CN106831478B - Asphalt emulsifier of type or slow breaking and preparation method thereof is split in a kind of polycation teritary amide class - Google Patents
Asphalt emulsifier of type or slow breaking and preparation method thereof is split in a kind of polycation teritary amide class Download PDFInfo
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- CN106831478B CN106831478B CN201710051043.6A CN201710051043A CN106831478B CN 106831478 B CN106831478 B CN 106831478B CN 201710051043 A CN201710051043 A CN 201710051043A CN 106831478 B CN106831478 B CN 106831478B
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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
- C07C237/08—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 atom of at least one of the carboxamide groups bound to an acyclic carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms
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- 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
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
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- 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
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- 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
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Abstract
The invention discloses asphalt emulsifiers that type or slow breaking are split in a kind of polycation teritary amide class and preparation method thereof, solves the deficiency for preparing asphalt emulsifier using acrylamide as raw material in the prior art, N, N dimethacrylamide is compared with acrylamide, emulsified asphalt de-emulsification speed is slow, so as to split type or slow breaking asphalt emulsifier as in, emulsifiability is more prominent and excellent.The asphalt emulsifier is prepared by the raw material of following mol ratio：1,3 trimethylene diamines of N hydrogenated-tallow groups, alcohols solvent, N, N dimethacrylamide, low carbon number tertiary amine, technical hydrochloric acid, epoxychloropropane molar ratio be 1mol：(5.00‑11.00)mol：(3.00‑3.10)mol：(2.02‑2.10)mol：(2.02‑2.10)mol：(2.02‑2.08)mol.The alcohols solvent is ethyl alcohol, methanol or isopropanol.The low carbon number tertiary amine is trimethylamine aqueous solution, triethylamine or triethanolamine aqueous solution.
Description
Technical field
The invention belongs to technical field of fine, and in particular to split type or slow breaking in a kind of polycation teritary amide class
Asphalt emulsifier and preparation method thereof.
Background technology
Emulsified asphalt especially cationic emulsified bitumen is due to that with energy conservation and environmental protection, can improve execution conditions, and can have
Effect reduces many excellent application characteristics such as pitch overaging, and is widely used in road construction and pavement preservation.
More common road cationic emulsified bitumen type includes：(1) type is split soon soon coagulates, for crushed stone sealing, the repairing on existing road surface
And bituminous penetration pavement；(2) slow hardening type is split slowly, as priming oil etc.；(3) type is coagulated in splitting slowly, for mixing coarse grain formula pitch
Concrete；(4) it is slow to split solidifying type soon, for slurry seal, Sub-sealing Course and micro-surface area；(5) type is split in, for sticking layer oil etc..
The most critical factor for influencing emulsified asphalt pavement performance is exactly asphalt emulsifier, at present domestic and international cationic pitch
Emulsifier principal item has organic amine, quaternary ammonium salt, imidazolines, amides etc., the wherein application of quaternary ammonium salt emulsifier 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 with diethylenetriamine under certain condition
Asphalt emulsifier.The disadvantages of this method is that the asphalt emulsifier prepared is expensive, when constructing 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 disadvantages of this method be the raw material supply of emulsifier by severely restricts, being unfavorable for promoting should
With.Chinese patent CN1861721A is related to a kind of rosin cation asphalt emulgent.The emulsifier 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 shortcomings that this method is that reaction step is cumbersome, needs pyroreaction.Chinese patent CN101712625A is related to
And a kind of method for synthesizing amphoteric slow-breaking quick-setting asphalt emulsifier, generation polyamide-polyamino is reacted with polyamines using oleic acid, is then added in
Halogenating reaction occurs for monoxone, and asphalt emulsifier is made.The disadvantages 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 agent is obtained by the reaction by mixed organic acid and organic amine
Intermediate, then carry out quaternization reaction and be made, adjuvant is nonionic surfactant and modified additive；The disadvantages of this method is system
Standby complex steps, cost is higher, needs pyroreaction.Chinese patent 201310722961.9 discloses a kind of Acid modified starch
The preparation method of cationic slow-breaking slow-curing asphalt emulsifier provides for asphalt emulsion and splits slow hardening performance slowly, but during emulsified asphalt,
The usage amount of emulsifier is larger.
The deficiency split in above-mentioned cationic or split asphalt emulsifier and preparation method thereof generally existing slowly is：Prepare emulsification
The cost of material of agent is higher, and source is restricted, and when preparation needs pyroreaction, higher to productive experiment equipment requirement.
Present inventor proposes a kind of polycation acid amide type asphalt emulsifier and preparation method thereof in early-stage study,
It is using acrylamide as the reaction raw materials of asphalt emulsifier, by adding in acrylamide pair in the molecular structure of asphalt emulsifier
Title introduces bisamide base, increases the hydrophily of asphalt emulsifier and the compatibility of emulsifier and pitch.But subsequently into
It is found in the research of one step, asphalt emulsifier is prepared there are still some areas for improvement by raw material of acrylamide, such as：
What early stage prepared using acrylamide as raw material is to split type asphalt emulsifier soon, and actually China's Emulsified Asphalt Thin Paste Seal Technique
Slow breaking asphalt emulsifier is the absence of than more prominent problem, is mainly shown as that single varieties, quality are unstable, be demulsified molding
The shortcomings of time is long, price is high, split slowly or in split type emulsifier type emulsifier is more difficult to be prepared compared to splitting soon；In addition, third
Acrylamide is solid material, it has not been convenient to feed and be uniformly mixed and react with other raw materials；In addition, acrylamide participation is anti-
The endothermic reaction is should be, therefore needs to increase in the preparation process of asphalt emulsifier and introduces external source heat, increases energy consumption.
Therefore, for a kind of polycation acid amide type asphalt emulsifier of application inventor's early stage research and preparation method thereof
There are problem above, still lack effective solution.
Invention content
To overcome the shortcomings of to prepare asphalt emulsifier by raw material of acrylamide in the prior art, the present invention provides a kind of more
The asphalt emulsifier of type or slow breaking is split in cationic teritary amide class, molecular structure is：
Wherein, R=methyl (- CH3), ethyl (- C2H5), ethoxy (- C2H4OH)。
The emulsifier is the reaction raw materials using N,N-DMAA as asphalt emulsifier, N, N- dimethyl allenes
Amide is liquid charging stock, facilitates charging and the mixing of other raw materials and reacts；And reaction process is exothermic reaction, reduces reaction
Energy consumption.The production cost of asphalt emulsifier of the present invention is low, it is simple for process, do not need to pyroreaction.
Preferably, the asphalt emulsifier of type or slow breaking is split in polycation teritary amide class of the present invention, be by with
The raw material of lower mol ratio is prepared：
N- hydrogenated-tallow group -1,3- trimethylene diamines, alcohols solvent, N, N- dimethacrylamide, low carbon number tertiary amine, industry
Hydrochloric acid, epoxychloropropane molar ratio be 1mol：(5.00-11.00)mol：(3.00-3.10)mol：(2.02-2.10)mol：
(2.02-2.10)mol：(2.02-2.08)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 acrylamide in the prior art, the present invention provides a kind of institute
The preparation method for the asphalt emulsifier that type or slow breaking are split in polycation teritary amide class is stated, is included the following steps：
(1) by N- hydrogenated-tallow group -1,3- trimethylene diamines, alcohols solvent and N,N-DMAA hybrid reaction,
Reaction intermediate I is obtained, intermediate compound I is
(2) by low carbon number tertiary amine, technical hydrochloric acid and epoxychloropropane hybrid reaction, reaction intermediate II, low carbon number are obtained
Tertiary amine is trimethylamine aqueous solution, triethylamine or triethanolamine aqueous solution, intermediate II are
R is methyl (- CH3), ethyl (- C2H5) or ethoxy (- C2H4OH)；
(3) reaction intermediate II is added drop-wise in reaction intermediate I, reacted to get to polycation teritary amide type pitch
Emulsifier.
The preparation sequence of step (1) and (2) can exchange.
Preferably, in the present invention, N- hydrogenated-tallow groups -1,3- trimethylene diamines, alcohols solvent, N, N- dimethyl allenes
Amide, low carbon number tertiary amine, technical hydrochloric acid, epoxychloropropane molar ratio be 1mol：(5.00-11.00)mol：(3.00-3.10)
mol：(2.02-2.10)mol：(2.02-2.10)mol：(2.02-2.08)mol.
By lot of experiment validation and analysis, each raw material of above-mentioned molar ratio cause more sun that the present invention is prepared from
The performance of Zishu acid amide type asphalt emulsifier is more satisfactory, and the raw material of inappropriate proportion relation cannot form polycation teritary amide
Type asphalt emulsifier.Especially for the addition of N,N-DMAA, the excessive or very few of addition all can shadow
Ring the water-separating time of the performance, especially asphalt emulsifier of the asphalt emulsifier prepared.
In step (1), reaction temperature is 60~80 DEG C, and preferably 65~75 DEG C, the reaction time 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, reduces the introducing of external source heat in reaction process, reduces the energy consumption of reaction.The acryloyl of early stage research
The reaction process of amine is the endothermic reaction, needs more extra heat source so that reaction reaches optimal reaction temperature.
Preferably, the alcohols solvent is ethyl alcohol, methanol or isopropanol, by lot of experiment validation and analysis, and according to
The needs of polycation teritary amide class asphalt emulsifier produced by the present invention, select asphalt emulsifier made from above-mentioned alcohols solvent
Effect it 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 can cause anti-
The epoxy bond of intermediate II is answered to open, makes it that can not further react the type drip of generation polycation teritary amide with reaction intermediate I
Green emulsifier, so as to reduce the yield of target product；If the temperature of reaction is too low, reaction solution can be layered, Jin Erying
Reaction process is rung.To improve the yield of final products, this temperature condition is optimized in the present invention, and reaction temperature is
At 47-55 DEG C, the preparation effect of reaction intermediate II is optimal.
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.
The asphalt emulsifier of type or slow breaking is split in above-mentioned polycation teritary amide class, is specifically comprised the following steps：
(1) N- hydrogenated-tallow group -1,3- trimethylene diamines is added in reaction vessel, adds in alcohols solvent, heating stirring
Dissolving, then N,N-DMAA is added portionwise, after addition, 2-4h is stirred to react at 60-80 DEG C, is obtained in reaction
Mesosome I；
(2) low carbon number tertiary amine is added in the second reactor, and technical hydrochloric acid is added portionwise, after technical hydrochloric acid adds in,
Epoxychloropropane is added portionwise again, after epoxychloropropane adds in, 2-3h is stirred to react at 47-55 DEG C, 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 reaction 2-4h to get to it is more sun from
The asphalt emulsifier of type or slow breaking is split in Zishu amides；
The preparation sequence of step (1) and (2) can exchange.
The present invention also provides a kind of above-mentioned polycation teritary amide class asphalt emulsifiers to split type or slow breaking sun in preparation
Application in ion emulsified asphalt.
For overcome the shortcomings of it is of the prior art in split type or the more difficult preparation of slow breaking emulsified asphalt, the present invention provides a kind of
The preparation method of cationic emulsified bitumen, step are as follows：
Water is added to be configured to aqueous solution above-mentioned polycation teritary amide type asphalt emulsifier, adjust pH to 2-3, be heated to
60-70 DEG C, soap lye is made；Pitch after heating and emulsifier soap lye are prepared into cation emulsified drip by colloid mill emulsification
It is green；
The dosage of the polycation teritary amide type asphalt emulsifier is the 0.8- of the emulsified asphalt gross mass prepared
2.5%.
The cationic emulsified bitumen that above-mentioned preparation method is prepared, the type of the cationic emulsified bitumen split in being type or
Slow breaking emulsified asphalt.
Compared with prior art, the beneficial effects of the invention are as follows：
(1) present invention reasonably selects reaction raw materials, is made to filter out excellent asphalt emulsifier as starting point
It is standby to have obtained a kind of polycation teritary amide type asphalt emulsifier with prominent technique effect.
The present invention is for the first time using N,N-DMAA as the reaction raw materials for preparing cationic asphalt emulsifier, system
Standby obtained asphalt emulsifier has unexpected technique effect, which is embodied in：Compared to morning
Phase uses acrylamide as reaction raw materials, the present invention using N,N-DMAA as raw material be prepared be in split type or
The polycation asphalt emulsifier of slow breaking, and the polycation asphalt emulsifier has excellent emulsifiability, prepares breast
Volume is few when changing pitch.This is the unexpected technology of those skilled in the art on the basis of the research of early stage acrylamide
Effect.
(2) for N,N-DMAA compared with acrylamide, emulsifiability is more prominent and excellent.
Compared with acrylamide, two hydrogen are replaced by methyl on the amide groups nitrogen of acrylamide molecules, the hydrolysis of copolymer
Stability is significantly improved than acrylamide, active double bond in molecule, makes it easier to autohemagglutination or is copolymerized with other monomers.
Since hydrogen is replaced with methyl, the lipophilic group in the asphalt emulsifier molecular structure of preparation is increased, more conducively
Interfacial film is formed, reduces the interfacial tension between water and pitch；In addition, prepared using N,N-DMAA as reaction raw materials
The ionizing power of asphalt emulsifier in water is stronger, can ionize out more cations, and the effect for making interface charge layer is stronger；
So that pitch can emulsify and uniformly can disperse to form metastable asphalt emulsion in water.
(3) N,N-DMAA is compared with acrylamide, and emulsified asphalt de-emulsification speed is slow, so as to as in
Type or slow breaking asphalt emulsifier are split, is the prominent technique effect expected for those skilled in the art.
General those skilled in the art will be considered that the de-emulsification speed of cation asphalt emulgent is very fast, be suitable as splitting type soon
Emulsifier, for example, early stage using acrylamide as raw material, the polycation acid amide type asphalt emulsifier that is prepared.And the present invention adopts
With N,N-DMAA, emulsified asphalt de-emulsification speed is slow, and type or slow breaking asphalt emulsifier are split in being used as.
In pavement construction, after emulsified asphalt demulsification refers to that asphalt emulsion is contacted with building stones, bitumen particle divides from lotion
It separates out and, coalesce and sprawl in stone surface, form the process of one layer of continuous asphalt film, during demulsification, pitch breast
Moisture evaporation in liquid.
There are many factor for influencing emulsified asphalt demulsification, exclude the influence of building stones, and emulsifier is to influence emulsified asphalt demulsification speed
The key factor of degree.Those skilled in the art is unexpected, and two hydrogen on the amide groups nitrogen of acrylamide are replaced by methyl,
The type of emulsifier can be changed, by the analysis of inventor, tracing it to its cause, there may be both sides reasons：On the one hand, with
Acrylamide is compared, and since hydrogen is replaced with methyl, increases the lipophilic group in the asphalt emulsifier molecular structure of preparation, and
Lipophilic group can be more firmly inserted into bitumen particle, when being reacted with building stones, the time of contact of building stones and bitumen particle
It is elongated, so that demulsification time lengthening；On the other hand, since N,N-DMAA contains, there are two methyl so that breast
The steric hindrance of agent molecule is relatively large, and building stones need to overcome larger steric hindrance when contacting with bitumen particle, so as to
So that de-emulsification speed is slower.
(4) when preparing emulsified asphalt, the volume of asphalt emulsifier is less, about 0.8-2.5%, is split in being used as
Type or slow breaking asphalt emulsifier.
It is generally acknowledged that when the dosage of cation asphalt emulgent is larger, type or slow breaking emulsified asphalt are split in could preparing,
And the dosage of the emulsified asphalt of the present invention is less, illustrates to split the excellent effect of type or slow breaking emulsified asphalt in preparing.
(5) present invention is using N,N-DMAA as the reaction raw materials of asphalt emulsifier, due to N, N- dimethyl
The material state of acrylamide at normal temperatures is liquid, facilitates metered charge, and is more convenient to mix with other reaction raw materials
Uniform reaction, yield is higher, is more easy to realize production serialization.
In addition, the reaction process of N,N-DMAA is exothermic reaction, the heat needed for reaction itself can be provided
Amount, reduces the introducing of external source heat in reaction process, reduces the energy consumption of reaction.
(6) present invention use specific raw material N, N- dimethacrylamide, N- hydrogenated-tallow group -1,3- trimethylene diamines,
Low carbon number tertiary amine, hydrochloric acid and epoxychloropropane, the pitch of polycation teritary amide type chemical constitution of the generation with certain HLB value
Emulsifier has good emulsifiability using polycation teritary amide type asphalt emulsifier prepared by the present invention, is prepared
Emulsified asphalt property indices it is excellent, the pitch of emulsifiable a variety of different models, the emulsified asphalt of preparation is fine and smooth uniformly,
It is good gather materials wrap up in attached property.Emulsified asphalt obtained presses the cationic emulsified bitumen professional standard that Chinese transportation portion works out
(JTJ052-2000) it is detected, properties can meet standard requirement.Suitable for spilling for highway priming oil or sticking layer oil
Cloth and for constructions such as slurry seal and micro-surface areas, splits and splits slowly the characteristic of asphalt emulsifier in having.It is using the present invention
Emulsifier is split in being prepared or slow-breaking emulsified asphalt, and mixture can be made to have preferable mobility and permeability, be conducive to
The compactibility and water proofing property on road surface are improved in filling and the crack on repairing road surface.
(7) the raw materials used in the present invention N- hydrogenated-tallow groups -1,3- trimethylene diamines is cheap, derives from a wealth of sources, asphalt emulsifier life
It produces at low cost, and splits type in polycation teritary amide class or slow breaking asphalt emulsifier provides good basis to prepare.
(8) in the prior art amide groups amine emulsifier reaction temperature general control at 140~180 DEG C, and the present invention
The preparation method of polycation teritary amide type asphalt emulsifier is simple for process, does not need to pyroreaction, reduces energy consumption, greatlys 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.It is 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 singulative
It is also 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 combination thereof.
On Research foundation based on a kind of polycation acid amide type asphalt emulsifier and preparation method thereof, it is more suitable to select
Reaction raw materials, advanced optimized the performance of asphalt emulsifier, which has more aobvious compared to the result of study of early stage
The difference of work.There is provided the asphalt emulsifications that type or slow breaking are split in a kind of polycation teritary amide class for specific technical solution
Agent, molecular structure are：
Wherein, R=methyl (- CH3), ethyl (- C2H5), ethoxy (- C2H4OH)。
In one embodiment, the present invention provides the drip that type or slow breaking are split in a kind of polycation teritary amide class
The preparation method of green emulsifier, includes the following steps：
(1) by N- hydrogenated-tallow group -1,3- trimethylene diamines, alcohols solvent and N,N-DMAA hybrid reaction,
Reaction intermediate I is obtained, intermediate compound I is
(2) by low carbon number tertiary amine, technical hydrochloric acid and epoxychloropropane hybrid reaction, reaction intermediate II, low carbon number are obtained
Tertiary amine is trimethylamine aqueous solution, triethylamine or triethanolamine aqueous solution, intermediate II are
R is methyl (- CH3), ethyl (- C2H5) or ethoxy (- C2H4OH)；
(3) reaction intermediate II is added drop-wise in reaction intermediate I, reacted to get to polycation teritary amide type pitch
Emulsifier.
The preparation sequence of step (1) and (2) can exchange.
Preferably, in the present invention, N- hydrogenated-tallow groups -1,3- trimethylene diamines, alcohols solvent, N, N- dimethyl allenes
Amide, low carbon number tertiary amine, technical hydrochloric acid, epoxychloropropane molar ratio be 1mol：(5.00-11.00)mol：(3.00-3.10)
mol：(2.02-2.10)mol：(2.02-2.10)mol：(2.02-2.08)mol.
By lot of experiment validation and analysis, each raw material of above-mentioned molar ratio cause more sun that the present invention is prepared from
The performance of Zishu acid amide type asphalt emulsifier is more satisfactory, and the raw material of inappropriate proportion relation cannot form polycation teritary amide
Type asphalt emulsifier.Especially for the addition of N,N-DMAA, the excessive or very few of addition all can shadow
Ring the water-separating time of the performance, especially asphalt emulsifier of the asphalt emulsifier prepared.
In another embodiment of the present invention, in step (1), reaction temperature be 60~80 DEG C, preferably 65~75
DEG C, the reaction time is 2~4h.
Preferably, 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.It finds after further study, the reaction temperature of the step is low to the high income of final reacting product most important, the temperature of reaction
Height is spent, then the epoxy bond of reaction intermediate II can be caused to open, makes it that can not further react generation with reaction intermediate I more
Cationic teritary amide type asphalt emulsifier, so as to reduce the yield of target product；If the temperature of reaction is too low, reaction can be made
Solution is layered, and then affects reaction process.To improve the yield of final products, the present invention has carried out this temperature condition excellent
Change, when reaction temperature is 47-55 DEG C, the preparation effect of reaction intermediate II is optimal.
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.
What the present invention was prepared by above method is pitch breast that type or slow breaking are split in polycation teritary amide class
Agent.
The present invention also provides type or slow breaking emulsified asphalt is split in one kind, the preparation method of the emulsified asphalt includes following step
Suddenly：
Water is added to be configured to aqueous solution above-mentioned polycation teritary amide type asphalt emulsifier, adjust pH to 2-3, be heated to
60-70 DEG C, soap lye is made；Pitch after heating and emulsifier soap lye are prepared into cation emulsified drip by colloid mill emulsification
It is green.
In one embodiment of the invention, using Nacl acid for adjusting pH value to 2-3.
In yet another embodiment of the present invention, the dosage of the polycation teritary amide type asphalt emulsifier is what is prepared
The 0.8-2.5% of emulsified asphalt gross mass.It is generally acknowledged that when the dosage of cation asphalt emulgent is larger, type is split in could preparing
Or slow breaking emulsified asphalt, and the dosage of the emulsified asphalt of the present invention is less, illustrates to split type or slow breaking emulsified asphalt in preparing
Excellent effect, be very suitable for prepare in split type or slow breaking emulsified asphalt, type or slow breaking asphalt emulsifier are split in enriching
Type.
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 with comparative example for the embodiment of body.
Embodiment 1
(1) preparation of polycation teritary amide type asphalt emulsifier：
1) addition 326.0gN- hydrogenated-tallow group -1,3- trimethylene diamines, 330g isopropanols, heating stirring are molten in the reactor
Solution.Then 302.4g N,N-DMAAs are gradually added into, 70 DEG C are stirred to react 3h.
The above-mentioned intermediate product of synthesis carries out FTIR detections after recrystallizing separating-purifying, as a result as follows：2927cm-1For Asia
The asymmetric stretching vibration absworption peak of methyl, 2846cm-1Symmetrical stretching vibration for methylene receives peak, 1652cm-1For amide groups
Middle C=O stretching vibration absworption peaks, 1500cm-1And 1471cm-1Asymmetric curvature for methylene is vibrated, 1404cm-1For methyl
Asymmetric curvature vibration, 1271cm-1And 1139cm-1For C-N stretching vibration absworption peaks, 1053cm-1It shakes for C-H in-plane bendings
Dynamic absorption peak, 723cm-1For methylene rocking vibration absorption peak.
2) 371.9g 33% (mass fraction) trimethylamine aqueous solution is added in the reactor, is gradually added into 252.7g 30%
(mass fraction) technical hydrochloric acid, then 189.5g epoxychloropropane is gradually added into, 50 DEG C are stirred to react 2.5h, obtain reaction intermediate
A.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.Obtain polycation uncle
Acid amide type asphalt emulsifier gives over to emulsified asphalt experiment.
Synthetic product carries out FTIR detections after recrystallizing separating-purifying, as a result as follows：3400cm-1For O-H stretching vibrations
Absorption peak, 2925cm-1For the asymmetric stretching vibration absworption peak of methylene, 2848cm-1Symmetrical stretching vibration for methylene is received
Peak, 1629cm-1For C=O stretching vibration absworption peaks, 1470cm in amide groups-1Asymmetric curvature for methylene is vibrated,
1407cm-1Asymmetric curvature for methyl is vibrated, 1263cm-1And 1145cm-1For C-N stretching vibration absworption peaks, 1060cm-1For
C-OH stretching vibration absworption peaks, 958cm-1For O-H out-of-plane bending vibration absorption peaks, 630cm-1For methylene rocking vibration
Absorption peak.
Reaction equation is as follows：
(2) preparation of emulsified asphalt：
AH-90# pitch 300g are taken, are heated to 125 DEG C, 7.5g asphalt emulsifiers manufactured in the present embodiment are added to 200g
In 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 colloid mill
Cationic emulsified asphalt is prepared in 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, it is as a result as follows：Emulsified asphalt manufactured in the present embodiment is uniform, fine and smooth, bitumen content 59%, and surplus is on sieve
0.01%, area is wrapped more than 2/3 with mineral aggregate, and storage stability (1d) is 0.8%；In de-emulsification speed experiment, using B classes
Material the mixing time can be more than 1min；It is mixed and stirred, (as a comparison, can on an equal basis tested for 65 seconds the mixing time using material is mixed and stirred
Under the conditions of, reaction raw materials N,N-DMAA is replaced with into acrylamide, is mixed and stirred using material is mixed and stirred, can mix when
Between be 4s).Show that asphalt emulsion prepared by the emulsifier is slow breaking cationic emulsified bitumen, properties can meet standard
It is required that.
Embodiment 2
(1) preparation of polycation teritary amide type asphalt emulsifier：
1) addition 326.0gN- hydrogenated-tallow group -1,3- trimethylene diamines, 330g isopropanols, heating stirring are molten in the reactor
Solution.Then 302.4g N,N-DMAAs are gradually added into, 70 DEG C are stirred to react 3h.
2) 210.1g triethylamines are added in the reactor, are gradually added into 252.7g 30% (mass fraction) technical hydrochloric acid, then
189.5g epoxychloropropane is gradually added into, 47 DEG C are stirred to react 3h, obtain reaction intermediate B.By the reaction intermediate B drops of preparation
It is added to above-mentioned steps 1) in synthetic product, 65 DEG C are stirred to react 3h.Polycation teritary amide type asphalt emulsifier is obtained, gives over to breast
Change asphalt test.
Synthetic product carries out FTIR detections after recrystallizing separating-purifying, as a result as follows：3406cm-1For O-H stretching vibrations
Absorption peak, 2927cm-1For the asymmetric stretching vibration absworption peak of methylene, 2854cm-1Symmetrical stretching vibration for methylene is received
Peak, 1620cm-1For C=O stretching vibration absworption peaks, 1471cm in amide groups-1Asymmetric curvature for methylene is vibrated,
1400cm-1Asymmetric curvature for methyl is vibrated, 1270cm-1And 1163cm-1For C-N stretching vibration absworption peaks, 1085cm-1For
C-OH stretching vibration absworption peaks, 709cm-1For methylene rocking vibration absorption peak.
Reaction equation is as follows：
(2) preparation of emulsified asphalt：
AH-70# pitch 300g are taken, are heated to 125 DEG C, 7.5g asphalt emulsifiers manufactured in the present embodiment are added to 200g
In 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 colloid mill
Cationic emulsified asphalt is prepared in emulsification.
(3) emulsified asphalt performance detection：
Detection method is with embodiment 1, testing result：Emulsified asphalt is uniform, fine and smooth, bitumen content 60%, is remained on sieve
Surplus is 0.02%, wraps area more than 2/3 with mineral aggregate, storage stability (1d) is 0.8%；In de-emulsification speed experiment, adopt
With B class material, the mixing time 1min can be more than；Mixed and stirred using material is mixed and stirred, can the mixing time for 125 seconds (as a comparison, same
It waits under experiment conditions, reaction raw materials N,N-DMAA is replaced with into acrylamide, is mixed and stirred using material is mixed and stirred, it can
Duration of mixing is 4s).Show that asphalt emulsion prepared by the emulsifier is slow breaking cationic emulsified bitumen, properties can be full
Sufficient standard requirement.
Embodiment 3
(1) preparation of polycation teritary amide type asphalt emulsifier：
1) addition 326.0gN- hydrogenated-tallow group -1,3- trimethylene diamines, 330g isopropanols, heating stirring are molten in the reactor
Solution.Then 302.4g N,N-DMAAs are gradually added into, 65 DEG C are stirred to react 4h.
2) 365.1g 85% (mass fraction) triethanolamine is added in the reactor, is gradually added into 30% (matter of 252.7g
Measure score) technical hydrochloric acid, then 189.5g epoxychloropropane is gradually added into, 55 DEG C are stirred to react 2h, obtain reaction intermediate C.It will
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.Obtain polycation teritary amide
Type asphalt emulsifier gives over to emulsified asphalt experiment.
Synthetic product carries out FTIR detections after recrystallizing separating-purifying, as a result as follows：3373cm-1For O-H stretching vibrations
Absorption peak, 2924cm-1For the asymmetric stretching vibration absworption peak of methylene, 2847cm-1Symmetrical stretching vibration for methylene is received
Peak, 1627cm-1For C=O stretching vibration absworption peaks, 1463cm in amide groups-1Asymmetric curvature for methylene is vibrated,
1398cm-1Asymmetric curvature for methyl is vibrated, 1265cm-1And 1153cm-1For C-N stretching vibration absworption peaks, 1060cm-1For
C-OH stretching vibration absworption peaks, 931cm-1For O-H out-of-plane bending vibration absorption peaks, 670cm-1For methylene rocking vibration
Absorption peak.
Reaction equation is as follows：
(2) preparation of emulsified asphalt：
A-100# pitch 300g are taken, are heated to 125 DEG C, 7.5g asphalt emulsifiers manufactured in the present embodiment are added to 200g
In 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 colloid mill
Cationic emulsified asphalt is prepared in emulsification.
(3) emulsified asphalt performance detection：
Detection method is with embodiment 1, testing result：Emulsified asphalt is uniform, fine and smooth, bitumen content 58%, is remained on sieve
Surplus is 0.02%, wraps area more than 2/3 with mineral aggregate, storage stability (1d) is 0.9%；In de-emulsification speed experiment, adopt
With B class material, the mixing time 1min can be more than；Mixed and stirred using material is mixed and stirred, can the mixing time for 31 seconds (as a comparison, same
It waits under experiment conditions, reaction raw materials N,N-DMAA is replaced with into acrylamide, is mixed and stirred using material is mixed and stirred, it can
Duration of mixing is 3s).The asphalt emulsion for showing emulsifier preparation splits type cationic emulsified bitumen in being, properties can be full
Sufficient standard requirement.
Comparative example 1
Reaction raw materials " N,N-DMAA " in embodiment 1 are replaced with " 216.8g acrylamides ", are prepared
Method with embodiment 1 (i.e.：Embodiment 1 in 105399645 A of CN), asphalt emulsifier is prepared.
The emulsifying capacity of asphalt emulsifier prepared to embodiment 1 and comparative example 1 is measured, signified breast in the present invention
Change ability refers to：Liquid immiscible with oily two classes asphalt emulsifier Jiang Shui is changed into the ability of emulsion.
The present invention measures emulsifying capacity using graduated cylinder method, and breast is thoroughly mixed to form according to asphalt emulsifier and atoleine
Thus shape liquid, then the 10ml water required time is separated after standing, that is, water-separating time evaluates the emulsification of asphalt emulsifier
Performance.
Specific method is as follows：
The asphalt emulsifier for measuring 0.1% (mass fraction) respectively with pipette (is made by embodiment 1 and comparative example 1 respectively
It is standby) aqueous solution 40ml, in the conical flask for the 100ml for being placed in glass stopper, then measure with pipette the atoleine of 40ml
It is placed in this conical flask.It is then fierce up and down to vibrate 5 times by tight glass stopper, it is vibrated again 5 times, then stand 1min after standing 1min；
After being so repeated 5 times, this lotion is poured into the tool plug graduated cylinder of 100ml, record the time with stopwatch at once.Water phase and an oil phase is gradual
Separation, water phase can appear in the lower floor of graduated cylinder slowly, when water phase separates 10ml water, record separate at this time used in water when
Between, using this time as emulsifying capacity relatively, the more long then emulsifying capacity of water-separating time is stronger.
Repeat experiment three times, after testing, the water-separating time average out to of asphalt emulsifier prepared by the embodiment of the present invention 1
152s；The water-separating time average out to 82s of asphalt emulsifier prepared by comparative example 1.With N, N- diformazans it can be seen from water-separating time
Base acrylamide is that the emulsifying capacity of asphalt emulsifier prepared by raw material will be significantly better than the drip prepared by raw material of acrylamide
Green emulsifier.
Comparative example 2
By the preparation process 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 asphalt emulsifier is prepared, the particularly 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 process 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 asphalt emulsifier is prepared, the particularly 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 so that reaction intermediate II and reaction intermediate I, which cannot further react, is prepared asphalt emulsifier, reduces
The yield of final product asphalt emulsifier.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (12)
1. the asphalt emulsifier of type or slow breaking is split in a kind of polycation teritary amide class, it is characterized in that, molecular structural formula is：
Wherein, R=methyl, ethyl, ethoxy.
2. the preparation method of the asphalt emulsifier of type or slow breaking is split in polycation teritary amide class described in claim 1,
It is characterized in, includes the following steps：
(1) it by N- hydrogenated-tallow group -1,3- trimethylene diamines, alcohols solvent and N,N-DMAA hybrid reaction, obtains
Reaction intermediate I, intermediate compound I are
(2) by low carbon number tertiary amine, technical hydrochloric acid and epoxychloropropane hybrid reaction, reaction intermediate II, low carbon number tertiary amine are obtained
It is for trimethylamine aqueous solution, triethylamine or triethanolamine aqueous solution, intermediate IIR is
Methyl, ethyl or ethoxy；
(3) reaction intermediate II is added drop-wise in reaction intermediate I, react to get to split in polycation teritary amide class type or
The asphalt emulsifier of slow breaking；
Above step does not influence to prepare, and can exchange sequence.
3. preparation method as claimed in claim 2, it is characterized in that：N- hydrogenated-tallow groups -1,3- trimethylene the diamines, alcohols are molten
Agent, N, N- dimethacrylamide, low carbon number tertiary amine, technical hydrochloric acid, epoxychloropropane molar ratio be 1mol：(5.00-
11.00)mol：(3.00-3.10)mol：(2.02-2.10)mol：(2.02-2.10)mol：(2.02-2.08)mol.
4. preparation method as claimed in claim 2, it is characterized in that：In step (1), the temperature of reaction is 60-80 DEG C, reaction
Time is 2-4h.
5. preparation method as claimed in claim 4, it is characterized in that：In step (1), the temperature of reaction is 65-75 DEG C.
6. preparation method as claimed in claim 2, it is characterized in that：In step (1), the alcohols solvent for ethyl alcohol, methanol or
Isopropanol.
7. preparation method as claimed in claim 2, it is characterized in that：In step (2), the temperature of reaction is 47-55 DEG C, reaction
Time is 2-3h.
8. preparation method as claimed in claim 2, it is characterized in that：In step (3), the temperature of reaction is 60-80 DEG C, reaction
Time is 2-4h.
9. preparation method as claimed in claim 8, it is characterized in that：In step (3), the temperature of reaction is 65-75 DEG C.
10. polycation teritary amide class asphalt emulsifier described in claim 1 splits type or slow breaking cationic galactomannan in preparation
Change the application in pitch.
11. a kind of preparation method of cationic emulsified bitumen, includes the following steps：By polycation uncle described in claim 1
Acid amide type asphalt emulsifier adds water to be configured to aqueous solution, adjusts pH to 2-3, is heated to 60-70 DEG C, and soap lye is made；After heating
Pitch and emulsifier soap lye by colloid mill emulsification prepare cationic emulsified bitumen；
The dosage of the polycation teritary amide type asphalt emulsifier is the 0.8-2.5% of the emulsified asphalt gross mass prepared.
12. the cationic emulsified bitumen that the preparation method described in claim 11 obtains.
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| CN110305336B (en) * | 2018-03-20 | 2020-05-08 | 山东大学 | Amide polyamine asphalt emulsifier, emulsified asphalt, and preparation method and application thereof |
| CN110144023B (en) * | 2019-06-17 | 2021-08-31 | 河北工业大学 | Preparation method of modified polyvinyl alcohol cation slow-breaking asphalt emulsifier |
| CN113694823B (en) * | 2021-02-25 | 2022-04-22 | 山东大学 | Secondary amide sulfonic acid surfactant, and preparation method and application thereof |
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| CN103980147A (en) * | 2014-05-23 | 2014-08-13 | 山东大学 | Method for preparing amphoteric betaine asphalt emulsifier |
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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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