polyamine cation rapid-cracking type asphalt emulsifier and preparation method thereof |
| CN105860092B (en) * | 2016-06-22 | 2018-03-16 | 山东大学 | A kind of lignin diamine cationoid type asphalt emulsifier and preparation method thereof |
| CN105968382B (en) * | 2016-06-22 | 2018-03-20 | 山东大学 | A kind of more amine cations of lignin split type asphalt emulsifier and preparation method thereof soon |
| CN105885060B (en) * | 2016-06-22 | 2018-03-20 | 山东大学 | A kind of more amine quaternary ammonium salt cationic type asphalt emulsifiers of lignin and preparation method thereof |
| CN105885060A (en) * | 2016-06-22 | 2016-08-24 | 山东大学 | Lignin polyamine quaternary ammonium salt cationic asphalt emulsifier and preparation method thereof |
| CN105860092A (en) * | 2016-06-22 | 2016-08-17 | 山东大学 | Lignin diamine cationic asphalt emulsifier and preparation method thereof |
| CN106008996A (en) * | 2016-06-22 | 2016-10-12 | 山东大学 | Lignin polyamine cation type asphalt emulsifier as well as preparation method and application thereof |
| CN106084250A (en) * | 2016-06-22 | 2016-11-09 | 山东大学 | A kind of lignin cyclammonium cationoid type asphalt emulsifier and preparation method thereof |
| CN106831478B (en) * | 2017-01-23 | 2018-06-26 | 山东大学 | Asphalt emulsifier of type or slow breaking and preparation method thereof is split in a kind of polycation teritary amide class |
| CN107056639A (en) * | 2017-01-23 | 2017-08-18 | 山东大学 | A kind of dication single anion teritary amide type asphalt emulsifier and preparation method thereof |
| CN107056637A (en) * | 2017-01-23 | 2017-08-18 | 山东大学 | A kind of dication teritary amide type asphalt emulsifier and preparation method thereof |
| CN106831478A (en) * | 2017-01-23 | 2017-06-13 | 山东大学 | Asphalt emulsifier of type or slow breaking and preparation method thereof is split in a kind of polycation teritary amide class |
| CN107056639B (en) * | 2017-01-23 | 2019-05-07 | 山东大学 | A kind of dication single anion teritary amide type asphalt emulsifier and preparation method thereof |
| CN106905943A (en) * | 2017-02-28 | 2017-06-30 | 陕西延长石油(集团)有限责任公司研究院 | A kind of preparation method of amphion molecule deposition film oil-displacing agent used for tertiary oil recovery |
| CN107383391A (en) * | 2017-04-13 | 2017-11-24 | 山东大学 | A kind of secondary amide double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier and preparation method thereof |
| CN108041035A (en) * | 2017-12-12 | 2018-05-18 | 中海油天津化工研究设计院有限公司 | A kind of dication epoxy type fungicide and preparation method thereof |
| CN108047269A (en) * | 2018-01-05 | 2018-05-18 | 山东大学 | A kind of quaternary Hydroxypropyl phosphate ester sodium splits type asphalt emulsifier and preparation method thereof soon |
| CN108047269B (en) * | 2018-01-05 | 2019-08-13 | 山东大学 | A kind of quaternary Hydroxypropyl phosphate ester sodium splits type asphalt emulsifier and preparation method thereof fastly |
| CN108752223A (en) * | 2018-05-16 | 2018-11-06 | 南京林业大学 | Cation acrylic epoxy monoesters emulsifier and preparation method thereof |
| CN112138603A (en) * | 2020-09-11 | 2020-12-29 | 塔里木大学 | Preparation method of double-ended single-tail surfactant |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105384948B (en) | 2017-10-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105384948A (en) | Dication and dianion type asphalt emulsifier and preparation method thereof | |
| CN105399645B (en) | A kind of polycation acid amide type asphalt emulsifier and preparation method thereof | |
| CN105418942B (en) | A kind of dication acid amide type asphalt emulsifier and preparation method thereof | |
| CN104151179B (en) | A kind of dication type asphalt emulsifier and preparation method thereof | |
| CN106008996B (en) | A kind of more amine cation type asphalt emulsifiers of lignin and preparation method and application | |
| CN103980147B (en) | A kind of preparation method of both sexes betaine type asphalt emulsifier | |
| CN106084250B (en) | A kind of lignin cyclammonium cationoid type asphalt emulsifier and preparation method thereof | |
| CN106977431B (en) | A kind of primary amide quaternary hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier and preparation method thereof | |
| CN106946747A (en) | A kind of carboxylic acid double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier and preparation method thereof | |
| CN105860092B (en) | A kind of lignin diamine cationoid type asphalt emulsifier and preparation method thereof | |
| CN106977432B (en) | A kind of teritary amide quaternary hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier and preparation method thereof | |
| CN104694114A (en) | Supramolecular clean fracturing fluid, and preparation method and application thereof | |
| CN105885060B (en) | A kind of more amine quaternary ammonium salt cationic type asphalt emulsifiers of lignin and preparation method thereof | |
| CN107383391A (en) | A kind of secondary amide double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier and preparation method thereof | |
| CN107056637A (en) | A kind of dication teritary amide type asphalt emulsifier and preparation method thereof | |
| CN107903194A (en) | A kind of amidoquat salt form hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier and preparation method thereof | |
| CN105968382B (en) | A kind of more amine cations of lignin split type asphalt emulsifier and preparation method thereof soon | |
| CN106947093B (en) | A kind of primary amide double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier and preparation method thereof | |
| CN106831477B (en) | A kind of both sexes teritary amide type asphalt emulsifier and preparation method thereof | |
| CN109694481B (en) | Carboxylic acid bis-quaternary ammonium salt type sodium hydroxypropyl phosphate asphalt emulsifier and preparation method thereof | |
| CN106928470A (en) | A kind of teritary amide double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier and preparation method thereof | |
| CN110305336B (en) | Amide polyamine asphalt emulsifier, emulsified asphalt, and preparation method and application thereof | |
| CN108467495A (en) | A kind of lignin quaternary ammonium salt cation asphalt emulsifier and preparation method thereof | |
| CN111978561B (en) | Quaternary ammonium salt polyamine amphoteric asphalt emulsifier, emulsified asphalt, and preparation method and application thereof | |
| CN108517040A (en) | A kind of cellulose family quaternary ammonium salt cation asphalt emulsifier and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20171024 Termination date: 20181221 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |