CN106831477B - A kind of both sexes teritary amide type asphalt emulsifier and preparation method thereof - Google Patents
A kind of both sexes teritary amide type asphalt emulsifier and preparation method thereof Download PDFInfo
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- CN106831477B CN106831477B CN201710050399.8A CN201710050399A CN106831477B CN 106831477 B CN106831477 B CN 106831477B CN 201710050399 A CN201710050399 A CN 201710050399A CN 106831477 B CN106831477 B CN 106831477B
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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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- 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
- 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 a kind of both sexes teritary amide type asphalt emulsifier, molecular structural formula is：
Description
Technical field
The invention belongs to technical field of fine, and in particular to a kind of both sexes teritary amide type asphalt emulsifier and its preparation
Method.
Background technology
The amphipathic molecule that emulsifier is made of the hydrophilic group of nonpolar hydrophobic group and polarity, this structure make emulsification
Agent forms orientation close-packed arrays in solution table (boundary) face, changes table (boundary) face chemical property of system.When the concentration of emulsifier
More than its critical micelle concentration CMC, table (boundary) face tension minimizes, and so as to have the function of emulsification, defoaming, dispersion etc., is building
The fields such as material chemical industry, oil exploitation, daily necessities, textile printing and dyeing are widely used.
According to the difference of emulsifier hydrophilic group property, emulsifier is divided into anionic, cationic, amphoteric ion type, non-
Ion emulsifying and complex ionic etc..Wherein, both sexes asphalt emulsifier carries negative ions charge simultaneously, its surface is lived
Property ion hydrophilic group not only there is anionicsite, but also with cationic moiety；Its structure is both different from anionic pitch
Emulsifier, and cationic asphalt emulsifier is different from, therefore, there are many excellent performances, such as：(1) good emulsibility
And dispersibility；(2) hypotoxicity；(3) resistance to hard water, calcium dispersibility are stronger, have good match with the emulsifier of other kinds type
Wu Xing.
But the exploitation in relation to both sexes asphalt emulsifier is later, and kind and quantity are all few；The both sexes pitch reported at present
Emulsifier mainly has betaine type, amino acid pattern, imidazoline type etc..United States Patent (USP) USP3342840 introductions have synthesized a kind of hydrophilic
Base be amino and the simultaneous amphoteric emulsifier of hydroxyl, due to zwitterionic electriferous state can with the variation of environment and
Variation, therefore application range is wider；But the manufacturing cost of the emulsifier is higher.Chinese patent CN101712625A is related to a kind of both sexes
Slowly quick-setting asphalt emulsifier synthetic method is split, reacts generation polyamide-polyamino with polyamines using oleic acid, then add in monoxone
Asphalt emulsifier is made in halogenating reaction.The disadvantages of this method is to need pyroreaction when preparing.
Present inventor proposes a kind of preparation method of both sexes betaine type asphalt emulsifier in early-stage study, should
Emulsifier uses cocamidopropyl dimethyl tertiary amine as raw material, and in alcohols solvent, centre is obtained with epichlorohydrin reaction
Body；Continuation is reacted with dimethylamine agueous solution, sodium chloroacetate, obtains both sexes betaine type asphalt emulsifier.The asphalt emulsifier
Synthesis material is easy to get, production cost is low, it is simple for process, do not need to pyroreaction.But the both sexes betaine type asphalt emulsifier system
It is standby to obtain splitting type cationic emulsified bitumen in being, it is difficult to meet the application of crushed stone sealing, screening seal coat etc..Therefore, have
Necessity develops new both sexes asphalt emulsifier, to meet the requirement of the different application of road construction and pavement preservation.
Invention content
Deficiency in for the above-mentioned prior art, the present invention provide a kind of both sexes teritary amide type asphalt emulsifier and its preparation
Method.The present invention is prepared a kind of novel for the first time using N,N-DMAA as the reaction raw materials of asphalt emulsifier
Both sexes teritary amide type asphalt emulsifier, the both sexes teritary amide type asphalt emulsifier have good emulsifiability, be 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,
With it is good gather materials wrap up in attached property.
To achieve the above object, the present invention uses following technical proposals：
The first aspect of the present invention, provides a kind of both sexes teritary amide type asphalt emulsifier, and molecular structural formula is：
Preferably, both sexes teritary amide type asphalt emulsifier of the present invention is the raw material preparation by following mol ratio
It obtains：
Octadecylamine, alcohols solvent, N, N- dimethacrylamide, the molar ratio of sodium chloroacetate are 1mol：(4.00-9.00)
mol：(2.00-2.10)mol：(1.02-1.10)mol.
The alcohols solvent is ethyl alcohol, methanol or isopropanol.
The second aspect of the present invention provides the preparation method of above-mentioned both sexes teritary amide type asphalt emulsifier, including walking as follows
Suddenly：
(1) by octadecylamine, alcohols solvent and N,N-DMAA hybrid reaction, reaction intermediate I is obtained, it is described
The molecular formula of reaction intermediate I is C18H37N(CH2CH2CON(CH3)2)2；
(2) sodium chloroacetate aqueous solution is added drop-wise in reaction intermediate I, reacted to get newborn to both sexes teritary amide type pitch
Agent.
Preferably, in step (1), the temperature of reaction is 60-80 DEG C, and preferably 65-75 DEG C, the time of reaction is 2-4h.
Preferably, in step (2), the sodium chloroacetate aqueous solution is reacted by monoxone and sodium hydroxide to be made, concentration
For 28-38% (mass fraction).
Preferably, in step (2), the temperature of reaction is 60-80 DEG C, and preferably 65-75 DEG C, the time of reaction is 2-7h.
Preferably, octadecylamine, alcohols solvent, N,N-DMAA, sodium chloroacetate molar ratio be 1mol：
(4.00-9.00)mol：(2.00-2.10)mol：(1.02-1.10)mol.
By lot of experiment validation and analysis, each raw material of above-mentioned molar ratio causes the both sexes uncle that the present invention is prepared
The performance of acid amide type asphalt emulsifier is more satisfactory, and the raw material of inappropriate proportion relation cannot form both sexes teritary amide type pitch breast
Agent.Especially for the addition of N,N-DMAA, the excessive or very few of addition can all influence to prepare
The water-separating time of the performance of asphalt emulsifier, especially asphalt emulsifier.
Preferably, the alcohols solvent is ethyl alcohol, methanol or isopropanol, by lot of experiment validation and analysis, and according to
The needs of both sexes teritary amide type asphalt emulsifier produced by the present invention select the effect of asphalt emulsifier made from above-mentioned alcohols solvent
Fruit is preferable.
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.
The preparation method of above-mentioned both sexes teritary amide type asphalt emulsifier, specifically comprises the following steps：
(1) octadecylamine is added in reaction vessel, adds in alcohols solvent, heating stirring dissolving, then N is added portionwise, N-
After addition, 2-4h is stirred to react at 60-80 DEG C, obtains reaction intermediate I for dimethacrylamide；
(2) 28-38% (mass fraction) sodium chloroacetate aqueous solution is added portionwise in reaction intermediate I, at 60-80 DEG C
2-7h is reacted to get to both sexes teritary amide type asphalt emulsifier.
The present invention also provides above-mentioned both sexes teritary amide type asphalt emulsifier prepare split soon type cationic emulsified bitumen and/or
The application in type anionic emulsified bitumen is split soon.
The third aspect of the present invention, provides a kind of preparation method of cationic emulsified bitumen, and step is as follows：
Water is added to be configured to aqueous solution above-mentioned both sexes teritary amide type asphalt emulsifier, adjust pH to 2-3 with technical hydrochloric acid, add
Soap lye is made to 60-70 DEG C in heat；Pitch after heating and emulsifier soap lye are prepared by colloid mill emulsification cation emulsified
Pitch；
The dosage of the both sexes teritary amide type asphalt emulsifier is the 0.8-2.5% of the emulsified asphalt gross mass prepared.
The cationic emulsified bitumen that above-mentioned preparation method is prepared, the type of the cationic emulsified bitumen is splits type breast soon
Change pitch.
The fourth aspect of the present invention, provides a kind of preparation method of anionic emulsified bitumen, and step is as follows：
Water is added to be configured to aqueous solution above-mentioned both sexes teritary amide type asphalt emulsifier, pH to 10-11 is adjusted with sodium hydroxide,
60-70 DEG C is heated to, soap lye is made；Pitch after heating and emulsifier soap lye are prepared into anion breast by colloid mill emulsification
Change pitch；
The dosage of the both sexes teritary amide type asphalt emulsifier is the 0.8-2.5% of the emulsified asphalt gross mass prepared.
The anionic emulsified bitumen that above-mentioned preparation method is prepared, the type of the anionic emulsified bitumen is splits type breast soon
Change pitch.
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 both sexes teritary amide type asphalt emulsifier with prominent technique effect.
The present invention for the first time using N,N-DMAA as preparation cationic asphalt emulsifier reaction raw materials,
Amide group is introduced by adding in N,N-DMAA in the molecular structure of the asphalt emulsifier of preparation, increases drip
The hydrophily and emulsifier of green emulsifier and the compatibility of pitch；In addition, compared with acrylamide, acyl in acrylamide molecules
Two hydrogen are replaced by methyl on amido nitrogen, and the hydrolytic stability of copolymer is significantly improved than acrylamide, living in molecule
Bold and vigorous double bond makes it easier to autohemagglutination or is copolymerized with other monomers.
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 had accumulated, pitch particle to including, form a stratum boundary facial mask.In addition, due to pitch breast
After agent molecule ionizes in water so that interfacial film has corresponding charge, thus forms interface charge layer.Interfacial film
It is formed such that water and pitch separate, reduces the interfacial tension between water and pitch, a kind of mechanical protection is played to pitch particle
Effect 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, it maintains a certain distance, so that pitch particle aggregation is gone less than one piece, plays and mutually divide
Scattered effect.
N,N-DMAA, since hydrogen is replaced with methyl, increases the pitch of preparation compared with acrylamide
Lipophilic group in emulsifier molecules structure is more conducive to form interfacial film, reduces the interfacial tension between water and pitch；In addition, with
N,N-DMAA is that the ionizing power of the asphalt emulsifier of reaction raw materials preparation in water is stronger, can be ionized out more
More cations, the effect for making interface charge layer are stronger；So that pitch can be emulsified and can uniformly be divided in water
It dissipates and forms 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 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.
(3) present invention also consider carbon chain lengths for the HLB value (hydrophilic/lipophilic balance value) of asphalt emulsifier and
The influence of CMC (critical micelle concentration) selects the raw material using octadecylamine, monoxone and sodium hydroxide as reaction, makes preparation
The HLB value of asphalt emulsifier improves the emulsifiability to pitch within optimum range.By testing different carbon atoms
Alkyl (uses lauryl amine, tetradecy lamine) in such as synthesis material, emulsifier of the present invention has better asphalt emulsifier HLB
Value, smaller CMC value have good emulsifying effectiveness to pitch, split type emulsified asphalt soon suitable for preparing.
(4) present invention is raw using specific raw material N,N-DMAA, octadecylamine, monoxone and sodium hydroxide
Into the asphalt emulsifier of the both sexes teritary amide type chemical constitution with certain HLB value, the both sexes teritary amide prepared using the present invention
Type asphalt emulsifier has good emulsifiability, and the property indices for the emulsified asphalt being prepared are excellent, emulsifiable more
The pitch of kind of different model, the emulsified asphalt of preparation is fine and smooth uniformly, it is good gather materials wrap up in attached property.Emulsified asphalt obtained is by China
The cationic emulsified bitumen professional standard (JTJ052-2000) that Ministry of Communications works out is detected, and properties can meet standard
It is required that.Spread suitable for highway priming oil or sticking layer oil and for crushed stone sealing, screening seal coat, mist sealing and repair way
Slight check crack in face etc. has the characteristic for splitting asphalt emulsifier soon.
(5) the raw material octadecylamine of both sexes teritary amide type asphalt emulsifier of the invention is relative to current cationic pitch
Raw material used in emulsifier is cheap, derives from a wealth of sources, and asphalt emulsifier production cost is low, and to prepare both sexes teritary amide type pitch
Emulsifier provides good basis.
(6) 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 both sexes teritary amide type asphalt emulsifier is simple for process, does not need to pyroreaction, reduces energy consumption, greatlys save production
Cost.
(7) there are anionic group and cation group, both sexes simultaneously in asphalt emulsifier molecular structure of the present invention
Asphalt emulsifier is applicable to different environment, the feature of cationic surface active agent is presented in an acidic solution, in alkalinity
The feature of anionic surfactant is presented in solution.
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.
As background technology is introduced, in the prior art also not about the report of both sexes teritary amide type asphalt emulsifier
Road, the technical issues of in order to solve as above, present applicant proposes a kind of both sexes teritary amide type asphalt emulsifier, molecular structures
For：
In one embodiment of the application, the present invention provides the preparation sides of above-mentioned both sexes teritary amide type asphalt emulsifier
Method includes the following steps：
(1) octadecylamine is added in reaction vessel, adds in alcohols solvent, heating stirring dissolving, then N is added portionwise, N-
After addition, 2-4h is stirred to react at 60-80 DEG C, obtains reaction intermediate I for dimethacrylamide；Reaction intermediate I's
Molecular formula is C18H37N(CH2CH2CON(CH3)2)2。
(2) 28-38% (mass fraction) sodium chloroacetate aqueous solution is added portionwise in reaction intermediate I, at 60-80 DEG C
2-7h is reacted to get to both sexes teritary amide type asphalt emulsifier.
As preferred embodiment, octadecylamine, alcohols solvent, N,N-DMAA, sodium chloroacetate mole
Than for 1mol：(4.00-9.00)mol：(2.00-2.10)mol：(1.02-1.10)mol.
By lot of experiment validation and analysis, each raw material of above-mentioned molar ratio causes the both sexes uncle that the present invention is prepared
The performance of acid amide type asphalt emulsifier is more satisfactory, and the raw material of inappropriate proportion relation cannot form both sexes teritary amide type pitch breast
Agent.Especially for the addition of N,N-DMAA, the excessive or very few of addition can all influence to prepare
The water-separating time of the performance of asphalt emulsifier, especially asphalt emulsifier.
As preferred embodiment, the alcohols solvent be ethyl alcohol, methanol or isopropanol, by lot of experiment validation with
Analysis, and according to the needs of both sexes teritary amide type asphalt emulsifier produced by the present invention, select above-mentioned alcohols solvent is obtained to drip
The effect of green emulsifier is preferable.
In another embodiment of the present invention, the present invention provides a kind of preparation method of cationic emulsified bitumen, steps
It is rapid as follows：
Water is added to be configured to aqueous solution above-mentioned both sexes teritary amide type asphalt emulsifier, adjust pH to 2-3 with technical hydrochloric acid, add
Soap lye is made to 60-70 DEG C in heat；Pitch after heating and emulsifier soap lye are prepared by colloid mill emulsification cation emulsified
Pitch；
The dosage of the both sexes teritary amide type asphalt emulsifier is the 0.8-2.5% of the emulsified asphalt gross mass prepared.
In yet another embodiment of the present invention, the present invention provides a kind of preparation method of anionic emulsified bitumen, steps
It is rapid as follows：
Water is added to be configured to aqueous solution above-mentioned both sexes teritary amide type asphalt emulsifier, pH to 10-11 is adjusted with sodium hydroxide,
60-70 DEG C is heated to, soap lye is made；Pitch after heating and emulsifier soap lye are prepared into anion breast by colloid mill emulsification
Change pitch；
The dosage of the both sexes teritary amide type asphalt emulsifier is the 0.8-2.5% of the emulsified asphalt gross mass prepared.
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 both sexes 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 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：2910cm-1For Asia
The asymmetric stretching vibration absworption peak of methyl, 2840cm-1Symmetrical stretching vibration for methylene receives peak, 1650cm-1And 1625cm-1For C=O stretching vibration absworption peaks, 1460cm in amide groups-1Asymmetric curvature for methylene is vibrated, 1390cm-1For methyl
Asymmetric curvature vibration, 1263cm-1And 1153cm-1For C-N stretching vibration absworption peaks, 777cm-1And 719cm-1For methylene
Rocking vibration absorption peak.
2) 42.4g sodium hydroxides are dissolved in 80.0g water and obtain sodium hydrate aqueous solution, 100.2g monoxones are dissolved in
Chloroethene aqueous acid is obtained in 200.0g water；Sodium hydrate aqueous solution is added drop-wise in chloroethene aqueous acid and obtains sodium chloroacetate water
Solution.The sodium chloroacetate aqueous solution of preparation is added drop-wise to above-mentioned steps 1) in synthetic product, 65 DEG C are stirred to react 5h.Obtain both sexes
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：2920cm-1For the non-right of methylene
Claim stretching vibration absworption peak, 2849cm-1Symmetrical stretching vibration for methylene receives peak, 1635cm-1It stretches for C=O in amide groups
C=O stretching vibration absworption peaks in vibration absorption peak and carboxylate (- COONa), 1469cm-1Asymmetric curvature for methylene is shaken
It is dynamic, 1400cm-1Asymmetric curvature for methyl is vibrated, 1270cm-1And 1153cm-1For C-N stretching vibration absworption peaks, 1070cm-1
For C-O symmetrical stretching vibration absorption peaks, 904cm-1For C-H out-of-plane bending vibration absorption peaks, 723cm-1To be waved in methylene basal plane
Vibration absorption peak.
Reaction equation is as follows：
C18H37NH2+2CH2=CHCON (CH3)2→C18H37N(CH2CH2CON(CH3)2)2 (1)
(2) preparation of emulsified asphalt：
AH-90# pitch 300g are taken, are heated to 125 DEG C, 12.5g asphalt emulsifiers manufactured in the present embodiment are added to
In 200g water, pH value is adjusted to 2-3 with technical hydrochloric acid, 65 DEG C is heated to, soap lye is made.Pitch and emulsifier soap lye are passed through into glue
Cationic emulsified asphalt is prepared in body mill emulsification.
(3) emulsified asphalt performance detection：
Emulsified asphalt obtained by Chinese transportation portion work out cationic emulsified bitumen professional standard (JTJ052-2000) into
Row detection, it is as a result as follows：Emulsified asphalt manufactured in the present embodiment is uniform, fine and smooth, bitumen content 58%, and surplus is on sieve
0.03%, area is wrapped more than 2/3 with mineral aggregate, and storage stability (1d) is 0.7%；It is mixed and stirred, can be mixed and stirred using material is mixed and stirred
Time is 5 seconds.Show that asphalt emulsion prepared by the emulsifier is to split type cationic emulsified bitumen soon, properties can meet mark
Alignment request.
Embodiment 2
(1) preparation of both sexes teritary amide type asphalt emulsifier：
1) 269.5g octadecylamines, 260g absolute ethyl alcohols, heating stirring dissolving are added in the reactor.Then it is gradually added into
203.2g N,N-DMAAs, 70 DEG C are stirred to react 3h.
2) 42.4g sodium hydroxides are dissolved in 80.0g water and obtain sodium hydrate aqueous solution, 100.2g monoxones are dissolved in
Chloroethene aqueous acid is obtained in 200.0g water；Sodium hydrate aqueous solution is added drop-wise in chloroethene aqueous acid and obtains sodium chloroacetate water
Solution.The sodium chloroacetate aqueous solution of preparation is added drop-wise to above-mentioned steps 1) in synthetic product, 75 DEG C are stirred to react 3h.Obtain both sexes
Teritary amide type asphalt emulsifier gives over to emulsified asphalt experiment.
(2) preparation of emulsified asphalt：
AH-70# pitch 300g are taken, are heated to 125 DEG C, 12.5g asphalt emulsifiers manufactured in the present embodiment are added to
In 200g water, pH value is adjusted to 2-3 with technical hydrochloric acid, 65 DEG C is heated to, soap lye is made.Pitch and emulsifier soap lye are passed through into glue
Cationic emulsified asphalt is prepared in body mill emulsification.
(3) emulsified asphalt performance detection：
Detection method is with embodiment 1, testing result：Emulsified asphalt is uniform, fine and smooth, bitumen content 59%, is remained on sieve
Surplus is 0.03%, wraps area more than 2/3 with mineral aggregate, storage stability (1d) is 0.6%；It is mixed and stirred using material is mixed and stirred,
Can it be 5 seconds the mixing time.Show that asphalt emulsion prepared by the emulsifier is to split type cationic emulsified bitumen, the equal energy of properties soon
Meet standard requirement.
Embodiment 3
(1) preparation of both sexes teritary amide type asphalt emulsifier：
1) 269.5g octadecylamines, 260g methanol, heating stirring dissolving are added in the reactor.Then it is gradually added into 203.2g
N,N-DMAA, 63 DEG C are stirred to react 4h.
2) 42.4g sodium hydroxides are dissolved in 80.0g water and obtain sodium hydrate aqueous solution, 100.2g monoxones are dissolved in
Chloroethene aqueous acid is obtained in 200.0g water；Sodium hydrate aqueous solution is added drop-wise in chloroethene aqueous acid and obtains sodium chloroacetate water
Solution.The sodium chloroacetate aqueous solution of preparation is added drop-wise to above-mentioned steps 1) in synthetic product, 60 DEG C are stirred to react 7h.Obtain both sexes
Teritary amide type asphalt emulsifier gives over to emulsified asphalt experiment.
(2) preparation of emulsified asphalt：
A-100# pitch 300g are taken, are heated to 125 DEG C, 12.5g asphalt emulsifiers manufactured in the present embodiment are added to
In 200g water, pH value is adjusted to 2-3 with technical hydrochloric acid, 65 DEG C is heated to, soap lye is made.Pitch and emulsifier soap lye are passed through into glue
Cationic emulsified asphalt is prepared in body mill emulsification.
(3) emulsified asphalt performance detection：
Detection method is with embodiment 1, testing result：Emulsified asphalt is uniform, fine and smooth, bitumen content 59%, is remained on sieve
Surplus is 0.02%, wraps area more than 2/3 with mineral aggregate, storage stability (1d) is 0.7%；It is mixed and stirred using material is mixed and stirred,
Can it be 4 seconds the mixing time.Show that asphalt emulsion prepared by the emulsifier is to split type cationic emulsified bitumen, the equal energy of properties soon
Meet standard requirement.
Comparative example 1
Reaction raw materials " N,N-DMAA " in embodiment 1 are replaced with " 145.7g acrylamides ", are prepared
Asphalt emulsifier is prepared with embodiment 1 in method.
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
237s；The water-separating time average out to 108s of asphalt emulsifier prepared by comparative example 1.With the application it can be seen from water-separating time
The emulsifying capacity of asphalt emulsifier prepared by embodiment 1 will be significantly better than the asphalt emulsifier prepared with comparative example 1.
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. a kind of both sexes teritary amide type asphalt emulsifier, which is characterized in that its molecular structural formula is：
2. both sexes teritary amide type asphalt emulsifier as described in claim 1, which is characterized in that by the raw material of following mol ratio
It is prepared：
Octadecylamine, alcohols solvent, N, N- dimethacrylamide, the molar ratio of sodium chloroacetate are 1mol：(4.00-9.00)mol：
(2.00-2.10)mol：(1.02-1.10)mol.
3. both sexes teritary amide type asphalt emulsifier as claimed in claim 2, which is characterized in that the alcohols solvent for ethyl alcohol,
Methanol or isopropanol.
4. the preparation method of claim 1-3 any one of them both sexes teritary amide type asphalt emulsifiers, which is characterized in that including
Following steps：
(1) by octadecylamine, alcohols solvent and N,N-DMAA hybrid reaction, reaction intermediate I, the reaction are obtained
The molecular formula of intermediate compound I is C18H37N(CH2CH2CON(CH3)2)2；
(2) sodium chloroacetate aqueous solution is added drop-wise in reaction intermediate I, reacted to get to both sexes teritary amide type asphalt emulsifier.
5. preparation method as claimed in claim 4, it is characterized in that：In step (1), the temperature of reaction is 60-80 DEG C, reaction
Time is 2-4h.
6. preparation method as claimed in claim 5, it is characterized in that：In step (1), the temperature of reaction is 65-75 DEG C.
7. preparation method as claimed in claim 4, it is characterized in that：In step (2), the temperature of reaction is 60-80 DEG C, reaction
Time is 2-7h.
8. preparation method as claimed in claim 7, it is characterized in that：In step (2), the temperature of reaction is 65-75 DEG C.
9. preparation method as claimed in claim 4, it is characterized in that：In step (2), the sodium chloroacetate aqueous solution it is a concentration of
28-38% (mass fraction), the sodium chloroacetate aqueous solution is reacted by monoxone and sodium hydroxide to be made.
10. claim 1-3 any one of them both sexes teritary amide type asphalt emulsifiers split the cation emulsified drip of type soon in preparation
It is green and/or split application in type anionic emulsified bitumen soon.
11. a kind of preparation method of cationic emulsified bitumen, which is characterized in that step is as follows：
Water is added to be configured to aqueous solution claim 1-3 any one of them both sexes teritary amide type asphalt emulsifiers, use Nacl
Acid for adjusting pH is heated to 60-70 DEG C, soap lye is made to 2-3；Pitch after heating and emulsifier soap lye are emulsified by colloid mill
Prepare cationic emulsified bitumen；
The dosage of the both sexes teritary amide type asphalt emulsifier is the 0.8-2.5% of the emulsified asphalt gross mass prepared.
12. a kind of preparation method of anionic emulsified bitumen, which is characterized in that step is as follows：
Water is added to be configured to aqueous solution claim 1-3 any one of them both sexes teritary amide type asphalt emulsifiers, use hydroxide
Sodium adjusts pH to 10-11, is heated to 60-70 DEG C, and soap lye is made；Pitch after heating and emulsifier soap lye are passed through into colloid mill breast
Anionic emulsified bitumen is prepared in change；
The dosage of the both sexes teritary amide type asphalt emulsifier is the 0.8-2.5% of the emulsified asphalt gross mass prepared.
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| CN109207132B (en) * | 2017-07-07 | 2020-11-03 | 中国石油天然气股份有限公司 | Amphiphilic surfactant and composition for oil displacement and preparation method thereof |
| CN112521624B (en) * | 2019-12-31 | 2022-05-20 | 济南圣泉集团股份有限公司 | Phenolated lignin, amphoteric lignin emulsifier, emulsified asphalt and preparation method |
| CN115872908B (en) * | 2022-09-21 | 2024-01-26 | 山东大学 | Sodium amide carboxylate sulfonate surfactant, and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB993460A (en) * | 1963-05-03 | 1965-05-26 | Shell Int Research | Heavy duty lubricants |
| US3198613A (en) * | 1962-08-20 | 1965-08-03 | Standard Oil Co | Fuel oil composition |
| CN102205214A (en) * | 2011-04-28 | 2011-10-05 | 孙安顺 | N,N-dialkyl propanamide fatty alkyl betaine amphoteric surfactant, preparation method and application thereof in tertiary recovery |
| CN103980147A (en) * | 2014-05-23 | 2014-08-13 | 山东大学 | Method for preparing amphoteric betaine asphalt emulsifier |
| JP5704384B2 (en) * | 2010-06-25 | 2015-04-22 | 株式会社リコー | Ink jet recording ink, cartridge, ink jet recording apparatus, image formed product |
-
2017
- 2017-01-23 CN CN201710050399.8A patent/CN106831477B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3198613A (en) * | 1962-08-20 | 1965-08-03 | Standard Oil Co | Fuel oil composition |
| GB993460A (en) * | 1963-05-03 | 1965-05-26 | Shell Int Research | Heavy duty lubricants |
| JP5704384B2 (en) * | 2010-06-25 | 2015-04-22 | 株式会社リコー | Ink jet recording ink, cartridge, ink jet recording apparatus, image formed product |
| CN102205214A (en) * | 2011-04-28 | 2011-10-05 | 孙安顺 | N,N-dialkyl propanamide fatty alkyl betaine amphoteric surfactant, preparation method and application thereof in tertiary recovery |
| CN103980147A (en) * | 2014-05-23 | 2014-08-13 | 山东大学 | Method for preparing amphoteric betaine asphalt emulsifier |
Non-Patent Citations (1)
| Title |
|---|
| 脂肪酰胺阳离子沥青乳化剂的应用研究;刘庆普 等;《石油沥青》;20100425;第24卷(第2期);59-62页 * |
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