CN107056637A - A kind of dication teritary amide type asphalt emulsifier and preparation method thereof - Google Patents
A kind of dication teritary amide type asphalt emulsifier and preparation method thereof Download PDFInfo
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- CN107056637A CN107056637A CN201710050812.0A CN201710050812A CN107056637A CN 107056637 A CN107056637 A CN 107056637A CN 201710050812 A CN201710050812 A CN 201710050812A CN 107056637 A CN107056637 A CN 107056637A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
- C07C237/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton
- C07C237/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
- C07C237/06—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/36—Compounds containing oxirane rings with hydrocarbon radicals, substituted by nitrogen atoms
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- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention discloses a kind of dication teritary amide type asphalt emulsifier, its molecular structure is：Wherein, R=methyl (CH3), ethyl (C2H5), ethoxy (C2H4OH)；It is to be prepared from by the raw material of following mol ratio：Octadecylamine, alcohols solvent, N, N DMAAs, low carbon number tertiary amine, technical hydrochloric acid, the mol ratio of epoxychloropropane are 1mol：(4.00‑9.00)mol：(2.00‑2.10)mol：(1.02‑1.10)mol：(1.02‑1.10)mol：(1.02‑1.08)mol.The present invention is with N, and N DMAAs are as the reaction raw materials of asphalt emulsifier, and it is liquid charging stock, convenient charging and the mixing of other raw materials；And course of reaction is exothermic reaction, reduces energy consumption of reaction.The production cost of asphalt emulsifier of the present invention is low, technique is simple, do not need pyroreaction.
Description
Technical field
The present invention relates to a kind of dication teritary amide type asphalt emulsifier and preparation method thereof, belong to fine chemical technology
Field.
Background technology
Emulsified asphalt especially cationic emulsified bitumen can have due to that with energy-conserving and environment-protective, can improve execution conditions
Effect reduces many excellent application characteristics such as pitch overaging, and is widely used in road construction and pavement preservation.
The most critical factor for influenceing emulsified asphalt pavement performance is exactly asphalt emulsifier, at present domestic and international cationic pitch
Emulsifying agent principal item has organic amine, quaternary ammonium salt, imidazolines, amide-type etc., the wherein application of quaternary ammonium salt emulsifying agent most
Extensively.With the application of cationic emulsified bitumen, the kind of asphalt emulsifier is also gradually enriched.
United States Patent (USP) USP4338136 is with C12-18Long carbon chain aliphatic acid reacts preparation under certain condition with diethylenetriamine
Asphalt emulsifier.The shortcoming of this method is that the asphalt emulsifier prepared is expensive, when being constructed for slurry seal, is demulsified the time
Long, molding time is slow, and the open to traffic time is long.Chinese patent CN1096714 utilizes oil plant by-product aphthenic acids and alkenyl polyamine
Reaction, prepares asphalt emulsifier.The shortcoming of this method be the raw material supply of emulsifying agent by severely restricts, be unfavorable for promote should
With.Chinese patent CN1861721A is related to a kind of rosin cation asphalt emulgent.The emulsifying agent is by rosin and alkenyl polyamine
Reaction, obtain rosin intermediate, then, with different types of quaternary ammonium salt intermediate be condensed, be made function admirable rosin sun from
Sub- asphalt emulsifier.The shortcoming of this method is that reactions steps are cumbersome, it is necessary to pyroreaction.Chinese patent CN101712625A is related to
And a kind of method for synthesizing amphoteric slow-breaking quick-setting asphalt emulsifier, using oleic acid and polyamines reaction generation polyamide-polyamino, then add
Halogenating reaction occurs for monoxone, and asphalt emulsifier is made.The shortcoming of this method is to need pyroreaction when preparing.Chinese patent
CN101745340A is related to a kind of cation asphalt emulgent preparation method, and host is obtained by mixed organic acid and organic amine reaction
Intermediate, then carry out quaterisation be made, assistant agent be nonionic surfactant and modified additive.The shortcoming of this method is system
Standby complex steps, cost is higher, it is necessary to pyroreaction.Chinese patent 201310722961.9 discloses a kind of Acid modified starch
The preparation method of cation slow-breaking slow-curing asphalt emulsifier, provides for asphalt emulsion and splits slow hardening performance slowly.
The deficiency of above-mentioned cationic asphalt emulsifier and preparation method thereof generally existing is：Prepare the raw material of emulsifying agent into
This is higher, and source is restricted, and pyroreaction is needed during preparation, higher to productive experiment equipment requirement.
Present inventor proposes a kind of dication acid amide type asphalt emulsifier in early-stage Study, and it is first with third
Acrylamide as asphalt emulsifier reaction raw materials, by adding acrylamide to citing approvingly in the molecular structure of asphalt emulsifier
Entered bisamide base, added the hydrophily of asphalt emulsifier, and emulsifying agent and pitch compatibility.But follow-up further
Research in find, asphalt emulsifier is prepared by raw material of acrylamide and still suffers from some areas for improvement, for example：Propylene
Acid amides is solid material, it has not been convenient to feeds and is mixed with other raw materials；In addition, the reaction that acrylamide is participated in is anti-for heat absorption
Should, therefore need increase to introduce external source heat in the preparation process of asphalt emulsifier, add energy consumption.
The content of the invention
For above-mentioned prior art, it is an object of the invention to provide a kind of dication teritary amide type asphalt emulsifier and its
Preparation method.The present invention is using N,N-DMAA as the reaction raw materials of asphalt emulsifier, and it is liquid charging stock, convenient
Charging and the mixing of other raw materials；And course of reaction is exothermic reaction, reduces energy consumption of reaction.The life of asphalt emulsifier of the present invention
Production cost is low, technique is simple, do not need pyroreaction.
To achieve the above object, the present invention uses following technical proposals：
A kind of dication teritary amide type asphalt emulsifier, its molecular structure is：
Wherein, R=methyl (- CH3), ethyl (- C2H5), ethoxy (- C2H4OH)。
It is preferred that, dication teritary amide type asphalt emulsifier of the present invention, by the raw material system of following mol ratio
It is standby to form：
Octadecylamine, alcohols solvent, N, N- DMAAs, low carbon number tertiary amine, technical hydrochloric acid, epoxychloropropane rub
You are than being 1mol：(4.00-9.00)mol：(2.00-2.10)mol：(1.02-1.10)mol：(1.02-1.10)mol：(1.02-
1.08)mol。
The alcohols solvent is ethanol, methanol or isopropanol.
The low carbon number tertiary amine is trimethylamine aqueous solution, triethylamine or the triethanolamine aqueous solution.
The present invention also provides the preparation method of above-mentioned dication teritary amide type asphalt emulsifier, comprises the following steps：
(1) octadecylamine, alcohols solvent and N,N-DMAA are mixed, reaction obtains reaction intermediate I, institute
The molecular formula for stating reaction intermediate I is：C18H37N(CH2CH2CON(CH3)2)2；
(2) low carbon number tertiary amine, technical hydrochloric acid and epoxychloropropane are mixed, reaction, obtains reaction intermediate II, it is described anti-
The structural formula for answering intermediate II is：
(3) reaction intermediate II is added drop-wise in reaction intermediate I, reacts, that is, obtain dication teritary amide type pitch
Emulsifying agent.
In above-mentioned preparation method, octadecylamine, alcohols solvent, N,N-DMAA, low carbon number tertiary amine, Nacl
The mol ratio that acid, epoxychloropropane are added is 1mol：(4.00-9.00)mol：(2.00-2.10)mol：(1.02-1.10)mol：
(1.02-1.10)mol：(1.02-1.08)mol.
By lot of experiment validation and analysis, each raw material of above-mentioned molar ratio cause double 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 dication teritary amide
Type asphalt emulsifier.Especially for the addition of N,N-DMAA, the excessive or very few of its addition all can shadow
Ring the water-separating time of the performance, especially asphalt emulsifier of the asphalt emulsifier prepared.
It is preferred that, in step (1), the temperature of reaction is 60-80 DEG C, more preferably 65-75 DEG C, and the time of reaction is
2-4h。
It is preferred that, in step (2), the temperature of reaction is 47-55 DEG C, and the reaction time is 2-3h.In the step, the temperature of reaction
Degree condition is very crucial for reaction intermediate II preparation.Present invention research finds that the temperature of reaction is too high, then can cause anti-
Answer the epoxy bond of intermediate II to open, it can not be further reacted the type drip of generation dication teritary amide with reaction intermediate I
Blue or green emulsifying agent, 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.Verify and analyze through test of many times, when reaction temperature is 47-55 DEG C, reaction intermediate II preparation effect is most
It is excellent.
It is preferred that, in step (3), the temperature of reaction is 60-80 DEG C, more preferably 65-75 DEG C, and the time of reaction is
2-4h。
It is preferred that, in step (2), the concentration of the technical hydrochloric acid is 30% (mass fraction), trimethylamine aqueous solution it is dense
Spend for 33% (mass fraction).
The preparation method of above-mentioned dication teritary amide type asphalt emulsifier, specifically includes following steps：
(1) octadecylamine is added in reaction vessel, adds alcohols solvent, heating stirring dissolving, then N, N- is added portionwise
DMAA, after addition is finished, in 60-80 DEG C of stirring reaction 2-4h, obtains reaction intermediate I；
(2) low carbon number tertiary amine is added in another reactor, technical hydrochloric acid is added portionwise, after technical hydrochloric acid addition is finished,
Epoxychloropropane is added portionwise again, after epoxychloropropane addition is finished, in 47-55 DEG C of stirring reaction 2-3h, obtains 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 added portionwise in reaction intermediate I, 60-80 DEG C of reaction 2-4h, that is, obtain double sun from
Zishu acid amide type asphalt emulsifier.
Above-mentioned dication teritary amide type asphalt emulsifier is also preparing the application split soon in type cationic emulsified bitumen
Protection scope of the present invention.
The present invention also provides a kind of preparation method of cationic emulsified bitumen, and step is as follows：
Above-mentioned dication 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 made；Pitch after heating and emulsifying agent soap lye are prepared into cation emulsified drip by colloid mill emulsification
It is blue or green；
The consumption of the dication teritary amide type asphalt emulsifier is the 0.8- of the emulsified asphalt gross mass prepared
2.5%.
Beneficial effects of the present invention：
(1) present invention is by the reasonable selection to reaction raw materials, prepared a kind of double sun with brand new from
Zishu acid amide type asphalt emulsifier.Wherein, the present invention is used as preparation cationic pitch using N,N-DMAA first
The reaction raw materials of emulsifying agent, compared with acrylamide, two hydrogen are replaced by methyl on the amide groups nitrogen of acrylamide molecules, copolymerization
The hydrolytic stability of thing is significantly improved than acrylamide, active double bond in molecule, make it easier to autohemagglutination or and other
Monomer copolymerization.
Asphalt emulsifier includes hydrophilic group and lipophilic group, the lipophilic group in emulsification in asphalt emulsification agent molecule
Start close to pitch particle after into water, then enter back into pitch particle so that the surface of each pitch particle
Countless emulsifier molecules are all have accumulated, pitch particle to including, a stratum boundary facial mask are formed.Further, since pitch is newborn
After agent molecule is ionized in water so that interfacial film has corresponding electric charge, interface charge layer thus form.Interfacial film
It is formed such that water and pitch are separated, reduces the interfacial tension between water and pitch, a kind of mechanical protection is played to pitch particle
Effect so that asphalt emulsion can keep stability and uniformity within a certain period of time；Interface charge layer can make pitch particle
It is mutually exclusive between particle, maintain a certain distance, hence in so that pitch particle aggregation is gone less than one piece, serve and mutually divide
Scattered effect.
N,N-DMAA, due to hydrogen atom is replaced with into methyl, adds preparation compared with acrylamide
Lipophilic group in asphalt emulsifier molecular structure, is more conducive to form interfacial film, the interfacial tension between reduction water and pitch；Separately
Outside, ionizing power of the asphalt emulsifier prepared by reaction raw materials of N,N-DMAA in water is stronger, Ke Yi electricity
More cations are separated out, make the effect of interface charge layer stronger；So that pitch can emulsify in water and can be equal
It is even scattered to form metastable asphalt emulsion.
(2) 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
It is even.
In addition, the course of reaction 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 course of reaction, reduces the energy consumption of reaction.
(3) present invention uses specific raw material N, N- DMAAs, octadecylamine, low carbon number tertiary amine, hydrochloric acid and ring
Oxygen chloropropane, the asphalt emulsifier of dication teritary amide type chemical constitution of the generation with certain HLB value, using present invention system
Standby dication teritary amide type asphalt emulsifier has good emulsifiability, the properties of the emulsified asphalt prepared
Index is excellent, the pitch of emulsifiable a variety of different models, and the emulsified asphalt of preparation is fine and smooth uniform, and attached property is wrapped up in good gathering materials.System
The cationic emulsified bitumen professional standard (JTJ052-2000) worked out by Chinese transportation portion of emulsified asphalt detected, respectively
Item performance can meet standard requirement.Sealed suitable for the spread of highway priming oil or sticking layer oil, and for crushed stone sealing, aggregate chips
Layer, mist sealing and reparation slight check crack in road surface etc., with the characteristic for splitting asphalt emulsifier soon.
(4) the raw material octadecylamine of dication teritary amide type asphalt emulsifier of the invention is relative to current cationic
Raw material used in asphalt emulsifier is cheap, wide material sources, and asphalt emulsifier production cost is low, and to prepare the tertiary acyl of dication
Amine type asphalt emulsifier provides good basis.
(5) in the prior art amide groups amine emulsifying agent reaction temperature general control at 140~180 DEG C, and the present invention
The preparation method technique of dication teritary amide type asphalt emulsifier is simple, do not need pyroreaction, reduces energy consumption, greatlys save
Production cost.
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 embodiment, and be not intended to restricted root
According to the illustrative 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 this manual using term "comprising" and/or " bag
Include " when, it indicates existing characteristics, step, operation, component and/or combinations thereof.
As background technology is introduced, cation asphalt emulgent is prepared still by raw material of acrylamide in the prior art
Come with some shortcomings, in order to solve technical problem as above, present applicant proposes a kind of dication teritary amide type asphalt emulsification
Agent, its molecular structure is：
There is provided the preparation side of above-mentioned dication teritary amide type asphalt emulsifier in one embodiment of the invention
Method, comprises the following steps：
(1) octadecylamine is added in reaction vessel, adds alcohols solvent, heating stirring dissolving, then N, N- is added portionwise
DMAA, after addition is finished, in 60-80 DEG C of stirring reaction 2-4h, obtains reaction intermediate I；
(2) low carbon number tertiary amine is added in another reactor, technical hydrochloric acid is added portionwise, after technical hydrochloric acid addition is finished,
Epoxychloropropane is added portionwise again, after epoxychloropropane addition is finished, in 47-55 DEG C of stirring reaction 2-3h, obtains 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 added portionwise in reaction intermediate I, 60-80 DEG C of reaction 2-4h, that is, obtain double sun from
Zishu acid amide type asphalt emulsifier.
It is used as preferred embodiment, octadecylamine, alcohols solvent, N,N-DMAA, low carbon number tertiary amine, industry
Hydrochloric acid, the mol ratio of epoxychloropropane are 1mol：(4.00-9.00)mol：(2.00-2.10)mol：(1.02-1.10)mol：
(1.02-1.10)mol：(1.02-1.08)mol.
The alcohols solvent is ethanol, methanol or isopropanol.
The low carbon number tertiary amine is trimethylamine aqueous solution, triethylamine or the triethanolamine aqueous solution.
By lot of experiment validation and analysis, each raw material of above-mentioned molar ratio cause double 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 dication teritary amide
Type asphalt emulsifier.Especially for the addition of N,N-DMAA, the excessive or very few of its addition all can shadow
Ring the water-separating time of the performance, especially asphalt emulsifier of the asphalt emulsifier prepared.
In order that the technical scheme of the application can clearly be understood by obtaining those skilled in the art, below with reference to tool
The embodiment of body describes the technical scheme of the application in detail with comparative example.
Used raw material, reagent are conventional chemical product in the embodiment of the present invention and comparative example, can pass through market
It is commercially available.
Embodiment 1：
(1) preparation of dication teritary amide type asphalt emulsifier：
1) 269.5g octadecylamines, 260g isopropanols, heating stirring dissolving are added in the reactor.Then it is gradually added into
203.2g N,N-DMAAs, 70 DEG C of stirring reaction 3h, obtain reaction intermediate I.
The above-mentioned reaction intermediate I of synthesis carries out FTIR detections after recrystallizing separating-purifying, as a result as follows：2910cm-1
For the asymmetric stretching vibration absworption peak of methylene, 2840cm-1Peak, 1650cm are received for the symmetrical stretching vibration of methylene-1With
1625cm-1For C=O stretching vibration absworption peaks, 1460cm in amide groups-1Vibrated for the asymmetric curvature of methylene, 1390cm-1
Vibrated for the asymmetric curvature of methyl, 1263cm-1And 1153cm-1For C-N stretching vibration absworption peaks, 777cm-1And 719cm-1For
Methylene rocking vibration absworption peak.
2) 193.1g 33% (mass fraction) trimethylamine aqueous solution is added in another reactor, 131.2g is gradually added into
30% (mass fraction) technical hydrochloric acid, then 97.1g epoxychloropropane is gradually added into, 50 DEG C of stirring reaction 2.5h are obtained in reaction
Mesosome II.
3) by above-mentioned steps 2) prepare reaction intermediate II be added drop-wise to above-mentioned steps 1) synthesis reaction intermediate I in,
70 DEG C of stirring reaction 2h.Dication teritary amide type asphalt emulsifier is obtained, emulsified asphalt experiment is given over to.
Synthetic product carries out FTIR detections after recrystallizing separating-purifying, as a result as follows：3404cm-1For O-H stretching vibrations
Absworption peak, 2920cm-1For the asymmetric stretching vibration absworption peak of methylene, 2852cm-1Received for the symmetrical stretching vibration of methylene
Peak, 1629cm-1For C=O stretching vibration absworption peaks, 1471cm in amide groups-1Vibrated for the asymmetric curvature of methylene,
1417cm-1Vibrated for the asymmetric curvature of methyl, 1262cm-1And 1152cm-1For C-N stretching vibration absworption peaks, 1053cm-1For
C-OH stretching vibration absworption peaks, 723cm-1For methylene rocking vibration absworption peak.
Reaction equation is as follows：
(2) preparation of emulsified asphalt：
AH-90# pitch 300g are taken, 125 DEG C are heated to, 10.0g asphalt emulsifiers manufactured in the present embodiment are added to
In 200g water, pH value is adjusted to 2-3 with technical hydrochloric acid, 65 DEG C are heated to, soap lye is made.Pitch and emulsifying agent soap lye are passed through into glue
Cationic emulsified asphalt is prepared in body mill emulsification.
(3) emulsified asphalt performance detection：
The cationic emulsified bitumen professional standard (JTJ052-2000) that obtained emulsified asphalt is worked out by Chinese transportation portion is entered
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 60%, and surplus is on sieve
0.02%, area is wrapped more than 2/3 with mineral aggregate, and storage stability (1d) is 0.9%；In de-emulsification speed experiment, using B classes
Material, can be 8 seconds the mixing time；Mixed and stirred using material is mixed and stirred, can be 5 seconds the mixing time.Show pitch prepared by the emulsifying agent
Emulsion is splits type cationic emulsified bitumen soon, and properties can meet standard requirement.
Embodiment 2：
(1) preparation of dication teritary amide type asphalt emulsifier：
1) 269.5g octadecylamines, 260g isopropanols, heating stirring dissolving are added in the reactor.Then it is gradually added into
203.2g N,N-DMAAs, 70 DEG C of stirring reaction 3h, obtain reaction intermediate I.
2) 109.1g triethylamines are added in another reactor, 131.2g 30% (mass fraction) Nacl is gradually added into
Acid, then 97.1g epoxychloropropane is gradually added into, 47 DEG C of stirring reaction 3h obtain reaction intermediate II.
3) the reaction intermediate II of preparation is added drop-wise to above-mentioned steps 1) in the reaction intermediate I of synthesis, 65 DEG C of stirrings are anti-
Answer 3h.Dication teritary amide type asphalt emulsifier is obtained, emulsified asphalt experiment is given over to.
Synthetic product carries out FTIR detections after recrystallizing separating-purifying, as a result as follows：3410cm-1For O-H stretching vibrations
Absworption peak, 2925cm-1For the asymmetric stretching vibration absworption peak of methylene, 2846cm-1Received for the symmetrical stretching vibration of methylene
Peak, 1622cm-1For C=O stretching vibration absworption peaks, 1471cm in amide groups-1Vibrated for the asymmetric curvature of methylene,
1409cm-1Vibrated for the asymmetric curvature of methyl, 1263cm-1And 1163cm-1For C-N stretching vibration absworption peaks, 1047cm-1For
C-OH stretching vibration absworption peaks, 725cm-1For methylene rocking vibration absworption peak.
Reaction equation is as follows：
(2) preparation of emulsified asphalt：
AH-70# pitch 300g are taken, 125 DEG C are heated to, 10.0g asphalt emulsifiers manufactured in the present embodiment are added to
In 200g water, pH value is adjusted to 2-3 with technical hydrochloric acid, 65 DEG C are heated to, soap lye is made.Pitch and emulsifying agent soap lye are passed through into glue
Cationic emulsified asphalt is prepared in body mill emulsification.
(3) emulsified asphalt performance detection：
Detection method be the same as Example 1, testing result is：Emulsified asphalt is uniform, fine and smooth, and bitumen content is 57%, is remained on sieve
Surplus is 0.03%, and area is wrapped more than 2/3 with mineral aggregate, and storage stability (1d) is 0.8%；In de-emulsification speed experiment, adopt
Can it be 12 seconds the mixing time with B class material；Mixed and stirred using material is mixed and stirred, can be 5 seconds the mixing time.Show prepared by the emulsifying agent
Asphalt emulsion to split type cationic emulsified bitumen soon, properties can meet standard requirement.
Embodiment 3：
(1) preparation of dication teritary amide type asphalt emulsifier：
1) 269.5g octadecylamines, 260g isopropanols, heating stirring dissolving are added in the reactor.Then it is gradually added into
203.2g N,N-DMAAs, 65 DEG C of stirring reaction 4h, obtain reaction intermediate I.
2) 189.6g 85% (mass fraction) triethanolamine is added in the reactor, is gradually added into (the matter of 131.2g 30%
Measure fraction) technical hydrochloric acid, then 97.1g epoxychloropropane is gradually added into, 55 DEG C of stirring reaction 2h obtain reaction intermediate II.
3) the reaction intermediate II of preparation is added drop-wise to above-mentioned steps 1) in the reaction intermediate I of synthesis, 70 DEG C of stirrings are anti-
Answer 2h.Dication teritary amide type asphalt emulsifier is obtained, emulsified asphalt experiment is given over to.
Synthetic product carries out FTIR detections after recrystallizing separating-purifying, as a result as follows：3396cm-1For O-H stretching vibrations
Absworption peak, 2920cm-1For the asymmetric stretching vibration absworption peak of methylene, 2852cm-1Received for the symmetrical stretching vibration of methylene
Peak, 1629cm-1For C=O stretching vibration absworption peaks, 1469cm in amide groups-1Vibrated for the asymmetric curvature of methylene,
1398cm-1Vibrated for the asymmetric curvature of methyl, 1270cm-1And 1162cm-1For C-N stretching vibration absworption peaks, 1049cm-1For
C-OH stretching vibration absworption peaks, 719cm-1For methylene rocking vibration absworption peak.
Reaction equation is as follows：
(2) preparation of emulsified asphalt：
A-100# pitch 300g are taken, 125 DEG C are heated to, 10.0g asphalt emulsifiers manufactured in the present embodiment are added to
In 200g water, pH value is adjusted to 2-3 with technical hydrochloric acid, 65 DEG C are heated to, soap lye is made.Pitch and emulsifying agent soap lye are passed through into glue
Cationic emulsified asphalt is prepared in body mill emulsification.
(3) emulsified asphalt performance detection：
Detection method be the same as Example 1, testing result is：Emulsified asphalt is uniform, fine and smooth, and bitumen content is 59%, is remained on sieve
Surplus is 0.03%, and area is wrapped more than 2/3 with mineral aggregate, and storage stability (1d) is 0.8%；In de-emulsification speed experiment, adopt
Can it be 10 seconds the mixing time with B class material；Mixed and stirred using material is mixed and stirred, can be 4 seconds the mixing time.Show prepared by the emulsifying agent
Asphalt emulsion to split type cationic emulsified bitumen soon, properties can meet standard requirement.
Comparative example 1：
Reaction raw materials " N,N-DMAA " in embodiment 1 are replaced with " 145.7g acrylamides ", prepared
Method be the same as Example 1 is (i.e.：Embodiment 1 in the A of CN 105418942), 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 10ml water, that is, water-separating time are separated after standing, thus 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 being placed in the 100ml of glass stopper, then measure with pipette 40ml atoleine
It is placed in this conical flask.It is then fierce up and down to vibrate 5 times by tight glass stopper, vibrated again 5 times after standing 1min, then stand 1min；
After being so repeated 5 times, in the tool plug graduated cylinder that this emulsion is poured into 100ml, the time is recorded with stopwatch at once.Water phase and an oil phase is gradual
Separation, aqueous phase can appear in the lower floor of graduated cylinder slowly, when aqueous phase separates 10ml water, record now separate used in water when
Between, using this time as emulsifying capacity relatively, the more long then emulsifying capacity of water-separating time is stronger.
After testing, the water-separating time of asphalt emulsifier prepared by the embodiment of the present invention 1 is 125s；Drip prepared by comparative example 1
The water-separating time of blue or green emulsifying agent is 19s.The drip prepared it can be seen from water-separating time by raw material of N,N-DMAA
The emulsifying capacity of blue or green emulsifying agent will be significantly better than the asphalt emulsifier prepared by raw material of acrylamide.
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 be the same as Example 1,
Prepare asphalt emulsifier.
As a result find：Comparative example 2 is during asphalt emulsifier is prepared, particularly reaction intermediate II preparation process
In, reaction system is layered, and reduces reaction rate and reaction intermediate II yield.
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 be the same as Example 1,
Prepare asphalt emulsifier.
As a result find, comparative example 3 is during asphalt emulsifier is prepared, particularly reaction intermediate II preparation process
In, through to reaction product --- reaction intermediate II detects that reaction intermediate II epoxy bond is much opened, epoxy bond
After being opened so that reaction intermediate II and reaction intermediate I, which can not further react, prepares asphalt emulsifier, reduction
The yield of final product asphalt emulsifier.
The preferred embodiment of the application is the foregoing is only, the application is not limited to, for the skill of this area
For art personnel, the application can have various modifications and variations.It is all within spirit herein and principle, made any repair
Change, equivalent substitution, improvement etc., should be included within the protection domain of the application.
Claims (10)
1. a kind of dication teritary amide type asphalt emulsifier, it is characterised in that its molecular structure is：
Wherein, R=methyl (- CH3), ethyl (- C2H5), ethoxy (- C2H4OH)。
2. dication teritary amide type asphalt emulsifier as claimed in claim 1, it is characterised in that by following mol ratio
Raw material is prepared from：
Octadecylamine, alcohols solvent, N, N- DMAAs, low carbon number tertiary amine, technical hydrochloric acid, the mol ratio of epoxychloropropane
For 1mol：(4.00-9.00)mol：(2.00-2.10)mol：(1.02-1.10)mol：(1.02-1.10)mol：(1.02-
1.08)mol。
3. dication teritary amide type asphalt emulsifier as claimed in claim 2, it is characterised in that the alcohols solvent is second
Alcohol, methanol or isopropanol；
The low carbon number tertiary amine is trimethylamine aqueous solution, triethylamine or the triethanolamine aqueous solution.
4. the preparation method of the dication teritary amide type asphalt emulsifier described in claim any one of 1-3, it is characterised in that
Comprise the following steps：
(1) octadecylamine, alcohols solvent and N,N-DMAA are mixed, reaction, obtains reaction intermediate I, it is described anti-
The molecular formula for answering intermediate compound I is：C18H37N(CH2CH2CON(CH3)2)2；
(2) low carbon number tertiary amine, technical hydrochloric acid and epoxychloropropane are mixed, reaction obtains reaction intermediate II, in the reaction
Mesosome II structural formula is：
(3) reaction intermediate II is added drop-wise in reaction intermediate I, reacts, that is, obtain dication teritary amide type asphalt emulsification
Agent.
5. preparation method as claimed in claim 4, it is characterised in that octadecylamine, alcohols solvent, N, N- dimethyl allene acyls
The mol ratio that amine, low carbon number tertiary amine, technical hydrochloric acid, epoxychloropropane are added is 1mol：(4.00-9.00)mol：(2.00-
2.10)mol：(1.02-1.10)mol：(1.02-1.10)mol：(1.02-1.08)mol.
6. preparation method as claimed in claim 4, it is characterised in that in step (1), the temperature of reaction is 60-80 DEG C, preferably
For 65-75 DEG C, the time of reaction is 2-4h.
7. preparation method as claimed in claim 4, it is characterised 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 4, it is characterised in that in step (3), the temperature of reaction is 60-80 DEG C, preferably
For 65-75 DEG C, the time of reaction is 2-4h.
It is cation emulsified that 9. the dication teritary amide type asphalt emulsifier described in claim any one of 1-3 splits type soon in preparation
Application in pitch.
10. a kind of preparation method of cationic emulsified bitumen, it is characterised in that step is as follows：
Dication teritary amide type asphalt emulsifier described in claim any one of 1-3 is added water and is configured to the aqueous solution, is adjusted
PH is heated to 60-70 DEG C to 2-3, and soap lye is made；Pitch after heating and emulsifying agent soap lye are prepared by colloid mill emulsification
Cationic emulsified bitumen；
The consumption of the dication teritary amide type asphalt emulsifier is the 0.8-2.5% of the emulsified asphalt gross mass prepared.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107298725A (en) * | 2017-08-23 | 2017-10-27 | 黄河三角洲京博化工研究院有限公司 | A kind of preparation method of the miscellaneous Shuangzi asphalt emulsifier of chitosan-based cationic |
| CN107827772A (en) * | 2017-11-16 | 2018-03-23 | 江苏苏博特新材料股份有限公司 | A kind of cation modified asphalt emulsifying agent, its preparation method and its application |
| CN112552894A (en) * | 2019-12-31 | 2021-03-26 | 西南石油大学 | Ultra-high temperature resistant low-viscosity low-corrosion emulsifier and emulsified acid system containing same |
| CN115819266A (en) * | 2022-08-19 | 2023-03-21 | 山东大学 | Gemini type surfactant and preparation method and application thereof |
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| CN105384948A (en) * | 2015-12-21 | 2016-03-09 | 山东大学 | Dication and dianion type asphalt emulsifier and preparation method thereof |
| CN105418942A (en) * | 2015-12-21 | 2016-03-23 | 山东大学 | Dicationic amide type asphalt emulsifier and preparation method therefor |
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| CN105384948A (en) * | 2015-12-21 | 2016-03-09 | 山东大学 | Dication and dianion type asphalt emulsifier and preparation method thereof |
| CN105418942A (en) * | 2015-12-21 | 2016-03-23 | 山东大学 | Dicationic amide type asphalt emulsifier and preparation method therefor |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107298725A (en) * | 2017-08-23 | 2017-10-27 | 黄河三角洲京博化工研究院有限公司 | A kind of preparation method of the miscellaneous Shuangzi asphalt emulsifier of chitosan-based cationic |
| CN107298725B (en) * | 2017-08-23 | 2019-07-12 | 黄河三角洲京博化工研究院有限公司 | A kind of preparation method of the miscellaneous Shuangzi asphalt emulsifier of chitosan-based cationic |
| CN107827772A (en) * | 2017-11-16 | 2018-03-23 | 江苏苏博特新材料股份有限公司 | A kind of cation modified asphalt emulsifying agent, its preparation method and its application |
| CN107827772B (en) * | 2017-11-16 | 2020-05-26 | 江苏苏博特新材料股份有限公司 | Cation modified asphalt emulsifier, preparation method and application thereof |
| CN112552894A (en) * | 2019-12-31 | 2021-03-26 | 西南石油大学 | Ultra-high temperature resistant low-viscosity low-corrosion emulsifier and emulsified acid system containing same |
| CN115819266A (en) * | 2022-08-19 | 2023-03-21 | 山东大学 | Gemini type surfactant and preparation method and application thereof |
| CN115819266B (en) * | 2022-08-19 | 2024-03-08 | 山东大学 | Gemini type surfactant and preparation method and application thereof |
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Application publication date: 20170818 |