CN107056639B - A kind of dication single anion teritary amide type asphalt emulsifier and preparation method thereof - Google Patents
A kind of dication single anion teritary amide type asphalt emulsifier and preparation method thereof Download PDFInfo
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- CN107056639B CN107056639B CN201710051103.4A CN201710051103A CN107056639B CN 107056639 B CN107056639 B CN 107056639B CN 201710051103 A CN201710051103 A CN 201710051103A CN 107056639 B CN107056639 B CN 107056639B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
- C07C237/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton
- C07C237/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
- C07C237/06—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
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- C07D301/00—Preparation of oxiranes
- C07D301/27—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms
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- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
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- 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
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
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Abstract
The present invention discloses a kind of dication single anion teritary amide type asphalt emulsifier and preparation method thereof, the asphalt emulsifier is prepared by the raw material of following mol ratio: octadecylamine, alcohols solvent, N,N-DMAA, low carbon number tertiary amine, technical hydrochloric acid, epoxychloropropane, sodium chloroacetate molar ratio be 1mol:(4.00-9.00) mol:(1.00-1.08) mol:(1.02-1.10) mol:(1.02-1.10) mol:(1.02-1.08) mol:(1.02-1.10) mol.The present invention is in the molecular structure of the asphalt emulsifier of preparation by the way that N is added, N- dimethylacrylamide introduces amide group, dication single anion teritary amide type asphalt emulsifier is formd, the hydrophily of asphalt emulsifier and the compatibility of emulsifier and pitch are increased.
Description
Technical field
The present invention relates to a kind of dication single anion teritary amide type asphalt emulsifier and preparation method thereof, belong to fine
Chemical technology field.
Background technique
The amphipathic molecule that emulsifier is made of nonpolar hydrophobic group and polar hydrophilic group, this structure make to emulsify
Agent forms orientation close-packed arrays in solution table (boundary) face, changes table (boundary) face chemical property of system.When the concentration of emulsifier
More than its critical micelle concentration CMC, table (boundary) face tension is minimized, to have the function of emulsification, defoaming, dispersion etc., is being built
The fields such as material chemical industry, oil exploitation, daily necessities, textile printing and dyeing are widely used.
According to the difference of emulsifier hydrophilic group property, emulsifier is divided into anionic, cationic, amphoteric ion type, non-
Ion emulsifying and complex ionic etc..Wherein, both sexes asphalt emulsifier carries negative ions charge simultaneously, its surface is living
Property ion hydrophilic group not only there is anion part, but also there is cationic portion；Its structure had both been different from anionic pitch
Emulsifier, and it is different from cationic asphalt emulsifier, therefore, there are many excellent performances, such as: (1) good emulsibility
And dispersibility；(2) hypotoxicity；(3) resistance to hard water, calcium dispersibility are stronger, have good match with the emulsifier of other kinds type
Wu Xing.
But the exploitation in relation to both sexes asphalt emulsifier is later, and kind and quantity are all few；Both sexes pitch reported at present
Emulsifier mainly has betaine type, amino acid pattern, imidazoline type etc..United States Patent (USP) USP3342840 introduction has synthesized a kind of hydrophilic
Base be amino and the simultaneous amphoteric emulsifier of hydroxyl, due to zwitterionic electriferous state can with the variation of environment and
Variation, therefore application range is wider；But the preparation cost of the emulsifier is higher.Chinese patent CN101712625A is related to a kind of both sexes
Slowly quick-setting asphalt emulsifier synthetic method is split, is reacted using oleic acid with polyamines and generate polyamide-polyamino, monoxone is then added
Asphalt emulsifier is made in halogenating reaction.The disadvantages of the method are as follows needing pyroreaction when preparation.
Present inventor proposes dication dual anion type asphalt emulsifier in early-stage study, it is a kind of non-
Acid amide type both sexes asphalt emulsifier, the emulsifier is using acrylic acid as raw material, in alcohols solvent, reacts to obtain 18 with octadecylamine
Alkyl amine group propionic acid；Low carbon number tertiary amine is added concentrated hydrochloric acid, then is gradually added into epoxychloropropane, and reaction obtains three alkane of glycidyl
Octadecyl amido propionic acid is added in glycidyl tri alkyl ammomium chloride hydrochloride intermediate by ammonium chloride hydrochloride intermediate I
In obtain intermediate II；Sodium chloroacetate solution is added in the reaction solution of intermediate II, obtains dication dual anion type pitch
Emulsifier.The advantages of dication dual anion type asphalt emulsifier is: synthesis material is easy to get, production cost is low, does not need
Pyroreaction.But find after study, the performance of the dication dual anion type asphalt emulsifier need further to mention
It is high；In addition, irritation is larger using acrylic acid as raw material, it is unfavorable for the health of direct labor.
Therefore, for deficiency existing for both sexes asphalt emulsifier of present inventor's early-stage study and preparation method thereof,
It is necessary to develop new both sexes asphalt emulsifier, so that asphalt emulsification performance is more excellent, product yield is higher, enriches it
The type of both sexes asphalt emulsifier.
Summary of the invention
To overcome the shortcomings of to prepare asphalt emulsifier by raw material of acrylic acid in the prior art, the present invention provides a kind of double sun
Ion single anion teritary amide type asphalt emulsifier, molecular structural formula are as follows:
The dication single anion teritary amide type asphalt emulsifier is with N, and N- dimethylacrylamide is as pitch cream
The reaction raw materials of agent, N,N-DMAA are liquid charging stock, facilitate charging and the mixing of other raw materials and react；And
Reaction process is exothermic reaction, reduces energy consumption of reaction, and its toxicity and irritation are low.The production of asphalt emulsifier of the present invention
At low cost, simple process does not need pyroreaction.
There is anionic group and cation group, dication simultaneously in asphalt emulsifier molecular structure of the present invention
Single anion teritary amide type asphalt emulsifier is applicable to different environment, and cationic surfactant is presented in an acidic solution
The feature of anionic surfactant is presented in the feature of agent in alkaline solution.
Preferably, which prepared by the raw material of following mol ratio
It obtains:
Octadecylamine, alcohols solvent, N, N- dimethylacrylamide, low carbon number tertiary amine, technical hydrochloric acid, epoxychloropropane, chlorine
The molar ratio of sodium acetate is 1mol:(4.00-9.00) mol:(1.00-1.08) mol:(1.02-1.10) mol:(1.02-1.10)
Mol:(1.02-1.08) mol:(1.02-1.10) mol.
The alcohols solvent is ethyl alcohol, methanol or isopropanol.
The low carbon number tertiary amine trimethylamine aqueous solution, triethylamine or triethanolamine aqueous solution.
To overcome the shortcomings of to prepare asphalt emulsifier by raw material of acrylic acid in the prior art, the present invention is provided described in one kind
The preparation method of dication single anion teritary amide type asphalt emulsifier, comprising the following steps:
(1) by octadecylamine, alcohols solvent and N,N-DMAA hybrid reaction, reaction intermediate I is obtained, it is intermediate
Body I is C18H37NHCH2CH2CON(CH3)2；
(2) low carbon number tertiary amine, technical hydrochloric acid and epoxychloropropane are mixed, reaction obtains reaction intermediate II, low carbon number
Tertiary amine is that trimethylamine aqueous solution, triethylamine or triethanolamine aqueous solution, intermediate II are
R is methyl (- CH3), ethyl (- C2H5) or ethoxy (- C2H4OH)；
(3) the reaction intermediate II of preparation is added drop-wise in reaction intermediate I, hybrid reaction obtains reaction intermediate
III, intermediate III areR is methyl (- CH3), ethyl (- C2H5) or ethoxy (-
C2H4OH)；
(4) sodium chloroacetate aqueous solution is added drop-wise in reaction intermediate III, is reacted to get dication single anion is arrived
Teritary amide type asphalt emulsifier；
As long as above step does not influence to prepare, interchangeable.
Preferably, octadecylamine, alcohols solvent, N,N-DMAA, low carbon number tertiary amine, technical hydrochloric acid, epoxy chlorine
Propane, sodium chloroacetate molar ratio be 1mol:(4.00-9.00) mol:(1.00-1.08) mol:(1.02-1.10) mol:
(1.02-1.10) mol:(1.02-1.08) mol:(1.02-1.10) mol.
By lot of experiment validation and analysis, the present invention is prepared in each raw material of above-mentioned molar ratio double sun from
The performance of sub- single anion teritary amide type asphalt emulsifier is more satisfactory, the raw material of inappropriate proportion relation cannot be formed double sun from
Sub- single anion teritary amide type asphalt emulsifier.Especially for the additional amount of N,N-DMAA, the mistake being added
The performance of the more or very few asphalt emulsifier that can all influence preparation, the especially water-separating time of asphalt emulsifier.
In step (1), the temperature of reaction is 60-80 DEG C, and preferably 65-75 DEG C, the time of reaction is 2-4h.
Present inventor has found that the reaction process of N,N-DMAA is exothermic reaction, itself can provide anti-
Required heat is answered, the introducing of external source heat in reaction process is reduced, reduces the energy consumption of reaction.
Preferably, the alcohols solvent is ethyl alcohol, methanol or isopropanol, by lot of experiment validation and analysis, and according to
The needs of dication single anion teritary amide type asphalt emulsifier produced by the present invention select the drip obtained of above-mentioned alcohols solvent
The effect of green emulsifier is preferable.
In step (2), the temperature of reaction is 47-55 DEG C, and the time of reaction is 2-3h.By further investigation revealed that,
The reaction temperature condition of the step is very crucial for the preparation of reaction intermediate II, and the temperature of reaction is excessively high, then will lead to anti-
It answers the epoxy bond of intermediate II to open, react it can not with reaction intermediate I further and generate dication single anion uncle
Acid amide type asphalt emulsifier, to reduce the yield of target product；If the temperature of reaction is too low, reaction solution point can be made
Layer, and then affect reaction process.For the yield for improving final products, this temperature condition is optimized in the present invention, instead
Answer temperature be 47-55 DEG C when, the preparation effect of reaction intermediate II is optimal.
Preferably, the concentration of the technical hydrochloric acid is 30% (mass fraction), and the concentration of trimethylamine aqueous solution is 33% (matter
Measure score).
In step (3), the temperature of reaction is 60-80 DEG C, and preferably 65-75 DEG C, the time of reaction is 2-4h.
In step (4), the temperature of reaction is 60-80 DEG C, and preferably 65-75 DEG C, the time of reaction is 2-7h.
Preferably, the sodium chloroacetate aqueous solution is reacted by monoxone and sodium hydroxide and is made, concentration 28-38%
(mass fraction).
The preparation method of above-mentioned dication single anion teritary amide type asphalt emulsifier, specifically comprises the following steps:
(1) octadecylamine is added in reaction vessel, alcohols solvent, heating stirring dissolution is added, then N is added portionwise, N-
Dimethylacrylamide after addition, is stirred to react 2-4h at 60-80 DEG C, obtains reaction intermediate I；
(2) low carbon number tertiary amine is added in the second reactor, technical hydrochloric acid is added portionwise, after technical hydrochloric acid is added,
Epoxychloropropane is added portionwise again and is stirred to react 2-3h at 47-55 DEG C after epoxychloropropane is added, it is intermediate to obtain reaction
Body II, wherein low carbon number tertiary amine is trimethylamine aqueous solution, triethylamine or triethanolamine aqueous solution；
(3) reaction intermediate II is added portionwise in reaction intermediate I, 60-80 DEG C of reaction 2-4h, it is intermediate obtains reaction
Body III；
(4) 28-38% (mass fraction) sodium chloroacetate aqueous solution is added in reaction intermediate III, it is anti-at 60-80 DEG C
2-7h is answered to get dication single anion teritary amide type asphalt emulsifier is arrived；
As long as above step does not influence to prepare, interchangeable.
The present invention also provides a kind of above-mentioned dication single anion teritary amide type asphalt emulsifiers to split type sun in preparation fastly
Ion emulsified asphalt splits application in type anionic emulsified bitumen fastly.
Preferably above-mentioned dication single anion teritary amide type asphalt emulsifier splits the cation emulsified drip of type in preparation fastly
Application in blueness.
For above-mentioned dication single anion teritary amide type asphalt emulsifier, the present invention also provides a kind of cation emulsified
The preparation method of pitch, steps are as follows:
Water is added to be configured to aqueous solution above-mentioned dication single anion teritary amide type asphalt emulsifier, with technical hydrochloric acid tune
PH to 2-3 is saved, is heated to 60-70 DEG C, soap lye is made；By after heating pitch and emulsifier soap lye pass through colloid mill emulsification preparation
Cationic emulsified bitumen out；
The dosage of the dication single anion teritary amide type asphalt emulsifier is the emulsified asphalt gross mass of preparation
0.8-2.5%.
The cationic emulsified bitumen that above-mentioned preparation method is prepared, the type of the cationic emulsified bitumen are to split type cream fastly
Change pitch.
For above-mentioned dication single anion teritary amide type asphalt emulsifier, the present invention also provides a kind of anionic emulsifying
The preparation method of pitch, steps are as follows:
Water is added to be configured to aqueous solution above-mentioned dication single anion teritary amide type asphalt emulsifier, with sodium hydroxide tune
PH to 10-11 is saved, is heated to 60-70 DEG C, soap lye is made；By after heating pitch and emulsifier soap lye pass through colloid mill emulsification system
Standby anionic emulsified bitumen out；
The dosage of the dication single anion teritary amide type asphalt emulsifier is the emulsified asphalt gross mass of preparation
0.8-2.5%.
The anionic emulsified bitumen that above-mentioned preparation method is prepared, the type of the anionic emulsified bitumen are to split type cream fastly
Change pitch.
Compared with prior art, the beneficial effects of the present invention are:
(1) present invention reasonably selects reaction raw materials, shape using filtering out excellent asphalt emulsifier as starting point
At a kind of dication single anion teritary amide type asphalt emulsifier with specific structure.
For the present invention for the first time with N, N- dimethylacrylamide is newborn as dication single anion teritary amide type pitch is prepared
The reaction raw materials of agent, compared to acrylic acid, by the way that N, N- dimethyl is added in the molecular structure of the asphalt emulsifier of preparation
Acrylamide introduces amide group, forms dication single anion teritary amide type asphalt emulsifier, increases pitch cream
The hydrophily and emulsifier of agent and the compatibility of pitch.
It include hydrophilic group and lipophilic group, the lipophilic group in emulsification in asphalt emulsification agent molecule in asphalt emulsifier
Start into after in water close to pitch particle, then enters back into pitch particle, so that the surface of each pitch particle
Countless emulsifier molecules are all had accumulated, pitch particle to including, form a stratum boundary facial mask.In addition, due to pitch cream
After agent molecule ionizes in water, so that interfacial film has corresponding charge, interface charge layer is thus formed.Interfacial film
It is formed such that water and pitch separate, reduces the interfacial tension between water and pitch, a kind of mechanical protection is played to pitch particle
Effect, allows asphalt emulsion to keep stability and uniformity within a certain period of time；Interface charge layer can make pitch particle
It is mutually exclusive between particle, it maintains a certain distance, so that pitch particle aggregation is gone less than one piece, plays and mutually divide
Scattered effect.
For N,N-DMAA compared with acrylic acid, the two is not belonging to homologue, and it includes amide groups and amide groups
Two methyl on upper nitrogen；The presence of two of them methyl increases the lipophilic group in the asphalt emulsifier molecular structure of preparation
Group is more conducive to form interfacial film, reduces the interfacial tension between water and pitch；The presence of amide groups, so that the pitch being prepared
The ionizing power of emulsifier in water is stronger, can ionize out more cations, keep the effect of interface charge layer stronger；The two
Synergistic effect, so that pitch can emulsify in water and uniformly can disperse to form metastable asphalt emulsion.
In addition, the hydrophilic group contained in asphalt emulsifier structural formula of the invention is more, carboxylate, quaternary ammonium salt and amide
Base improves emulsion intercalation method so that interfacial film, hydration layer and interface charge layer all enhance accordingly.
(2) compared to acrylic acid is used early period, for reaction raw materials, the present invention is using N,N-DMAA as raw material system
The standby dication single anion teritary amide type asphalt emulsifier arrived, with those skilled in the art's technology effect beyond expectation
Fruit, the unexpected technical effect are embodied in: having more excellent emulsifiability；Be embodied in emulsifiability divides water
On time, dication single anion teritary amide type asphalt emulsifier water-separating time of the invention is 120s, and the present application
People's early-stage study is only 4s by the water-separating time of the dication dianion asphalt emulsifier of raw material of acrylic acid, the two
Significant difference.
(3) it has been investigated that, the reaction process of N,N-DMAA is exothermic reaction, itself can provide reaction
Required heat reduces the introducing of external source heat in reaction process, reduces the energy consumption of reaction.
(4) present invention use specific raw material N, N- dimethylacrylamide, octadecylamine, low carbon number tertiary amine, technical hydrochloric acid,
Epoxychloropropane, monoxone and sodium hydroxide generate the dication single anion teritary amide type chemistry knot with certain HLB value
The asphalt emulsifier of structure has cream well using dication single anion teritary amide type asphalt emulsifier prepared by the present invention
Change performance, the performance indexes for the emulsified asphalt being prepared is excellent, the pitch of emulsifiable a variety of different models, the cream of preparation
It is fine and smooth uniformly to change pitch, it is good gather materials wrap up in attached property.Emulsified asphalt obtained presses the cation emulsified drip that Chinese transportation portion works out
Green professional standard (JTJ052-2000) is detected, and properties are able to satisfy standard requirements.Suitable for highway priming oil or glue
The spread of layer oil, and for crushed stone sealing, screening seal coat, mist sealing and reparation slight check crack in road surface etc., have and split pitch fastly
The characteristic of emulsifier.
(5) the raw material octadecylamine of dication single anion teritary amide type asphalt emulsifier of the invention is relative to current
Raw material used in cationic asphalt emulsifier is cheap, from a wealth of sources, and asphalt emulsifier production cost is low, and is the double sun of preparation
Ion single anion teritary amide type asphalt emulsifier provides good basis.
(6) amide groups amine emulsifier reaction temperature general control is and of the invention at 140~180 DEG C in the prior art
The preparation method simple process of dication single anion teritary amide type asphalt emulsifier does not need pyroreaction, reduces energy consumption,
Greatly save production cost.
Specific embodiment
It is noted that described further below be all exemplary, it is intended to provide further instruction to the present invention.Unless another
It indicates, all technical and scientific terms used herein has usual with general technical staff of the technical field of the invention
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root
According to exemplary embodiments of the present invention.As used herein, unless the context clearly indicates otherwise, otherwise singular
Also it is intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet
Include " when, indicate existing characteristics, step, operation, component and/or their combination.
To overcome the shortcomings of to prepare asphalt emulsifier by raw material of acrylic acid in the prior art, the present invention provides a kind of double sun
Ion single anion teritary amide type asphalt emulsifier, molecular structural formula are as follows:
In one embodiment, the present invention provides a kind of dication single anion teritary amide type asphalt emulsifiers
Preparation method, comprising the following steps:
(1) by octadecylamine, alcohols solvent and N,N-DMAA hybrid reaction, reaction intermediate I is obtained, it is intermediate
Body I is C18H37NHCH2CH2CON(CH3)2；
(2) low carbon number tertiary amine, technical hydrochloric acid and epoxychloropropane are mixed, reaction obtains reaction intermediate II, low carbon number
Tertiary amine is that trimethylamine aqueous solution, triethylamine or triethanolamine aqueous solution, intermediate II areR is methyl (- CH3), ethyl (- C2H5) or ethoxy (- C2H4OH)；
(3) the reaction intermediate II of preparation is added drop-wise in reaction intermediate I, hybrid reaction obtains reaction intermediate
III, intermediate III are
R is methyl (- CH3), ethyl (- C2H5) or ethoxy (- C2H4OH)；
(4) sodium chloroacetate aqueous solution is added drop-wise in reaction intermediate III, is reacted to get dication single anion is arrived
Teritary amide type asphalt emulsifier；As long as above step does not influence to prepare, interchangeable.
Preferably, octadecylamine, alcohols solvent, N,N-DMAA, low carbon number tertiary amine, technical hydrochloric acid, epoxy chlorine
Propane, sodium chloroacetate molar ratio be 1mol:(4.00-9.00) mol:(1.00-1.08) mol:(1.02-1.10) mol:
(1.02-1.10) mol:(1.02-1.08) mol:(1.02-1.10) mol.
By lot of experiment validation and analysis, the present invention is prepared in each raw material of above-mentioned molar ratio double sun from
The performance of sub- single anion teritary amide type asphalt emulsifier is more satisfactory, the raw material of inappropriate proportion relation cannot be formed double sun from
Sub- single anion teritary amide type asphalt emulsifier.
In another embodiment of the present invention, in step (1), the temperature of reaction is 60-80 DEG C, preferably 65-75 DEG C,
The time of reaction is 2-4h.The alcohols solvent is ethyl alcohol, methanol or isopropanol.
In another embodiment of the present invention, in step (2), the temperature of reaction is 47-55 DEG C, and the time of reaction is 2-
3h.By further investigation revealed that, the reaction temperature condition of the step is very crucial for the preparation of reaction intermediate II, instead
The temperature answered is excessively high, then the epoxy bond that will lead to reaction intermediate II is opened, and react it can not with reaction intermediate I further
Dication single anion teritary amide type asphalt emulsifier is generated, to reduce the yield of target product；If the temperature of reaction
It is too low, then reaction solution can be made to be layered, and then affect reaction process.For the yield for improving final products, the present invention is to this
Temperature condition is optimized, and when reaction temperature is 47-55 DEG C, the preparation effect of reaction intermediate II is optimal.
The concentration of the technical hydrochloric acid is 30% (mass fraction), and the concentration of trimethylamine aqueous solution is 33% (quality point
Number).
In another embodiment of the present invention, in step (3), the temperature of reaction is 60-80 DEG C, preferably 65-75 DEG C,
The time of reaction is 2-4h.
In another embodiment of the present invention, in step (4), the temperature of reaction is 60-80 DEG C, preferably 65-75 DEG C,
The time of reaction is 2-7h.The sodium chloroacetate aqueous solution is reacted by monoxone and sodium hydroxide to be made, concentration 28-38%
(mass fraction).
In another embodiment of the present invention, the present invention also provides a kind of preparation method of cationic emulsified bitumen, steps
It is rapid as follows:
Water is added to be configured to aqueous solution above-mentioned dication single anion teritary amide type asphalt emulsifier, with technical hydrochloric acid tune
PH to 2-3 is saved, is heated to 60-70 DEG C, soap lye is made；By after heating pitch and emulsifier soap lye pass through colloid mill emulsification preparation
Cationic emulsified bitumen out；
The dosage of the dication single anion teritary amide type asphalt emulsifier is the emulsified asphalt gross mass of preparation
0.8-2.5%.
The cationic emulsified bitumen that above-mentioned preparation method is prepared, the type of the cationic emulsified bitumen are to split type cream fastly
Change pitch.
In another embodiment of the present invention, the present invention also provides a kind of preparation method of anionic emulsified bitumen, steps
It is rapid as follows:
Water is added to be configured to aqueous solution above-mentioned dication single anion teritary amide type asphalt emulsifier, with sodium hydroxide tune
PH to 10-11 is saved, is heated to 60-70 DEG C, soap lye is made；By after heating pitch and emulsifier soap lye pass through colloid mill emulsification system
Standby anionic emulsified bitumen out；
The dosage of the dication single anion teritary amide type asphalt emulsifier is the emulsified asphalt gross mass of preparation
0.8-2.5%.
The anionic emulsified bitumen that above-mentioned preparation method is prepared, the type of the anionic emulsified bitumen are to split type cream fastly
Change pitch.
In order to enable those skilled in the art can clearly understand the technical solution of the application, below with reference to tool
The technical solution of the application is described in detail in the embodiment and comparative example of body.
Embodiment 1
(1) preparation of dication single anion teritary amide type asphalt emulsifier:
1) 269.5g octadecylamine, 260g isopropanol, heating stirring dissolution are added in the reactor.Then it is gradually added into
104.1g N,N-DMAA, 70 DEG C are stirred to react 3h.
2) 193.1g 33% (mass fraction) trimethylamine aqueous solution is added in another reactor, is gradually added into 131.2g
30% (mass fraction) technical hydrochloric acid, then it is gradually added into 97.1g epoxychloropropane, 50 DEG C are stirred to react 2.5h, obtain in reaction
Mesosome A.
3) the reaction intermediate A of preparation is added drop-wise to above-mentioned steps 1) in synthetic product, 70 DEG C are stirred to react 2h.
4) 42.4g sodium hydroxide is dissolved in 80.0g water and obtains sodium hydrate aqueous solution, 100.2g monoxone is dissolved in
Chloroethene aqueous acid is obtained in 200.0g 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 3) in synthetic product, 65 DEG C are stirred to react 5h.Obtain double sun
Ion single anion teritary amide type asphalt emulsifier gives over to emulsified asphalt test.
Synthetic product carries out FTIR detection after recrystallizing separating-purifying, as a result as follows: 3404cm-1For O-H stretching vibration
Absorption peak, 2920cm-1For the asymmetric stretching vibration absworption peak of methylene, 2852cm-1It is received for the symmetrical stretching vibration of methylene
Peak, 1629cm-1For C=O stretching vibration absworption peak in C=O stretching vibration absworption peak in amide groups and carboxylate (- COONa),
1471cm-1It is vibrated for the asymmetric curvature of methylene, 1417cm-1It is vibrated for the asymmetric curvature of methyl, 1262cm-1With
1152cm-1For C-N stretching vibration absworption peak, 1053cm-1For C-OH stretching vibration absworption peak, 723cm-1To be shaken in methylene basal plane
Pendular oscillation absorption peak.
Reaction equation is as follows:
C18H37NH2+CH2=CHCON (CH3)2→C18H37NHCH2CH2CON(CH3)2 (1)
(2) preparation of emulsified asphalt:
AH-90# pitch 300g is taken, is heated to 125 DEG C, 12.5g asphalt emulsifier manufactured in the present embodiment is added to
In 200g water, pH value is adjusted to 2-3 with technical hydrochloric acid, 65 DEG C is heated to, soap lye is made.Pitch and emulsifier soap lye are passed through into glue
Cationic emulsified asphalt is prepared in body mill emulsification.
(3) emulsified asphalt performance detection:
Emulsified asphalt obtained by Chinese transportation portion work out cationic emulsified bitumen professional standard (JTJ052-2000) into
Row detection, as a result as follows: emulsified asphalt manufactured in the present embodiment is uniform, fine and smooth, bitumen content 56%, and surplus is on sieve
0.03%, area is wrapped greater than 2/3 with mineral aggregate, and storage stability (1d) is 0.8%；It is mixed and stirred, can be mixed and stirred using material is mixed and stirred
Time is 3 seconds.The asphalt emulsion for showing emulsifier preparation is to split type cationic emulsified bitumen fastly, and properties are able to satisfy mark
Alignment request.
Embodiment 2
(1) preparation of dication single anion teritary amide type asphalt emulsifier:
1) 269.5g octadecylamine, 260g isopropanol, heating stirring dissolution are added in the reactor.Then it is gradually added into
104.1gN, N- dimethylacrylamide, 70 DEG C are stirred to react 3h.
2) 109.1g triethylamine is added in another reactor, is gradually added into 131.2g30% (mass fraction) Nacl
Acid, then it is gradually added into 97.1g epoxychloropropane, 50 DEG C are stirred to react 2.5h, obtain reaction intermediate B.
3) the reaction intermediate B of preparation is added drop-wise to above-mentioned steps 1) in synthetic product, 65 DEG C are stirred to react 3h.
4) 42.4g sodium hydroxide is dissolved in 80.0g water and obtains sodium hydrate aqueous solution, 100.2g monoxone is dissolved in
Chloroethene aqueous acid is obtained in 200.0g 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 3) in synthetic product, 75 DEG C are stirred to react 3h.Obtain double sun
Ion single anion teritary amide type asphalt emulsifier gives over to emulsified asphalt test.
Synthetic product carries out FTIR detection after recrystallizing separating-purifying, as a result as follows: 3411cm-1For O-H stretching vibration
Absorption peak, 2920cm-1For the asymmetric stretching vibration absworption peak of methylene, 2850cm-1It is received for the symmetrical stretching vibration of methylene
Peak, 1633cm-1For C=O stretching vibration absworption peak in C=O stretching vibration absworption peak in amide groups and carboxylate (- COONa),
1461cm-1It is vibrated for the asymmetric curvature of methylene, 1404cm-1It is vibrated for the asymmetric curvature of methyl, 1262cm-1With
1162cm-1For C-N stretching vibration absworption peak, 1087cm-1For C-OH stretching vibration absworption peak, 723cm-1To be shaken in methylene basal plane
Pendular oscillation absorption peak.
Reaction equation is as follows:
C18H37NH2+CH2=CHCON (CH3)2→C18H37NHCH2CH2CON(CH3)2 (1)
(2) preparation of emulsified asphalt:
AH-70# pitch 300g is taken, is heated to 125 DEG C, 12.5g asphalt emulsifier manufactured in the present embodiment is added to
In 200g water, pH value is adjusted to 2-3 with technical hydrochloric acid, 65 DEG C is heated to, soap lye is made.Pitch and emulsifier soap lye are passed through into glue
Cationic emulsified asphalt is prepared in body mill emulsification.
(3) emulsified asphalt performance detection:
Detection method is the same as embodiment 1, testing result are as follows: emulsified asphalt is uniform, fine and smooth, bitumen content 58%, remains on sieve
Surplus is 0.03%, wraps area greater than 2/3 with mineral aggregate, storage stability (1d) is 0.9%；It is mixed and stirred using material is mixed and stirred,
It can be 3 seconds the mixing time.The asphalt emulsion for showing emulsifier preparation is to split type cationic emulsified bitumen, the equal energy of properties fastly
Meet standard requirements.
Embodiment 3
(1) preparation of dication single anion teritary amide type asphalt emulsifier:
1) 269.5g octadecylamine, 260g isopropanol, heating stirring dissolution are added in the reactor.Then it is gradually added into
104.1gN, N- dimethylacrylamide, 65 DEG C are stirred to react 4h.
2) 189.6g85% (mass fraction) triethanolamine is added in another reactor, is gradually added into 131.2g30%
(mass fraction) technical hydrochloric acid, then it is gradually added into 97.1g epoxychloropropane, 50 DEG C are stirred to react 2.5h, obtain reaction intermediate
C。
3) the reaction intermediate C of preparation is added drop-wise to above-mentioned steps 1) in synthetic product, 70 DEG C are stirred to react 2h.
4) 42.4g sodium hydroxide is dissolved in 80.0g water and obtains sodium hydrate aqueous solution, 100.2g monoxone is dissolved in
Chloroethene aqueous acid is obtained in 200.0g 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 3) in synthetic product, 60 DEG C are stirred to react 7h.Obtain double sun
Ion single anion teritary amide type asphalt emulsifier gives over to emulsified asphalt test.
Synthetic product carries out FTIR detection after recrystallizing separating-purifying, as a result as follows: 3394cm-1For O-H stretching vibration
Absorption peak, 2918cm-1For the asymmetric stretching vibration absworption peak of methylene, 2854cm-1It is received for the symmetrical stretching vibration of methylene
Peak, 1627cm-1For C=O stretching vibration absworption peak in C=O stretching vibration absworption peak in amide groups and carboxylate (- COONa),
1454cm-1It is vibrated for the asymmetric curvature of methylene, 1390cm-1It is vibrated for the asymmetric curvature of methyl, 1255cm-1With
1139cm-1For C-N stretching vibration absworption peak, 1056cm-1For C-OH stretching vibration absworption peak, 921cm-1For the vibration of O-H out-of-plane bending
Dynamic absorption peak, 682cm-1For methylene rocking vibration absorption peak.
Reaction equation is as follows:
C18H37NH2+CH2=CHCON (CH3)2→C18H37NHCH2CH2CON(CH3)2 (1)
(2) preparation of emulsified asphalt:
A-100# pitch 300g is taken, is heated to 125 DEG C, 12.5g asphalt emulsifier manufactured in the present embodiment is added to
In 200g water, pH value is adjusted to 2-3 with technical hydrochloric acid, 65 DEG C is heated to, soap lye is made.Pitch and emulsifier soap lye are passed through into glue
Cationic emulsified asphalt is prepared in body mill emulsification.
(3) emulsified asphalt performance detection:
Detection method is the same as embodiment 1, testing result are as follows: emulsified asphalt is uniform, fine and smooth, bitumen content 60%, remains on sieve
Surplus is 0.02%, wraps area greater than 2/3 with mineral aggregate, storage stability (1d) is 0.8%；It is mixed and stirred using material is mixed and stirred,
It can be 3 seconds the mixing time.The asphalt emulsion for showing emulsifier preparation is to split type cationic emulsified bitumen, the equal energy of properties fastly
Meet standard requirements.
Comparative example 1
Experimental raw: the dication dual anion type in embodiment 1 and comparative example CN 105384948A in embodiment 1
Asphalt emulsifier, structural formula are as follows:
The emulsifying capacity of both the above emulsifier is measured, signified emulsifying capacity refers in the present invention: pitch cream
Liquid agent Jiang Shui immiscible with oily two classes is changed into the ability of emulsion.
The present invention measures emulsifying capacity using graduated cylinder method, is thoroughly mixed to form cream according to asphalt emulsifier and atoleine
Thus shape liquid, then time required for 10ml water, that is, water-separating time are separated after standing evaluates the emulsification of asphalt emulsifier
Performance.
The specific method is as follows:
Measure the asphalt emulsifier of 0.1% (mass fraction) respectively with pipette (respectively by embodiment 1 and comparative example)
Aqueous solution 40ml is placed in the conical flask of the 100ml of glass stopper, then is placed in this with the atoleine that pipette measures 40ml
In conical flask.By tight glass stopper, then fierce vibration 5 times up and down, vibrate 5 times, then stand 1min again after standing 1min；So weight
After 5 times multiple, this lotion is poured into the tool plug graduated cylinder of 100ml, records the time with stopwatch at once.Water phase and an oil phase is gradually separated,
Water phase can appear in the lower layer of graduated cylinder slowly, and when water phase separates 10ml water, record separates the time used in water at this time, with this
Time, relatively as emulsifying capacity the more long then emulsifying capacity of water-separating time was stronger.
Repeat experiment three times, through detecting, the water-separating time average out to of asphalt emulsifier prepared by the embodiment of the present invention 1
120s；The water-separating time average out to 4s of the asphalt emulsifier of comparative example；With the embodiment of the present invention 1 it can be seen from water-separating time
The asphalt emulsifier that the emulsifying capacity of the asphalt emulsifier of preparation will be significantly better than with comparative example.
Comparative example 2
By the preparation step 2 of 1 asphalt emulsifier of embodiment) in reaction temperature be adjusted to 30 DEG C, remaining with embodiment 1,
Asphalt emulsifier is prepared.
As a result, it has been found that: comparative example 2 is during preparing asphalt emulsifier, the especially preparation process of reaction intermediate II
In, reaction system is layered, and reduces the yield of reaction rate and reaction intermediate II.
Comparative example 3
By the preparation step 2 of 1 asphalt emulsifier of embodiment) in reaction temperature be adjusted to 70 DEG C, remaining with embodiment 1,
Asphalt emulsifier is prepared.
As a result, it has been found that comparative example 3 is during preparing asphalt emulsifier, the especially preparation process of reaction intermediate II
In, through to reaction product --- reaction intermediate II is detected, and the epoxy bond of reaction intermediate II is much opened, epoxy bond
After being opened, prevent asphalt emulsifier is prepared from further reacting in reaction intermediate II and reaction intermediate I, reduce
The yield of final product asphalt emulsifier.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (11)
1. a kind of dication single anion teritary amide type asphalt emulsifier, characterized in that its molecular structural formula are as follows:
Wherein, R=methyl, ethyl, ethoxy.
2. the preparation method of dication single anion teritary amide type asphalt emulsifier described in claim 1, characterized in that packet
Include following steps:
(1) by octadecylamine, alcohols solvent and N,N-DMAA hybrid reaction, reaction intermediate I, intermediate compound I are obtained
For C18H37NHCH2CH2CON(CH3)2；
Wherein, the temperature of reaction is 60-80 DEG C, and the time of reaction is 2-4h；
(2) low carbon number tertiary amine, technical hydrochloric acid and epoxychloropropane are mixed, reaction obtains reaction intermediate II, low carbon number tertiary amine
It is for trimethylamine aqueous solution, triethylamine or triethanolamine aqueous solution, intermediate IIR is
Methyl, ethyl or ethoxy；The temperature of reaction is 47-55 DEG C, and the time of reaction is 2-3h；
(3) the reaction intermediate II of preparation being added drop-wise in reaction intermediate I, hybrid reaction obtains reaction intermediate III, in
Mesosome III is
R is methyl, ethyl or ethoxy；
Wherein, the temperature of reaction is 60-80 DEG C, and the time of reaction is 2-4h；
(4) sodium chloroacetate aqueous solution is added drop-wise in reaction intermediate III, is reacted to get the tertiary acyl of dication single anion is arrived
Amine type asphalt emulsifier, structure areThe temperature of reaction is 60-80 DEG C,
The time of reaction is 2-7h；
Above step does not influence to prepare, and can exchange sequence；Octadecylamine, alcohols solvent, N, N- dimethylacrylamide, low carbon number
Tertiary amine, technical hydrochloric acid, epoxychloropropane, sodium chloroacetate molar ratio be 1mol:(4.00-9.00) mol:(1.00-1.08)
Mol:(1.02-1.10) mol:(1.02-1.10) mol:(1.02-1.08) mol:(1.02-1.10) mol.
3. preparation method as claimed in claim 2, it is characterized in that: the reaction temperature is 65-75 DEG C in step (1).
4. preparation method as claimed in claim 2, it is characterized in that: in step (1), the alcohols solvent be ethyl alcohol, methanol or
Isopropanol.
5. preparation method as claimed in claim 2, it is characterized in that: in step (2), the mass fraction of the technical hydrochloric acid is
30%, the mass fraction of trimethylamine aqueous solution is 33%.
6. preparation method as claimed in claim 2, it is characterized in that: the reaction temperature is 65-75 DEG C in step (3).
7. preparation method as claimed in claim 2, it is characterized in that: the reaction temperature is 65-75 DEG C in step (4).
8. preparation method as claimed in claim 2, it is characterized in that: the sodium chloroacetate aqueous solution is by monoxone in step (4)
It is made with sodium hydroxide reaction, mass fraction 28-38%.
9. dication single anion teritary amide type asphalt emulsifier described in claim 1 is in preparation, to split type fastly cation emulsified
Pitch splits application in type anionic emulsified bitumen fastly.
10. a kind of preparation method of cationic emulsified bitumen, characterized in that include the following steps:
Water is added to be configured to aqueous solution, recruitment dication single anion teritary amide type asphalt emulsifier described in claim 1
Industry salt acid for adjusting pH is heated to 60-70 DEG C, soap lye is made to 2-3；By after heating pitch and emulsifier soap lye pass through colloid mill
Cationic emulsified bitumen is prepared in emulsification；
The dosage of the dication single anion teritary amide type asphalt emulsifier is the 0.8- of the emulsified asphalt gross mass of preparation
2.5%.
11. a kind of preparation method of anionic emulsified bitumen, characterized in that steps are as follows:
Add water to be configured to aqueous solution dication single anion teritary amide type asphalt emulsifier described in claim 1, uses hydrogen
Sodium oxide molybdena adjusts pH to 10-11, is heated to 60-70 DEG C, and soap lye is made；By after heating pitch and emulsifier soap lye pass through colloid
Anionic emulsified bitumen is prepared in mill emulsification；
The dosage of the dication single anion teritary amide type asphalt emulsifier is the 0.8- of the emulsified asphalt gross mass of preparation
2.5%.
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| CN105384948A (en) * | 2015-12-21 | 2016-03-09 | 山东大学 | Dication and dianion type asphalt emulsifier and preparation method thereof |
| CN105418942A (en) * | 2015-12-21 | 2016-03-23 | 山东大学 | Dicationic amide type asphalt emulsifier and preparation method therefor |
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| CN105384948A (en) * | 2015-12-21 | 2016-03-09 | 山东大学 | Dication and dianion type asphalt emulsifier and preparation method thereof |
| CN105418942A (en) * | 2015-12-21 | 2016-03-23 | 山东大学 | Dicationic amide type asphalt emulsifier and preparation method therefor |
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