CN105384948B - A kind of dication dual anion type asphalt emulsifier and preparation method thereof - Google Patents
A kind of dication dual anion type asphalt emulsifier and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of dication dual anion type asphalt emulsifier, belong to field of fine chemical.Emulsifying agent of the present invention is made up of the raw material of following mol ratio：Octadecylamine：Alcohols solvent：Acrylic acid：Low carbon number tertiary amine：Technical hydrochloric acid：Epoxychloropropane：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.The synthesis material of asphalt emulsifier of the present invention is easy to get, production cost is low, technique is simple, do not need pyroreaction, the pitch of emulsifiable a variety of different models, the emulsified asphalt of preparation is fine and smooth uniform, storage stability is good, suitable for the spread of road metal sealing, priming oil or sticking layer oil, with the characteristic for splitting asphalt emulsifier soon.
Description
Technical field
The present invention relates to a kind of dication dual anion type asphalt emulsifier and preparation method thereof, belong to fine chemistry industry skill
Art field.
Background technology
Emulsified asphalt especially cationic emulsified bitumen can have due to that with energy-conserving and environment-protective, can improve execution conditions
Effect reduces many excellent application characteristics such as pitch overaging, and is widely used in road construction and pavement preservation.
The most critical factor for influenceing emulsified asphalt pavement performance is exactly asphalt emulsifier, at present domestic and international cationic pitch
Emulsifying agent principal item has organic amine, quaternary ammonium salt, imidazolines, amide-type etc., the wherein application of quaternary ammonium salt emulsifying agent most
Extensively.With the application of cationic emulsified bitumen, the kind of asphalt emulsifier is also gradually enriched.
United States Patent (USP) USP4338136 is with C12-18Long carbon chain aliphatic acid reacts preparation under certain condition with diethylenetriamine
Asphalt emulsifier.The shortcoming of this method is that the asphalt emulsifier prepared is expensive, when being constructed for slurry seal, is demulsified the time
Long, molding time is slow, and the open to traffic time is long.Chinese patent CN1096714 utilizes oil plant by-product aphthenic acids and alkenyl polyamine
Reaction, prepares asphalt emulsifier.The shortcoming of this method be the raw material supply of emulsifying agent by severely restricts, be unfavorable for promote should
With.Chinese patent CN1861721A is related to a kind of rosin cation asphalt emulgent.The emulsifying agent is by rosin and alkenyl polyamine
Reaction, obtain rosin intermediate, then, with different types of quaternary ammonium salt intermediate be condensed, be made function admirable rosin sun from
Sub- asphalt emulsifier.The shortcoming of this method is that reactions steps are cumbersome, it is necessary to pyroreaction.Chinese patent CN101712625A is related to
And a kind of method for synthesizing amphoteric slow-breaking quick-setting asphalt emulsifier, using oleic acid and polyamines reaction generation polyamide-polyamino, then add
Halogenating reaction occurs for monoxone, and asphalt emulsifier is made.The shortcoming of this method is to need pyroreaction when preparing.Chinese patent
CN101745340A is related to a kind of cation asphalt emulgent preparation method, and host is obtained by mixed organic acid and organic amine reaction
Intermediate, then carry out quaterisation be made, assistant agent be nonionic surfactant and modified additive.The shortcoming of this method is system
Standby complex steps, cost is higher, it is necessary to pyroreaction.
Although asphalt emulsifier species starts to enrich, due to the difference of asphalt source and refining process, cause pitch
Composition differs, and a kind of emulsifying agent is more difficult all to have good emulsifying effectiveness to various pitches；And the stabilization of emulsified asphalt
Property is poor；In addition, although above-mentioned prior art discloses a variety of cationic asphalt emulsifiers and preparation method thereof, but it is prepared
The cost of material of emulsifying agent is higher, and source is restricted, and pyroreaction is needed during preparation, higher to productive experiment equipment requirement.
The asphalt emulsifier for the new structure that how development cost is cheap, emulsifying effectiveness is good, is especially applicable different shaped
Number pitch, the asphalt emulsifier that soon splits type cationic emulsified bitumen good for preparing fine and smooth uniform, storage stability, are abilities
Problems faced in domain.
The content of the invention
For the deficiencies in the prior art, it is an object of the invention to provide a kind of production cost is low, technique is simple,
Dication dual anion type asphalt emulsifier of pyroreaction and preparation method thereof is not needed.
To achieve the above object, the present invention is adopted the following technical scheme that：
The invention provides a kind of dication dual anion type asphalt emulsifier, it is characterised in that the dication
The molecular structure of dual anion type asphalt emulsifier is：
Wherein, R=methyl (- CH3), ethyl (- C2H5), ethanol base (- C2H4OH)。
It is preferred that, dication dual anion type asphalt emulsifier of the present invention, by the raw material system of following mol ratio
It is standby to form：
Octadecylamine：Alcohols solvent：Acrylic acid：Low carbon number tertiary amine：Technical hydrochloric acid：Epoxychloropropane：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；
The alcohols solvent is ethanol, methanol or isopropanol；
The low carbon number tertiary amine is trimethylamine aqueous solution, triethylamine or triethanolamine.
Octadecylamine is used in dication dual anion type asphalt emulsifier synthesis of the present invention, the emulsifying agent is hydrophobic
Group is octadecyl, and the HLB value (hydrophilic group of herein described structure emulsifying agent can be influenceed using the alkyl of different carbon atoms
The equilibrium valve of lipophilic group), emulsifier hlb value of the invention is 8-18, and surfactant is due to the orientation on oil-water interface
The effect of reduction interfacial tension is arranged and has, so its hydrophilic and oleophylic ability answers appropriate balance.If hydrophilic or oleophylic energy
Power is excessive, then surfactant will be completely dissolved in aqueous phase or oil phase, be seldom present on interface, it is difficult to reach reduction interface
The effect of tension force.The alkyl (lauryl amine, tetradecy lamine are used in such as synthesis material) of different carbon atoms, the present invention by testing
The emulsifying agent has more preferable asphalt emulsifier HLB value.
In addition, the hydrophobic grouping of different carbon chain lengths and the emulsifying agent of hydrophilic radical formation, its CMC (critical micelle concentration)
Difference is also tended to, CMC can be measured as one kind of surfactant surface-active, and CMC is smaller, shows this surface-active dosage form
It is lower into the concentration needed for micella, reach that the concentration of surface saturation absorption is lower, emulsifying agent CMC value of the present invention is smaller, right
Pitch has good emulsifying effectiveness, belongs to and splits type asphalt emulsifier soon.
Present invention also offers the preparation method of the dication dual anion type asphalt emulsifier, comprise the following steps：
(1) prepare or obtain octadecyl amido propionic acid；
(2) intermediate is prepared：Low carbon number tertiary amine, adds concentrated hydrochloric acid, then is gradually added into epoxychloropropane, and reaction obtains epoxy
Propyl group tri alkyl ammomium chloride hydrochloride intermediate, shown in formula I, intermediate described in Formulas I is added in octadecyl amido propionic acid
60-80 DEG C of reaction, is made intermediate shown in Formula II；
(3) add sodium chloroacetate solution in the reaction solution obtained to step (2), 60-80 DEG C of stirring reaction obtain double sun from
Sub- dual anion type asphalt emulsifier.
Described low carbon number tertiary amine is trimethylamine, triethylamine or triethanolamine.
It should be noted that the reaction for preparing octadecyl amido propionic acid belongs to prior art, such as ten thousand loyal and righteous, " new sun
The synthesis of ion asphalt emulsifier and performance characterization " (Master's thesis) is disclosed by octadecylamine and propylene acid reaction generation 18
Alkyl amine group propionic acid Series of Asphalt emulsifying agent, the application is introduced by the content in the lump.
It is preferred that, the preparation method of the dication dual anion type asphalt emulsifier comprises the following steps：
(1) octadecylamine is added in reaction vessel, adds alcohols solvent, heating stirring dissolving adds acrylic acid,
60-80 DEG C of stirring reaction 2-4h；
(2) low carbon number tertiary amine is added in another reactor, technical hydrochloric acid is gradually added into, then be gradually added into epoxy chloropropionate
Alkane, 30-70 DEG C of stirring reaction 2h, obtains reaction intermediate, and the reaction intermediate of preparation is added drop-wise into above-mentioned steps (1) synthesis production
In thing, 60-80 DEG C of stirring reaction 2-4h；
(3) it is the 25-35% sodium chloroacetate aqueous solution mass concentration to be added into the reaction solution of step (2), is stirred at 60-80 DEG C
Reaction 2-7h is mixed, dication dual anion type asphalt emulsifier is obtained；
It is preferred that, in step (1), (2) and (3), octadecylamine, alcohols solvent, acrylic acid, low carbon number tertiary amine, technical hydrochloric acid,
Epoxychloropropane, the mol ratio of sodium chloroacetate are 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, it is greatly poor that its product structure generated can be produced
It is different.Verified by many experiments with analyzing, each raw material of above-mentioned molar ratio make it that the dication that the present invention is prepared is double
The yield and best performance of anionic asphalt emulsifier；
In step (1), described alcohols solvent is ethanol, methanol or isopropanol；
In step (2), described low carbon number tertiary amine is trimethylamine aqueous solution, triethylamine or triethanolamine；
In step (3), sodium chloroacetate is reacted by monoxone and sodium hydroxide to be made.
It is preferred that, in step (1), reaction temperature is 65-75 DEG C；
It is preferred that, in step (2), reaction temperature is 65-75 DEG C；
It is preferred that, in step (3), reaction temperature is 65-75 DEG C.
In addition, the dication dual anion type asphalt emulsifier that the present invention also provides the preparation is preparing emulsified asphalt
In application.
It is preferred that, the application process is：Dication dual anion type asphalt emulsifier is configured into mass concentration is
The 1.0-3.0% aqueous solution, with salt acid for adjusting pH value to 2-3, is heated to 65 DEG C, and soap lye is made；By pitch and emulsifying agent soap lye
Cationic emulsified asphalt is prepared by colloid mill emulsification.
It is preferred that, the application process is：Dication dual anion type asphalt emulsifier is configured into mass concentration is
The 1.0-3.0% aqueous solution, adjusts pH value to 10-11 with sodium hydroxide, is heated to 65 DEG C, soap lye is made；By pitch and emulsification
Agent soap lye prepares anionic emulsified asphalt by colloid mill emulsification.
The present invention has the advantages that relative to prior art：
(1) the raw material octadecylamine of dication dual anion type asphalt emulsifier of the invention is relative to current cation
Raw material used in type asphalt emulsifier is cheap, wide material sources, and asphalt emulsifier production cost is low.
(2) the preparation method technique of dication dual anion type asphalt emulsifier of the invention is simple, do not need high temperature
Reaction.
(3) pitch of the emulsifiable a variety of different models of dication dual anion type asphalt emulsifier prepared by the present invention,
The emulsified asphalt of preparation is fine and smooth uniform, and storage stability is good, it is adaptable to the spread of road metal sealing, priming oil or sticking layer oil,
With the characteristic for splitting asphalt emulsifier soon.Obtained emulsified asphalt properties can meet the cation of Chinese transportation portion formulation
Emulsified asphalt standard (JTJ052-2000).
(4) by adding acrylic acid, low carbon number tertiary amine, epoxychloropropane and sodium chloroacetate in raw material of the invention so that
The asphalt emulsification agent molecule of preparation has dication dual anion type, enhances the charge density of asphalt emulsification agent molecule, carries
The high hydrophily of asphalt emulsification agent molecule.The emulsifiability of asphalt emulsifier is so not only increased, and improves emulsification
The performance of pitch.
(5) there is anionic group and cation group, both sexes simultaneously in asphalt emulsifier molecular structure of the present invention
Asphalt emulsifier is applicable to different environment, the feature of cationic surface active agent is presented in an acidic solution, in alkalescence
The feature of anionic surfactant is presented in solution.
Embodiment
The present invention is further illustrated in conjunction with the embodiments, it should explanation, and the description below is merely to explain this
Invention, is not defined to its content.
Used raw material, reagent are conventional chemical product in the embodiment of the present invention, can be commercially available by market.
Embodiment 1
(1) preparation of dication dual anion type asphalt emulsifier：
1) 269.5g octadecylamines, 260g isopropanols, heating stirring dissolving are added in the reactor.Then 73.5g third is added dropwise
Olefin(e) acid, 70 DEG C of stirring reaction 2h.
2) trimethylamine aqueous solutions of 193.1g 33% are added in the reactor, are gradually added into the technical hydrochloric acids of 131.2g 30%,
97.1g epoxychloropropane is gradually added into again, and 30-70 DEG C of stirring reaction 2h obtains reaction intermediate A.In the middle of the reaction of preparation
Body A is added drop-wise to above-mentioned steps 1) in synthetic product, 70 DEG C of stirring reaction 2h.
3) 41.2g sodium hydroxides are dissolved in 80.0g water and obtain sodium hydrate aqueous solution, 97.3g monoxones are dissolved in
Chloroethene aqueous acid is obtained in 180.0g water；Sodium hydrate aqueous solution is added drop-wise in chloroethene aqueous acid and obtains sodium chloroacetate water
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 double sun
Ion dual anion type asphalt emulsifier, gives over to emulsified asphalt experiment.
Synthetic product carries out FTIR detections after recrystallizing separating-purifying, as a result as follows：3349cm-1Flexible for O-H shakes
Dynamic absworption peak, 2920cm-1And 2849cm-1The respectively asymmetric stretching vibration of methylene and symmetrical stretching vibration absworption peak,
1648cm-1For C=O stretching vibration absworption peaks, 1534cm in carboxylic acid-1For C=O stretching vibration absworption peaks, 1472cm in carboxylate-1For methylene scissoring vibration absworption peak, 1382cm-1For methyl symmetric curvature vibration absorption peak, 1237cm-1For C-N stretching vibrations
Absworption peak, 1064cm-1For C-OH stretching vibration absworption peaks, 926cm-1For the wagging vibration absworption peak of O-H in carboxylic acid,
717cm-1For methylene rocking vibration absworption peak.
Reaction equation is as follows：
(2) preparation of emulsified asphalt：
AH-90# pitch 300g are taken, 125 DEG C are heated to, 12.5g asphalt emulsifiers manufactured in the present embodiment are added to
In 200g water, pH value is adjusted to 2-3 with technical hydrochloric acid, 65 DEG C are heated to, soap lye is made.Pitch and emulsifying agent soap lye are passed through into glue
Cationic emulsified asphalt is prepared in body mill emulsification.
(3) emulsified asphalt performance detection：
The cationic emulsified bitumen standard (JTJ052-2000) that obtained emulsified asphalt is worked out by Chinese transportation portion is examined
Survey, it is as a result as follows：Emulsified asphalt manufactured in the present embodiment is uniform, fine and smooth, and bitumen content is 60%, and surplus is on sieve
0.01%, area is wrapped more than 2/3 with mineral aggregate, and storage stability (5d) is 3.6%；In de-emulsification speed experiment, using B classes
Material, can be 11 seconds the mixing time.Mixed and stirred using material is mixed and stirred, can be 3 seconds the mixing time.Show pitch prepared by the emulsifying agent
Emulsion is splits type cationic emulsified bitumen soon, and properties can meet the requirement of JTJ052-2000 standards.
Embodiment 2
(1) preparation of dication dual anion type asphalt emulsifier：
1) 269.5g octadecylamines, 260g isopropanols, heating stirring dissolving are added in the reactor.Then 73.5g third is added dropwise
Olefin(e) acid, 65 DEG C of stirring reaction 3h.
2) 109.1g triethylamines are added in the reactor, are gradually added into the technical hydrochloric acids of 131.2g 30%, then be gradually added into
97.1g epoxychloropropane, 30-70 DEG C of stirring reaction 2h, obtains reaction intermediate B.The reaction intermediate B of preparation is added drop-wise to
State step 1) in synthetic product, 65 DEG C of stirring reaction 3h.
3) 41.2g sodium hydroxides are dissolved in 80.0g water and obtain sodium hydrate aqueous solution, 97.3g monoxones are dissolved in
Chloroethene aqueous acid is obtained in 180.0g water；Sodium hydrate aqueous solution is added drop-wise in chloroethene aqueous acid and obtains sodium chloroacetate water
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 double sun
Ion dual anion type asphalt emulsifier, gives over to emulsified asphalt experiment.
Synthetic product carries out FTIR detections after recrystallizing separating-purifying, as a result as follows：3346cm-1Flexible for O-H shakes
Dynamic absworption peak, 2920cm-1And 2846cm-1The respectively asymmetric stretching vibration of methylene and symmetrical stretching vibration absworption peak,
1653cm-1For C=O stretching vibration absworption peaks, 1532cm in carboxylic acid-1For C=O stretching vibration absworption peaks, 1475cm in carboxylate-1For methylene scissoring vibration absworption peak, 1385cm-1For methyl symmetric curvature vibration absorption peak, 1239cm-1For C-N stretching vibrations
Absworption peak, 1063cm-1For C-OH stretching vibration absworption peaks, 927cm-1For the wagging vibration absworption peak of O-H in carboxylic acid,
723cm-1For methylene rocking vibration absworption peak.
Reaction equation is as follows：
(2) preparation of emulsified asphalt：
AH-70# pitch 300g are taken, 125 DEG C are heated to, 12.5g asphalt emulsifiers manufactured in the present embodiment are added to
In 200g water, pH value is adjusted to 2-3 with technical hydrochloric acid, 65 DEG C are heated to, soap lye is made.Pitch and emulsifying agent soap lye are passed through into glue
Cationic emulsified asphalt is prepared in body mill emulsification.
(3) emulsified asphalt performance detection：
Detection method be the same as Example 1, testing result is：Emulsified asphalt is uniform, fine and smooth, and bitumen content is 58%, is remained on sieve
Surplus is 0.02%, and area is wrapped more than 2/3 with mineral aggregate, and storage stability (5d) is 4.4%；In de-emulsification speed experiment, adopt
Can it be 25 seconds the mixing time with B class material.Mixed and stirred using material is mixed and stirred, can be 3 seconds the mixing time.Show prepared by the emulsifying agent
Asphalt emulsion to split type cationic emulsified bitumen soon, properties can meet the requirement of JTJ052-2000 standards.
(4) preparation of emulsified asphalt：
AH-90# pitch 300g are taken, 125 DEG C are heated to, 12.5g asphalt emulsifiers manufactured in the present embodiment are added to
In 200g water, pH value is adjusted to 10-11 with sodium hydroxide, 65 DEG C are heated to, soap lye is made.Pitch and emulsifying agent soap lye are passed through
Anionic emulsified asphalt is prepared in colloid mill emulsification.
(5) emulsified asphalt performance detection：
Detection method be the same as Example 1, testing result is：Emulsified asphalt is uniform, fine and smooth, and bitumen content is 59%, is remained on sieve
Surplus is 0.03%, and area is wrapped more than 2/3 with mineral aggregate, and storage stability (5d) is 4.1%；In de-emulsification speed experiment, adopt
Can it be 16 seconds the mixing time with B class material.Mixed and stirred using material is mixed and stirred, can be 5 seconds the mixing time.Show prepared by the emulsifying agent
Asphalt emulsion to split type anionic emulsified bitumen soon.
Embodiment 3
(1) preparation of dication dual anion type asphalt emulsifier：
1) 269.5g octadecylamines, 260g isopropanols, heating stirring dissolving are added in the reactor.Then 73.5g third is added dropwise
Olefin(e) acid, 70 DEG C of stirring reaction 2h.
2) triethanolamines of 189.6g 85% are added in the reactor, are gradually added into the technical hydrochloric acids of 131.2g 30%, then by
97.1g epoxychloropropane is gradually added, 30-70 DEG C of stirring reaction 2h obtains reaction intermediate C.By the reaction intermediate C drops of preparation
It is added to above-mentioned steps 1) in synthetic product, 70 DEG C of stirring reaction 2h.
3) 41.2g sodium hydroxides are dissolved in 80.0g water and obtain sodium hydrate aqueous solution, 97.3g monoxones are dissolved in
Chloroethene aqueous acid is obtained in 180.0g water；Sodium hydrate aqueous solution is added drop-wise in chloroethene aqueous acid and obtains sodium chloroacetate water
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 double sun
Ion dual anion type asphalt emulsifier, gives over to emulsified asphalt experiment.
Synthetic product carries out FTIR detections after recrystallizing separating-purifying, as a result as follows：3393cm-1Flexible for O-H shakes
Dynamic absworption peak, 2921cm-1And 2846cm-1The respectively asymmetric stretching vibration of methylene and symmetrical stretching vibration absworption peak,
1736cm-1For C=O stretching vibration absworption peaks, 1596cm in carboxylic acid-1For C=O stretching vibration absworption peaks, 1462cm in carboxylate-1For methylene scissoring vibration absworption peak, 1396cm-1For methyl symmetric curvature vibration absorption peak, 1253cm-1And 1208cm-1For C-
N stretching vibration absworption peaks, 1073cm-1For C-OH stretching vibration absworption peaks, 912cm-1For the wagging vibration of O-H in carboxylic acid
Absworption peak, 720cm-1For methylene rocking vibration absworption peak.
Reaction equation is as follows：
(2) preparation of emulsified asphalt：
A-100# pitch 300g are taken, 125 DEG C are heated to, 12.5g asphalt emulsifiers manufactured in the present embodiment are added to
In 200g water, pH value is adjusted to 2-3 with technical hydrochloric acid, 65 DEG C are heated to, soap lye is made.Pitch and emulsifying agent soap lye are passed through into glue
Cationic emulsified asphalt is prepared in body mill emulsification.
(3) emulsified asphalt performance detection：
Detection method be the same as Example 1, testing result is：Emulsified asphalt is uniform, fine and smooth, and bitumen content is 60%, is remained on sieve
Surplus is 0.02%, and area is wrapped more than 2/3 with mineral aggregate, and storage stability (5d) is 4.8%；In de-emulsification speed experiment, adopt
Can it be 4 seconds the mixing time with B class material.Mixed and stirred using material is mixed and stirred, can be 2 seconds the mixing time.Show prepared by the emulsifying agent
Asphalt emulsion is splits type cationic emulsified bitumen soon, and properties can meet the requirement of JTJ052-2000 standards.
Above-described embodiment is preferably embodiment, but embodiments of the present invention are not by above-described embodiment of the invention
Limitation, one of ordinary skill in the art should be understood that on the basis of technical scheme those skilled in the art need not
Pay various modifications or deform still within protection scope of the present invention that creative work can make.
Claims (10)
1. a kind of dication dual anion type asphalt emulsifier, it is characterised in that the dication dual anion type pitch
The molecular structure of emulsifying agent is：
Wherein, R=methyl (- CH3), ethyl (- C2H5), ethanol base (- C2H4OH)。
2. dication dual anion type asphalt emulsifier according to claim 1, it is characterised in that by following mol ratio
Raw material be prepared from：
Octadecylamine：Alcohols solvent：Acrylic acid：Low carbon number tertiary amine：Technical hydrochloric acid：Epoxychloropropane：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；
The alcohols solvent is ethanol, methanol or isopropanol；
The low carbon number tertiary amine is trimethylamine aqueous solution, triethylamine or triethanolamine.
3. the preparation method of the dication dual anion type asphalt emulsifier described in claim 1, comprises the following steps：
(1) prepare or obtain octadecyl amido propionic acid；
(2) intermediate is prepared：Low carbon number tertiary amine, adds concentrated hydrochloric acid, then is gradually added into epoxychloropropane, and reaction obtains glycidyl
Tri alkyl ammomium chloride hydrochloride intermediate, shown in formula I, 60-80 in octadecyl amido propionic acid is added by intermediate described in Formulas I
DEG C reaction, be made Formula II shown in intermediate；
(3) sodium chloroacetate solution is added in the reaction solution obtained to step (2), it is double that 60-80 DEG C of stirring reaction obtains dication
Anionic asphalt emulsifier；
Described low carbon number tertiary amine is trimethylamine aqueous solution, triethylamine or triethanolamine.
4. the preparation method of dication dual anion type asphalt emulsifier described in claim 3, it is characterised in that including following
Step：
(1) octadecylamine is added in reaction vessel, adds alcohols solvent, heating stirring dissolving adds acrylic acid, in 60-
80 DEG C of stirring reaction 2-4h；
(2) low carbon number tertiary amine is added in another reactor, technical hydrochloric acid is gradually added into, then be gradually added into epoxychloropropane, 30-
70 DEG C of stirring reaction 2h, obtain reaction intermediate, and 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) it is the 25-35% sodium chloroacetate aqueous solution that mass concentration is added into the reaction solution of step (2), anti-in 60-80 DEG C of stirring
2-7h is answered, dication dual anion type asphalt emulsifier is obtained.
5. the preparation method of dication dual anion type asphalt emulsifier according to claim 4, it is characterised in that step
(1), in (2) and (3), octadecylamine, alcohols solvent, acrylic acid, low carbon number tertiary amine, technical hydrochloric acid, epoxychloropropane, sodium chloroacetate
Mol ratio be 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 characterised in that step
(1) in, described alcohols solvent is ethanol, methanol or isopropanol.
7. the preparation method of dication dual anion type asphalt emulsifier according to claim 5, it is characterised in that step
(2) in, described low carbon number tertiary amine is trimethylamine aqueous solution, triethylamine or triethanolamine.
8. the preparation method of dication dual anion type asphalt emulsifier according to claim 5, it is characterised in that step
(3) in, sodium chloroacetate is reacted by monoxone and sodium hydroxide to be made.
9. application of the dication dual anion type asphalt emulsifier in emulsified asphalt is prepared described in claim 1.
10. apply according to claim 9, it is characterised in that the application process is：Dication dual anion type is dripped
Blue or green emulsifying agent is configured to 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, is made
Soap lye, cationic emulsified asphalt is prepared by pitch and emulsifying agent soap lye by colloid mill emulsification；Or, dication is double
Anionic asphalt emulsifier is configured to the aqueous solution that mass concentration is 1.0-3.0%, and pH value is adjusted to 10- with sodium hydroxide
11,65 DEG C are heated to, soap lye is made, pitch and emulsifying agent soap lye are prepared into anionic emulsification drip by colloid mill emulsification
It is blue or green.
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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 |
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