CN106831478A - 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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- CN106831478A CN106831478A CN201710051043.6A CN201710051043A CN106831478A CN 106831478 A CN106831478 A CN 106831478A CN 201710051043 A CN201710051043 A CN 201710051043A CN 106831478 A CN106831478 A CN 106831478A
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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 splitting asphalt emulsifier of type or slow breaking and preparation method thereof in a kind of polycation teritary amide class, solve the deficiency for preparing asphalt emulsifier as raw material with acrylamide in the prior art, N, N DMAAs are compared with acrylamide, emulsified asphalt de-emulsification speed is slow, such that it is able to split type or slow breaking asphalt emulsifier in, emulsifiability is more prominent and excellent.The asphalt emulsifier is prepared from by the raw material of following mol ratio：The trimethylene diamines of N hydrogenated-tallow groups 1,3, alcohols solvent, N, N DMAAs, low carbon number tertiary amine, technical hydrochloric acid, the mol ratio of epoxychloropropane are 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 ethanol, methyl alcohol or isopropanol.The low carbon number tertiary amine is trimethylamine aqueous solution, triethylamine or the 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
Especially cationic emulsified bitumen, due to that with energy-conserving and environment-protective, can improve execution conditions, and can have emulsified asphalt
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 influenceing emulsified asphalt pavement performance is exactly asphalt emulsifier, at present domestic and international cationic pitch
Emulsifying agent principal item has organic amine, quaternary ammonium salt, imidazolines, amide-type etc., the wherein application of quaternary ammonium salt emulsifying agent most
Extensively.With the application of cationic emulsified bitumen, the kind of asphalt emulsifier is also gradually enriched.
United States Patent (USP) USP4338136 is with C12-18Long carbon chain aliphatic acid reacts preparation under certain condition with diethylenetriamine
Asphalt emulsifier.The shortcoming of the method is that the asphalt emulsifier for preparing is expensive, when being constructed for slurry seal, is demulsified the time
Long, molding time is slow, and the open to traffic time is long.Chinese patent CN1096714 utilizes oil plant by-product aphthenic acids and alkenyl polyamine
Reaction, prepares asphalt emulsifier.The shortcoming of the method is that the raw material supply of emulsifying agent is subject to severely restricts, is unfavorable for promoting and answers
With.Chinese patent CN1861721A is related to a kind of rosin cation asphalt emulgent.The emulsifying agent is by rosin and alkenyl polyamine
Reaction, obtain rosin intermediate, then, with different types of quaternary ammonium salt intermediate condensation, be obtained function admirable rosin sun from
Sub- asphalt emulsifier.The shortcoming of this method is reactions steps cumbersome, it is necessary to pyroreaction.Chinese patent CN101712625A is related to
And a kind of method for synthesizing amphoteric slow-breaking quick-setting asphalt emulsifier, using oleic acid and polyamines reaction generation polyamide-polyamino, it is subsequently adding
There is halogenating reaction in monoxone, asphalt emulsifier is obtained.The shortcoming of the method is to need pyroreaction when preparing.Chinese patent
CN101745340A is related to a kind of cation asphalt emulgent preparation method, host to be obtained by mixed organic acid and organic amine reaction
Intermediate, then carry out quaterisation be obtained, assistant agent be nonionic surfactant and modified additive；The shortcoming of the method is system
Standby complex steps, it is relatively costly, it is necessary to pyroreaction.Chinese patent 201310722961.9 discloses a kind of Acid modified starch
The preparation method of cation slow-breaking slow-curing asphalt emulsifier, slow hardening performance is split for asphalt emulsion is provided slowly, but during emulsified asphalt,
The usage amount of emulsifying agent 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 pyroreaction is needed during preparation, higher to production experimental facilities requirement.
Present inventor proposes a kind of polycation acid amide type asphalt emulsifier and preparation method thereof in early-stage Study,
Its reaction raw materials with acrylamide as asphalt emulsifier, by adding acrylamide pair in the molecular structure of asphalt emulsifier
Title introduces bisamide base, increased the hydrophily of asphalt emulsifier, and emulsifying agent and pitch compatibility.But subsequently entering
Found in the research of one step, some areas for improvement are still suffered from as raw material prepares asphalt emulsifier with acrylamide, for example：
What early stage prepared with 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, it is mainly shown as, and single varieties, quality are unstable, be demulsified shaping
The shortcomings of time is long, price is high, split slowly or in split type emulsifying agent type emulsifying agent is more difficult to be prepared compared to splitting soon；In addition, third
Acrylamide is solid material, it has not been convenient to feeds and is well mixed and reacts with other raw materials；Further, what acrylamide was participated in is anti-
The endothermic reaction is should be, therefore needs to increase introducing external source heat in the preparation process of asphalt emulsifier, increased energy consumption.
Therefore, a kind of polycation acid amide type asphalt emulsifier studied early stage for application inventor and preparation method thereof
There is problem above, still lack effective solution.
The content of the invention
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 many
The asphalt emulsifier of type or slow breaking is split in cation teritary amide class, its molecular structure is：
Wherein, R=methyl (- CH3), ethyl (- C2H5), ethoxy (- C2H4OH)。
The emulsifying agent is the reaction raw materials using N,N-DMAA as asphalt emulsifier, N, N- dimethyl allene
Acid amides is liquid charging stock, and convenient charging and other raw materials mix and react；And course of reaction is exothermic reaction, reduces reaction
Energy consumption.The low production cost of asphalt emulsifier of the present invention, process is simple, pyroreaction is not needed.
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- DMAAs, low carbon number tertiary amine, industry
Hydrochloric acid, the mol ratio of epoxychloropropane are 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 ethanol, methyl alcohol or isopropanol.
The low carbon number tertiary amine trimethylamine aqueous solution, triethylamine or the 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 of the asphalt emulsifier that type or slow breaking are split in polycation teritary amide class is stated, is comprised 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 the triethanolamine aqueous solution, and intermediate II is
R is methyl (- CH3), ethyl (- C2H5) or ethoxy (- C2H4OH)；
(3) reaction intermediate II is added drop-wise in reaction intermediate I, is reacted, that is, obtain polycation teritary amide type pitch
Emulsifying agent.
The preparation order of step (1) and (2) can be exchanged.
Preferably, in the present invention, N- hydrogenated-tallow group -1,3- trimethylene diamines, alcohols solvent, N, N- dimethyl allenes
Acid amides, low carbon number tertiary amine, technical hydrochloric acid, the mol ratio of epoxychloropropane are 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 many 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 can not form polycation teritary amide
Type asphalt emulsifier.Especially for the addition of N,N-DMAA, the excessive or very few of its addition all can shadow
The performance of the asphalt emulsifier for preparing is rung, especially the water-separating time of asphalt emulsifier.
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 course of reaction of N,N-DMAA is exothermic reaction, itself can provide anti-
Required heat is answered, the introducing of external source heat in course of reaction is reduced, the energy consumption of reaction is reduced.The acryloyl of early stage research
The course of reaction of amine is the endothermic reaction, it is necessary to more extra heat source is so that reaction reaches optimal reaction temperature.
Preferably, the alcohols solvent is ethanol, methyl alcohol or isopropanol, by lot of experiment validation and analysis, and according to
The need for obtained polycation teritary amide class asphalt emulsifier of the invention, asphalt emulsifier obtained in above-mentioned alcohols solvent is selected
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 too high, then can cause anti-
Answer the epoxy bond of intermediate II to open, it is further reacted generation polycation teritary amide type with reaction intermediate I and drip
Blue or green emulsifying agent, so as to reduce the yield of target product；If the temperature of reaction is too low, can be layered reaction solution, Jin Erying
Reaction process is rung.To improve the yield of final products, the present invention is optimized to this temperature conditions, 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, following steps are specifically included：
(1) by N- hydrogenated-tallow group -1,3- trimethylene diamines is added in reaction vessel, adds alcohols solvent, heating stirring
Dissolving, then N,N-DMAA is dividedly in some parts, after addition is finished, in 60-80 DEG C of stirring reaction 2-4h, in being reacted
Mesosome I；
(2) low carbon number tertiary amine is added in second reactor, technical hydrochloric acid is dividedly in some parts, technical hydrochloric acid is added after finishing,
Epoxychloropropane is dividedly in some parts again, epoxychloropropane is added after finishing, in 47-55 DEG C of stirring reaction 2-3h, obtain in the middle of reaction
Body II, wherein, low carbon number tertiary amine is trimethylamine aqueous solution, triethylamine or the triethanolamine aqueous solution；
(3) reaction intermediate II is dividedly in some parts in reaction intermediate I, 60-80 DEG C of reaction 2-4h, that is, obtain many sun from
The asphalt emulsifier of type or slow breaking is split in Zishu amide-type；
The preparation order of step (1) and (2) can be exchanged.
The present invention also provides a kind of above-mentioned polycation teritary amide class asphalt emulsifier and type or slow breaking sun is split 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 is as follows：
Above-mentioned polycation teritary amide type asphalt emulsifier is added water and is configured to the aqueous solution, pH is to 2-3 for regulation, is heated to
60-70 DEG C, soap lye is obtained；Pitch after heating and emulsifying agent soap lye are emulsified by colloid mill and prepares cation emulsified drip
It is blue or green；
The consumption of the polycation teritary amide type asphalt emulsifier is the 0.8- of the emulsified asphalt gross mass for preparing
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 is starting point to filter out excellent asphalt emulsifier, and reaction raw materials are reasonably selected, and is made
It is standby to have obtained a kind of polycation teritary amide type asphalt emulsifier with prominent technique effect.
The present invention makes first using N,N-DMAA as the reaction raw materials for preparing cationic asphalt emulsifier
The standby asphalt emulsifier for obtaining has unexpected technique effect, and the unexpected technique effect is embodied in：Compared to morning
It is reaction raw materials that phase uses acrylamide, the present invention with N,N-DMAA as raw material prepare 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) N,N-DMAA is compared with acrylamide, and 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, make it easier to autohemagglutination or with other monomers copolymerization.
Due to hydrogen is replaced with into methyl, the lipophilic group in the asphalt emulsifier molecular structure of preparation is increased, more conducively
Interfacial film is formed, the interfacial tension between water and pitch is reduced；In addition, prepared as reaction raw materials with N,N-DMAA
Ionizing power of the asphalt emulsifier in water is stronger, can ionize out more cations, makes the effect of interface charge layer stronger；
So that pitch can emulsify in water and uniformly can disperse to form metastable asphalt emulsion.
(3) compared with acrylamide, emulsified asphalt de-emulsification speed is slow, such that it is able in for N,N-DMAA
Type or slow breaking asphalt emulsifier are split, is for those skilled in the art the prominent technique effect expected.
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
Emulsifying agent, such as in early days with acrylamide as raw material, the polycation acid amide type asphalt emulsifier for preparing.And the present invention is adopted
With N,N-DMAA, emulsified asphalt de-emulsification speed is slow, and type or slow breaking asphalt emulsifier can be split as in.
In pavement construction, emulsified asphalt demulsification refers to that after asphalt emulsion is contacted with building stones, bitumen particle divides from emulsion
Separate out and, coalesce and sprawl in stone surface, form one layer of process of continuous asphalt film, during demulsification, pitch breast
Moisture evaporation in liquid.
The factor of influence emulsified asphalt demulsification is a lot, excludes the influence of building stones, and emulsifying agent is 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 emulsifying agent can be changed, by the analysis of inventor, reason of both there may be of tracing it to its cause：On the one hand, with
Acrylamide is compared, and due to hydrogen is replaced with into methyl, increased the lipophilic group in the asphalt emulsifier molecular structure of preparation, and
Lipophilic group more can be inserted firmly in 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, because N,N-DMAA contains two methyl so that breast
The steric hindrance of agent molecule is relatively large, building stones when being contacted with bitumen particle, it is necessary to overcome larger steric hindrance so that
So that de-emulsification speed is slower.
(4) when emulsified asphalt is prepared, the volume of asphalt emulsifier is less, about 0.8-2.5%, can be split in
Type or slow breaking asphalt emulsifier.
It is generally acknowledged that during the large usage quantity of cation asphalt emulgent, type or slow breaking emulsified asphalt are split in could preparing,
And the consumption of emulsified asphalt of the invention is less, illustrate to split the excellent effect of type or slow breaking emulsified asphalt in preparing.
(5) it is of the invention using N,N-DMAA as the reaction raw materials of asphalt emulsifier, due to N, N- dimethyl
Acrylamide material state 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.
Additionally, the course of reaction of N,N-DMAA is exothermic reaction, the heat needed for itself can providing reaction
Amount, reduces the introducing of external source heat in course of reaction, reduces the energy consumption of reaction.
(6) present invention use specific raw material N, N- DMAAs, 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
Emulsifying agent, the polycation teritary amide type asphalt emulsifier prepared using the present invention has good emulsifiability, prepares
Emulsified asphalt property indices it is excellent, the pitch of emulsifiable various different models, the emulsified asphalt of preparation is fine and smooth uniform,
Attached property is wrapped up in good gathering materials.Obtained emulsified asphalt presses the cationic emulsified bitumen professional standard of Chinese transportation portion formulation
(JTJ052-2000) detected, properties can meet standard requirement.Suitable for spilling for highway priming oil or sticking layer oil
Cloth, and for the construction such as slurry seal and micro-surface area, the characteristic of asphalt emulsifier is split and split slowly in having.Using of the invention
Emulsifying agent is split or slow-breaking emulsified asphalt in preparing, and compound can be made to have preferable mobility and permeability, is conducive to
Filling and the crack on repairing road surface, improve the compactibility and water proofing property on road surface.
(7) raw materials used N- hydrogenated-tallow group -1 of the invention, 3- trimethylene diamines is cheap, wide material sources, asphalt emulsifier life
Produce low cost, and split type in polycation teritary amide class or slow breaking asphalt emulsifier provides good basis to prepare.
(8) amide groups amine emulsifying agent reaction temperature general control is and of the invention at 140~180 DEG C in the prior art
The preparation method process is simple of polycation teritary amide type asphalt emulsifier, pyroreaction is not needed, reducing energy consumption is greatlyd save
Production cost.
Specific embodiment
It is noted that described further below is all exemplary, it is intended to provide further instruction to the present invention.Unless another
Indicate, all technologies used herein and scientific terminology are with 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 illustrative embodiments of the invention.As used herein, unless the context clearly indicates otherwise, otherwise singulative
Be also intended to include plural form, additionally, it should be understood that, when in this manual use term "comprising" and/or " bag
Include " when, it indicates existing characteristics, step, operation, component and/or combinations 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, further optimize the performance of asphalt emulsifier, the performance compared to early stage result of study, with more show
The difference of work.Specific technical scheme there is provided the asphalt emulsification that type or slow breaking are split in a kind of polycation teritary amide class
Agent, its molecular structure is：
Wherein, R=methyl (- CH3), ethyl (- C2H5), ethoxy (- C2H4OH)。
In one embodiment, the drip of type or slow breaking is provided in a kind of polycation teritary amide class of present invention offer
The preparation method of blue or green emulsifying agent, comprises 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 the triethanolamine aqueous solution, and intermediate II is
R is methyl (- CH3), ethyl (- C2H5) or ethoxy (- C2H4OH)；
(3) reaction intermediate II is added drop-wise in reaction intermediate I, is reacted, that is, obtain polycation teritary amide type pitch
Emulsifying agent.
The preparation order of step (1) and (2) can be exchanged.
Preferably, in the present invention, N- hydrogenated-tallow group -1,3- trimethylene diamines, alcohols solvent, N, N- dimethyl allenes
Acid amides, low carbon number tertiary amine, technical hydrochloric acid, the mol ratio of epoxychloropropane are 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 many 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 can not form polycation teritary amide
Type asphalt emulsifier.Especially for the addition of N,N-DMAA, the excessive or very few of its addition all can shadow
The performance of the asphalt emulsifier for preparing is rung, especially the water-separating time of asphalt emulsifier.
In another embodiment of the present invention, in step (1), reaction temperature is 60~80 DEG C, preferably 65~75
DEG C, the reaction time is 2~4h.
Preferably, the alcohols solvent is ethanol, methyl alcohol 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.Find after further study, the reaction temperature of the step is low most important to the high income of final reacting product, the temperature of reaction
Height is spent, then the epoxy bond of reaction intermediate II can be caused to open, it is further reacted generation with reaction intermediate I many
Cation 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 have impact on reaction process.To improve the yield of final products, the present invention has carried out excellent to this temperature conditions
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 splits type or slow breaking emulsified asphalt in also providing one kind, and the preparation method of the emulsified asphalt includes following step
Suddenly：
Above-mentioned polycation teritary amide type asphalt emulsifier is added water and is configured to the aqueous solution, pH is to 2-3 for regulation, is heated to
60-70 DEG C, soap lye is obtained；Pitch after heating and emulsifying agent soap lye are emulsified by colloid mill and prepares cation emulsified drip
It is blue or 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 consumption 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 during the large usage quantity of cation asphalt emulgent, type is split in could preparing
Or slow breaking emulsified asphalt, and the consumption of emulsified asphalt of the invention is less, illustrates to split type or slow breaking emulsified asphalt in preparing
Excellent effect, be especially suitable for prepare in split type or slow breaking emulsified asphalt, type or slow breaking asphalt emulsifier are split in enriching
Species.
In order that obtaining those skilled in the art can clearly understand the technical scheme of the application, below with reference to tool
The embodiment of body describes the technical scheme of the application in detail with comparative example.
Embodiment 1
(1) preparation of polycation teritary amide type asphalt emulsifier：
1) 326.0gN- hydrogenated-tallow group -1 is added in the reactor, and 3- trimethylene diamines, 330g isopropanols, heating stirring is molten
Solution.Then 302.4g N,N-DMAAs, 70 DEG C of stirring reaction 3h are gradually added into.
The above-mentioned intermediate product of synthesis carries out FTIR detections after recrystallizing separating-purifying, as a result as follows：2927cm-1It is Asia
The asymmetric stretching vibration absworption peak of methyl, 2846cm-1For the symmetrical stretching vibration of methylene receives peak, 1652cm-1It is amide groups
Middle C=O stretching vibration absworption peaks, 1500cm-1And 1471cm-1For the asymmetric curvature of methylene is vibrated, 1404cm-1It is methyl
Asymmetric curvature vibration, 1271cm-1And 1139cm-1It is C-N stretching vibration absworption peaks, 1053cm-1For C-H in-plane bendings shake
Dynamic absworption peak, 723cm-1It is methylene rocking vibration absworption 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 of stirring reaction 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 of stirring reaction 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-1It is O-H stretching vibrations
Absworption peak, 2925cm-1It is the asymmetric stretching vibration absworption peak of methylene, 2848cm-1For the symmetrical stretching vibration of methylene is received
Peak, 1629cm-1It is C=O stretching vibration absworption peaks, 1470cm in amide groups-1For the asymmetric curvature of methylene is vibrated,
1407cm-1For the asymmetric curvature of methyl is vibrated, 1263cm-1And 1145cm-1It is C-N stretching vibration absworption peaks, 1060cm-1For
C-OH stretching vibration absworption peaks, 958cm-1It is O-H out-of-plane bending vibration absworption peaks, 630cm-1It is methylene rocking vibration
Absworption peak.
Reaction equation is as follows：
(2) preparation of emulsified asphalt：
AH-90# pitch 300g are taken, 125 DEG C are heated to, 7.5g asphalt emulsifiers manufactured in the present embodiment are added to 200g
In water, pH value being adjusted to 2-3 with technical hydrochloric acid, being heated to 65 DEG C, soap lye is obtained.Pitch and emulsifying agent soap lye are passed through into colloid mill
Cationic emulsified asphalt is prepared in emulsification.
(3) emulsified asphalt performance detection：
Obtained emulsified asphalt is entered by the cationic emulsified bitumen professional standard (JTJ052-2000) that Chinese transportation portion works out
Row detection, it is as a result as follows：Emulsified asphalt manufactured in the present embodiment is uniform, fine and smooth, and bitumen content is 59%, and surplus is on sieve
0.01%, area is wrapped more than 2/3 with mineral aggregate, storage stability (1d) is 0.8%；In de-emulsification speed experiment, using B classes
Material, the mixing time can be more than 1min；Mixed and stirred using material is mixed and stirred, (as a comparison, can tested on an equal basis for 65 seconds the mixing time
Under the conditions of, reaction raw materials N,N-DMAA is replaced with into acrylamide, mixed and stirred using material is mixed and stirred, can mix when
Between be 4s).Show that asphalt emulsion prepared by the emulsifying agent 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) 326.0gN- hydrogenated-tallow group -1 is added in the reactor, and 3- trimethylene diamines, 330g isopropanols, heating stirring is molten
Solution.Then 302.4g N,N-DMAAs, 70 DEG C of stirring reaction 3h are gradually added into.
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 of stirring reaction 3h obtain reaction intermediate B.The reaction intermediate B drops that will be prepared
It is added to above-mentioned steps 1) in synthetic product, 65 DEG C of stirring reaction 3h.Polycation teritary amide type asphalt emulsifier is obtained, breast is given over to
Change asphalt test.
Synthetic product carries out FTIR detections after recrystallizing separating-purifying, as a result as follows：3406cm-1It is O-H stretching vibrations
Absworption peak, 2927cm-1It is the asymmetric stretching vibration absworption peak of methylene, 2854cm-1For the symmetrical stretching vibration of methylene is received
Peak, 1620cm-1It is C=O stretching vibration absworption peaks, 1471cm in amide groups-1For the asymmetric curvature of methylene is vibrated,
1400cm-1For the asymmetric curvature of methyl is vibrated, 1270cm-1And 1163cm-1It is C-N stretching vibration absworption peaks, 1085cm-1For
C-OH stretching vibration absworption peaks, 709cm-1It is methylene rocking vibration absworption peak.
Reaction equation is as follows：
(2) preparation of emulsified asphalt：
AH-70# pitch 300g are taken, 125 DEG C are heated to, 7.5g asphalt emulsifiers manufactured in the present embodiment are added to 200g
In water, pH value being adjusted to 2-3 with technical hydrochloric acid, being heated to 65 DEG C, soap lye is obtained.Pitch and emulsifying agent 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, and bitumen content is 60%, is remained on sieve
Balance of 0.02%, area is wrapped 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 be 125 seconds (as a comparison, same
Under Deng experiment condition, reaction raw materials N,N-DMAA is replaced with into acrylamide, mixed and stirred using material is mixed and stirred, can
Duration of mixing is 4s).Show that asphalt emulsion prepared by the emulsifying agent 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) 326.0gN- hydrogenated-tallow group -1 is added in the reactor, and 3- trimethylene diamines, 330g isopropanols, heating stirring is molten
Solution.Then 302.4g N,N-DMAAs, 65 DEG C of stirring reaction 4h are gradually added into.
2) 365.1g 85% (mass fraction) triethanolamine is added in the reactor, is gradually added into (the matter of 252.7g 30%
Amount fraction) technical hydrochloric acid, then 189.5g epoxychloropropane is gradually added into, 55 DEG C of stirring reaction 2h obtain reaction intermediate C.Will
The reaction intermediate C of preparation is added drop-wise to above-mentioned steps 1) in synthetic product, 70 DEG C of stirring reaction 2h.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-1It is O-H stretching vibrations
Absworption peak, 2924cm-1It is the asymmetric stretching vibration absworption peak of methylene, 2847cm-1For the symmetrical stretching vibration of methylene is received
Peak, 1627cm-1It is C=O stretching vibration absworption peaks, 1463cm in amide groups-1For the asymmetric curvature of methylene is vibrated,
1398cm-1For the asymmetric curvature of methyl is vibrated, 1265cm-1And 1153cm-1It is C-N stretching vibration absworption peaks, 1060cm-1For
C-OH stretching vibration absworption peaks, 931cm-1It is O-H out-of-plane bending vibration absworption peaks, 670cm-1It is methylene rocking vibration
Absworption peak.
Reaction equation is as follows：
(2) preparation of emulsified asphalt：
A-100# pitch 300g are taken, 125 DEG C are heated to, 7.5g asphalt emulsifiers manufactured in the present embodiment are added to 200g
In water, pH value being adjusted to 2-3 with technical hydrochloric acid, being heated to 65 DEG C, soap lye is obtained.Pitch and emulsifying agent 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, and bitumen content is 58%, is remained on sieve
Balance of 0.02%, area is wrapped 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 be 31 seconds (as a comparison, same
Under Deng experiment condition, reaction raw materials N,N-DMAA is replaced with into acrylamide, mixed and stirred using material is mixed and stirred, can
Duration of mixing is 3s).The asphalt emulsion for showing emulsifying agent 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 ", is prepared
Method with embodiment 1 (i.e.：Embodiment 1 in the A of CN 105399645), prepare asphalt emulsifier.
The emulsifying capacity of the asphalt emulsifier prepared to embodiment 1 and comparative example 1 is measured, signified breast in the present invention
Change ability refers to：Asphalt emulsifier Jiang Shui and the immiscible liquid of oily two class are changed into the ability of emulsion.
The present invention determines emulsifying capacity using graduated cylinder method, and breast is thoroughly mixed to form according to asphalt emulsifier and atoleine
Shape liquid, then the time required for separating 10ml water after standing, that is, water-separating time, thus evaluate 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, be placed in the conical flask of the 100ml of glass stopper, then the atoleine of 40ml is measured with pipette
It is placed in this conical flask.By tight glass stopper, then fierce vibration 5 times up and down, vibrate 5 times, then stand 1min again after standing 1min；
After being so repeated 5 times, this emulsion 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
Separate, water is met and appears in the lower floor of graduated cylinder slowly, when water mutually separates 10ml water, record now separate used by water when
Between, using this time as emulsifying capacity relatively, water-separating time then emulsifying capacity more long is stronger.
Experiment three times is repeated, 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.By water-separating time as can be seen that with N, N- diformazans
Base acrylamide is that the emulsifying capacity of asphalt emulsifier prepared by raw material will be significantly better than the drip prepared as raw material with acrylamide
Blue or green emulsifying agent.
Comparative example 2
By the preparation process 2 of the asphalt emulsifier of embodiment 1) in reaction temperature be adjusted to 30 DEG C, remaining with embodiment 1,
Prepare asphalt emulsifier.
Result finds：Comparative example 2 during asphalt emulsifier is prepared, the particularly preparation process of reaction intermediate II
In, there is layering in reaction system, reduces the yield of reaction rate and reaction intermediate II.
Comparative example 3
By the preparation process 2 of the asphalt emulsifier of embodiment 1) in reaction temperature be adjusted to 70 DEG C, remaining with embodiment 1,
Prepare asphalt emulsifier.
Result finds, comparative example 3 during asphalt emulsifier is prepared, the particularly preparation process of reaction intermediate II
In, through to product --- reaction intermediate II detects that the epoxy bond of reaction intermediate II is much opened, epoxy bond
After being opened so that reaction intermediate II and reaction intermediate I can not further react and prepare asphalt emulsifier, reduce
The yield of final product asphalt emulsifier.
Above-described embodiment is the present invention preferably implementation method, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from Spirit Essence of the invention and the change, modification, replacement made under principle, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. the asphalt emulsifier of type or slow breaking is split in a kind of polycation teritary amide class, it is characterized in that, its molecular structural formula is：
Wherein, R=methyl (- CH3), ethyl (- C2H5), ethoxy (- C2H4OH)。
2. the preparation method of the asphalt emulsifier of type or slow breaking is split in the polycation teritary amide class described in claim 1, its
It is characterized in comprise the following steps：
(1) by N- hydrogenated-tallow group -1,3- trimethylene diamines, alcohols solvent and N,N-DMAA hybrid reaction are obtained
Reaction intermediate I, intermediate compound I is
(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 trimethylamine aqueous solution, triethylamine or the triethanolamine aqueous solution, intermediate II isR is
Methyl (- CH3), ethyl (- C2H5) or ethoxy (- C2H4OH)；
(3) reaction intermediate II is added drop-wise in reaction intermediate I, reacted, that is, obtain splitting in polycation teritary amide class type or
The asphalt emulsifier of slow breaking；
Above step does not influence to prepare, and can exchange order.
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- DMAAs, low carbon number tertiary amine, technical hydrochloric acid, the mol ratio of epoxychloropropane are 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, preferably
65-75 DEG C, the time of reaction is 2-4h.
5. preparation method as claimed in claim 2, it is characterized in that：In step (1), the alcohols solvent be ethanol, methyl alcohol or
Isopropanol.
6. 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.
7. preparation method as claimed in claim 2, it is characterized in that：In step (3), the temperature of reaction is 60-80 DEG C, preferably
65-75 DEG C, the time of reaction is 2-4h.
8. the polycation teritary amide class asphalt emulsifier described in claim 1 splits type in preparation or slow breaking is cation emulsified
Application in pitch.
9. a kind of preparation method of cationic emulsified bitumen, comprises the following steps：By the tertiary acyl of polycation described in claim 1
Amine type asphalt emulsifier adds water and is configured to the aqueous solution, and pH is to 2-3 for regulation, is heated to 60-70 DEG C, and soap lye is obtained；After heating
Pitch and emulsifying agent soap lye are emulsified by colloid mill prepares cationic emulsified bitumen；
The consumption of the polycation teritary amide type asphalt emulsifier is the 0.8-2.5% of the emulsified asphalt gross mass for preparing.
10. the cationic emulsified bitumen that the preparation method described in claim 9 is obtained.
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