CN106946747B - A kind of carboxylic acid double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier and preparation method thereof - Google Patents
A kind of carboxylic acid double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C309/13—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton
- C07C309/14—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton containing amino groups bound to the carbon skeleton
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/02—Formation of carboxyl groups in compounds containing amino groups, e.g. by oxidation of amino alcohols
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
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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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- C—CHEMISTRY; METALLURGY
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Abstract
The invention discloses a kind of carboxylic acid double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier, molecular structure is：
Description
Technical field
The present invention relates to a kind of carboxylic acid double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifiers and preparation method thereof, belong to essence
Thin chemical technology field.
Background technology
Emulsified asphalt especially cationic emulsified bitumen is due to that with energy conservation and environmental protection, can improve execution conditions, and can have
Effect reduces many excellent application characteristics such as pitch overaging, and is widely used in road construction and pavement preservation.
The most critical factor for influencing emulsified asphalt pavement performance is exactly asphalt emulsifier, at present domestic and international cationic pitch
Emulsifier principal item has organic amine, quaternary ammonium salt, imidazolines, amides etc., wherein quaternary ammonium salt asphalt emulsifier packet
Mono-quaternaries and bi-quaternary ammonium salt class are included, are that current China produces and apply most emulsifier kinds.Related asphalt emulsification at present
The main research of agent has：
United States Patent (USP) USP4338136 is with C12-18Long carbon chain aliphatic acid reacts preparation with diethylenetriamine under certain condition
Asphalt emulsifier.The disadvantages of this method is that the asphalt emulsifier prepared is expensive, when constructing for slurry seal, is demulsified the time
Long, molding time is slow, and the open to traffic time is long.Chinese patent CN1096714 utilizes oil plant by-product aphthenic acids and alkenyl polyamine
Reaction, prepares asphalt emulsifier.The disadvantages of this method be the raw material supply of emulsifier by severely restricts, being unfavorable for promoting should
With.Chinese patent CN1861721A is related to a kind of rosin cation asphalt emulgent.The emulsifier is by rosin and alkenyl polyamine
Reaction, obtain rosin intermediate, then, with different types of quaternary ammonium salt intermediate be condensed, be made function admirable rosin sun from
Sub- asphalt emulsifier.The shortcomings that this method is that reaction step is cumbersome, needs pyroreaction.Chinese patent CN101745340A is related to
And a kind of cation asphalt emulgent preparation method, intermediate is obtained by the reaction by mixed organic acid and organic amine in host agent, then carries out
Quaternization reaction is made, and adjuvant is nonionic surfactant and modified additive.The disadvantages of this method is that preparation process is cumbersome, into
This is higher, needs pyroreaction.It is slow that Chinese patent 201310722961.9 discloses that a kind of Acid modified starch cation is split slowly
The preparation method of solidifying 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 emulsifier into
This is higher, and source is restricted, and when preparation needs pyroreaction, higher to productive experiment equipment requirement.
The development of emulsified asphalt is influenced by various, and the material to meet the requirements is crucial, therefore, develops new valency of fine quality
Honest and clean emulsifier, the emulsified asphalt being had excellent performance, to meet the different application demand of road construction and pavement preservation.
3- chlorine-2-hydroxyl propyl sulfonic acid sodium is the alkyl chloride of a kind of hydroxyl and sulfonic acid group, is both contained in molecular structure
There are a hydrophilic sulfonate groups, and containing active stronger halogen atom and hydroxyl, be important organic chemical industry's intermediate, it can be with
Imidazoline occurs alkylated reaction and prepares containing sulfonic amphoteric surfactant；It is the important original of synthetic high polymer again simultaneously
Material can prepare thickening agent, filtrate reducing aqua, printing and dyeing protective agent etc. under alkaline condition.But do not have also utilize the chloro- 2- hydroxyls of 3- at present
Base propyl sulfonic acid sodium prepares carboxylic acid double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier as reaction intermediate or raw material
Report.
To sum up, during novel asphalt emulsifier is developed, due to reaction raw materials and the breast of the asphalt emulsifier prepared
Change the not predictability of performance, this just significantly increases the difficulty of novel asphalt emulsifier exploitation.
Invention content
For the above-mentioned prior art, the object of the present invention is to provide a kind of carboxylic acid double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium pitches
Emulsifier and preparation method thereof.The production cost of asphalt emulsifier of the present invention is low, it is simple for process, do not need to pyroreaction.
To achieve the above object, the present invention uses following technical proposals：
The first aspect of the invention provides a kind of carboxylic acid double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier, point
Minor structure is：
Preferably, carboxylic acid double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier of the present invention, is matched by following mole
The raw material of ratio is prepared：
N- hydrogenated-tallow group -1,3- trimethylene diamines, alcohols solvent, acrylic acid, epoxychloropropane, sodium hydrogensulfite mole
Than for 1mol：(5.00-11.00)mol：(3.00-3.10)mol：(2.00-2.30)mol：(2.10-2.50)mol.
The alcohols solvent is ethyl alcohol, methanol or isopropanol.
The second aspect of the invention provides the preparation of above-mentioned carboxylic acid double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier
Method includes the following steps：
(1) by N- hydrogenated-tallow group -1,3- trimethylene diamines, alcohols solvent and acrylic acid hybrid reaction, it is intermediate to obtain reaction
Body I, the structural formula of the reaction intermediate I are：
(2) it is sodium hydrogensulfite is soluble in water, heating stirring dissolving, then epoxychloropropane is gradually added into, hybrid reaction obtains
To reaction intermediate II, the structural formula of the reaction intermediate II is：
(3) reaction intermediate II is added drop-wise in reaction intermediate I, reacted to get to carboxylic acid double quaternary ammonium salt type hydroxypropyl
Sodium sulfonate asphalt emulsifier.
In above-mentioned preparation method, N- hydrogenated-tallow group -1,3- trimethylene diamines, alcohols solvent, acrylic acid, epoxychloropropane,
The molar ratio of sodium hydrogensulfite is 1mol：(5.00-11.00)mol：(3.00-3.10)mol：(2.00-2.30)mol：(2.10-
2.50)mol。
By lot of experiment validation and analysis, each raw material of above-mentioned molar ratio so that the carboxylic acid that the present invention is prepared is double
The performance of quaternary hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier is more satisfactory, and the raw material of inappropriate proportion relation cannot form carboxylic acid
Double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium 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 carboxylic acid double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier produced by the present invention, select made from above-mentioned alcohols solvent
The effect of asphalt emulsifier is preferable.
Preferably, in step 1), the temperature of reaction is 60-80 DEG C, further preferably 65-75 DEG C, the time of reaction
For 2-4h.
Preferably, in step (2), the temperature of reaction is 40-85 DEG C, further preferably 55-75 DEG C, and the time of reaction is
3-6h。
Preferably, in step (3), the temperature of reaction is 60-80 DEG C, further preferably 65-75 DEG C, and the time of reaction is
3-6h。
The preparation method of above-mentioned carboxylic acid double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier, specifically comprises the following steps：
(1) N- hydrogenated-tallow group -1,3- trimethylene diamines is added in reaction vessel, adds in alcohols solvent, heating stirring
Dissolving, then acrylic acid is added portionwise, after addition, 2-4h is stirred to react at 60-80 DEG C, obtains reaction intermediate I；
(2) sodium hydrogensulfite is added in another reaction vessel, adds water, heating stirring dissolving, then epoxy is added portionwise
After addition, 3-6h is stirred to react at 40-85 DEG C for chloropropane, obtains reaction intermediate II (3- chlorine-2-hydroxyl propyl sulfonic acids
Sodium)；
(3) reaction intermediate II is added portionwise in reaction intermediate I, 3-6h is reacted at 60-80 DEG C to get to carboxylic acid
Double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier.
Application of the above-mentioned carboxylic acid double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier in emulsified asphalt is prepared, particularly
Preparing the application in splitting type cationic emulsified bitumen soon.
The third aspect of the 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 carboxylic acid double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier, use technical hydrochloric acid
PH to 2-3 is adjusted, is heated to 60-70 DEG C, soap lye is made；Pitch after heating and emulsifier soap lye by colloid mill are emulsified and made
It is standby go out cationic emulsified bitumen；
Alternatively, providing a kind of preparation method of anionic emulsified bitumen, include the following steps：By above-mentioned carboxylic acid bi-quaternary ammonium salt
Type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier adds water to be configured to aqueous solution, adjusts pH value to 10-11 with sodium hydroxide, is heated to 60-
70 DEG C, soap lye is made；Pitch after heating and emulsifier soap lye are prepared into anionic emulsified bitumen by colloid mill emulsification；
The dosage of the carboxylic acid double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier is the emulsified asphalt gross mass prepared
1.0-3.0%.
Reaction raw materials of the present invention using acrylic acid as asphalt emulsifier, by adding in the molecular structure of asphalt emulsifier
Enter acrylic acid and introduce carboxylic acid group, increase the hydrophily of asphalt emulsifier and the compatibility of emulsifier and pitch.In addition,
Carbon chain lengths are considered for the HLB value (hydrophilic/lipophilic balance value) of asphalt emulsifier and the shadow of CMC (critical micelle concentration)
It rings, selects, with the raw material of N- hydrogenated-tallow group -1,3- trimethylene diamines, epoxychloropropane and sodium hydrogensulfite as reaction, to make system
The HLB value of standby asphalt emulsifier improves the emulsifiability to pitch within optimum range.
Beneficial effects of the present invention：
(1) it is double that a kind of carboxylic acid with brand new has been prepared by the reasonable selection to reaction raw materials in the present invention
Quaternary hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier.Wherein, by adding in acrylic acid in raw material of the invention so that present invention system
The standby obtained hydrophily of asphalt emulsification agent molecule is larger；The addition of epoxychloropropane and sodium hydrogensulfite, makes what is be prepared
Asphalt emulsification agent molecule has carboxylic acid double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium chemical constitution, enhances the electricity of asphalt emulsification agent molecule
Lotus intensity.
Asphalt emulsifier in the present invention is amphoteric, and electricity can occur in water for the hydrophilic group in emulsifier molecules of the present invention
From due to being the emulsifier of amphoteric, ionization is stronger, and interfacial film is made to carry corresponding more positive charge, occurs one
Thus there is interface charge layer in stratum boundary surface charge.The formation of interface charge layer makes them by making bitumen particle mutually exclusive
Certain distance is kept, so as to which pitch particle be allowed to maintain dispersity, peptizaiton is played to asphalt emulsion.Interface charge layer
Occur, dispersion in water phase of emulsification, pitch for pitch keeps the stabilization of asphalt emulsion to be of crucial importance.
Since the emulsifier of the present invention is ionizable compared with polycation in water, so the effect of interface charge layer is stronger, so that this hair
Its system is more stablized after bright asphalt emulsifier emulsified asphalt.
In addition, the hydrophilic group that contains is more in the asphalt emulsifier structural formula of the present invention, hydroxyl, sulfonate, quaternary ammonium salt and
Carboxyl so that interfacial film, hydration layer and interface charge layer all enhance accordingly, improve emulsion intercalation method.
(2) present invention using specific raw material propylene acid, N- hydrogenated-tallow group -1,3- trimethylene diamines, epoxychloropropane and
Sodium hydrogensulfite, asphalt emulsifier of the generation with certain HLB value, the carboxylic acid double quaternary ammonium salt type hydroxypropyl prepared using the present invention
Sodium sulfonate asphalt emulsifier has good emulsifiability, and the property indices for the emulsified asphalt being prepared are excellent, can breast
Change the pitch of a variety of different models, the emulsified asphalt of preparation is fine and smooth uniformly, have it is good gather materials wrap up in attached property and storage stability.
The cationic emulsified bitumen professional standard (JTJ052-2000) that emulsified asphalt obtained is worked out by Chinese transportation portion is detected,
Properties can meet standard requirement.Spread suitable for highway priming oil or sticking layer oil and for crushed stone sealing, aggregate chips
Sealing, mist sealing and reparation slight check crack in road surface etc., have the characteristic for splitting asphalt emulsifier soon.
(3) raw material N- hydrogenated-tallow group -1 of carboxylic acid double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier of the invention,
3- trimethylene diamines relative to the raw material used in current cationic asphalt emulsifier it is cheap, derive from a wealth of sources, asphalt emulsifier life
It produces at low cost, and provides good basis to prepare carboxylic acid double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier.
(4) 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 carboxylic acid double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier is simple for process, does not need to pyroreaction, reduces energy
Consumption, greatlys save production cost.
(5) there are anionic group and cation group, both sexes simultaneously in asphalt emulsifier molecular structure of the present invention
Emulsifier is applicable to different environment, the feature of cationic surface active agent is presented in an acidic solution, in alkaline solution
The middle feature that anionic surfactant is presented.
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, preparing cation asphalt emulgent in the prior art, there are still some shortcomings, are
The technical issues of solving as above, present applicant proposes a kind of carboxylic acid double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier,
Molecular structure is：
In one embodiment of the present invention, above-mentioned carboxylic acid double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsification is provided
The preparation method of agent, includes the following steps：
(1) N- hydrogenated-tallow group -1,3- trimethylene diamines is added in reaction vessel, adds in alcohols solvent, heating stirring
Dissolving, then acrylic acid is added portionwise, after addition, 2-4h is stirred to react at 60-80 DEG C, obtains reaction intermediate I；
(2) sodium hydrogensulfite is added in another reaction vessel, adds water, heating stirring dissolving, then epoxy is added portionwise
After addition, 3-6h is stirred to react at 40-85 DEG C for chloropropane, obtains reaction intermediate II (3- chlorine-2-hydroxyl propyl sulfonic acids
Sodium)；
(3) reaction intermediate II is added portionwise in reaction intermediate I, 3-6h is reacted at 60-80 DEG C to get to carboxylic acid
Double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier.
The application is found surprisingly that during experiment, 3- chlorine-2-hydroxyl propyl sulfonic acid sodium as reaction intermediate II, with
Another reaction intermediate I is reacted, and can be prepared asphalt emulsifier, and contain in prepared asphalt emulsifier compared with
More hydrophilic radical, including hydroxyl, sulfonate, quaternary ammonium salt and carboxyl so that interfacial film, hydration layer and interface charge layer are all corresponding
Enhancing, improve emulsifying capacity.
Moreover, the further experimental study of the application is found, in the only reaction intermediate I of specific structure and conduct reaction
The 3- chlorine-2-hydroxyl propyl sulfonic acid sodium of mesosome II, which is reacted, can just be prepared the double quaternary ammoniums of the carboxylic acid with preferable emulsifiability
Salt form hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier.If by the reaction raw materials (N- hydrogenated-tallow groups -1,3- third of reaction intermediate I is prepared
Support diamines, acrylic acid) replace with octadecylamine and acrylic acid (or propylene oxide), then the emulsifier prepared can not carry out breast to pitch
Change.
In the another embodiment of the application, a kind of preparation method of cationic emulsified bitumen is provided, step is such as
Under：
Water is added to be configured to aqueous solution above-mentioned carboxylic acid double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier, adjust pH to 2-
3,60-70 DEG C is heated to, soap lye is made；Pitch after heating and emulsifier soap lye are prepared into cation by colloid mill emulsification
Emulsified asphalt；
The dosage of the carboxylic acid double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier is the emulsified asphalt gross mass prepared
1.0-3.0%.
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.
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 carboxylic acid double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier：
1) 326.0g N- hydrogenated-tallow group -1,3- trimethylene diamines, 330g isopropanols, heating stirring are added in the reactor
Dissolving.Then 219.8g acrylic acid is gradually added into, 70 DEG C are stirred to react 3h.
2) 245.2g sodium hydrogensulfites and 785.4g water, stirring and dissolving are added in another reactor, is heated to 75 DEG C.Again
197.8g epoxychloropropane is added dropwise, 75 DEG C are stirred to react 3.5h, obtain 3- chlorine-2-hydroxyl propyl sulfonic acid sodium water solutions.
The above-mentioned intermediate product of synthesis carries out FTIR detections after recrystallizing separating-purifying, as a result as follows：3592cm-1With
3522cm-1For free O-H stretching vibration absworption peaks, 3362cm-1For O-H stretching vibration absworption peaks of associating, 2923cm-1For methylene
The asymmetric stretching vibration absworption peak of base, 2840cm-1Symmetrical stretching vibration for methylene receives peak, 1635cm-1It is not right for C-O
Claim stretching vibration absworption peak, 1425cm-1Asymmetric curvature for methylene is vibrated, 1239cm-1And 1188cm-1For sulfonate S=
O stretching vibration absworption peaks, 1049cm-1For sulfonate RSO3Asymmetric stretching vibration absorption peak, 812cm-1It shakes for C-H out-of-plane bendings
Dynamic absorption peak, 730cm-1For C-Cl stretching vibration absworption peaks, 621cm-1For and 545cm-1For O-H out-of-plane bending vibration absorption peaks.
3) 3- chlorine-2-hydroxyl propyl sulfonic acid sodium water solutions prepared by step 2) are added drop-wise to above-mentioned steps 1) synthetic product
In, 65 DEG C are stirred to react 4h.Carboxylic acid double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier is obtained, gives over to emulsified asphalt experiment.
Synthetic product carries out FTIR detections after recrystallizing separating-purifying, as a result as follows：3372cm-1For O-H stretching vibrations
Absorption peak, 2924cm-1For the asymmetric stretching vibration absworption peak of methylene, 2851cm-1Symmetrical stretching vibration for methylene is received
Peak, 1698cm-1For C=O stretching vibration absworption peaks, 1652cm in carboxyl-1For C-O asymmetric stretching vibrations absorption peak in carboxyl,
1561cm-1Asymmetric curvature for methylene is vibrated, 1451cm-1Asymmetric curvature for methyl is vibrated, 1341cm-1It is stretched for C-N
Contracting vibration absorption peak, 1213cm-1For sulfonate S=O stretching vibration absworption peaks, 1049cm-1For sulfonate RSO3Asymmetric stretch
Vibration absorption peak, 856cm-1For C-H out-of-plane bending vibration absorption peaks, 756cm-1For methylene rocking vibration absorption peak,
618cm-1And 527cm-1For O-H out-of-plane bending vibration absorption peaks.
Reaction equation is as follows：
(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 60%, and surplus is on sieve
0.02%, area is wrapped more than 2/3 with mineral aggregate, and charge is cation；It is mixed and stirred using material is mixed and stirred, can be 8 seconds the mixing time.
Show that asphalt emulsion prepared by the emulsifier can meet standard requirement to split type cationic emulsified bitumen, properties soon.
Embodiment 2：
(1) preparation of carboxylic acid double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier：
1) 326.0g N- hydrogenated-tallow group -1,3- trimethylene diamines, 330g absolute ethyl alcohols are added in the reactor, and heating is stirred
Mix dissolving.Then 219.8g acrylic acid is gradually added into, 70 DEG C are stirred to react 3h.
2) 245.2g sodium hydrogensulfites and 785.4g water, stirring and dissolving are added in another reactor, is heated to 75 DEG C.Again
197.8g epoxychloropropane is added dropwise, 75 DEG C are stirred to react 3.5h, obtain 3- chlorine-2-hydroxyl propyl sulfonic acid sodium water solutions.
3) 3- chlorine-2-hydroxyl propyl sulfonic acid sodium water solutions prepared by step 2) are added drop-wise to above-mentioned steps 1) synthetic product
In, 75 DEG C are stirred to react 3h.Carboxylic acid double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier is obtained, 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 60%, is remained on sieve
Surplus is 0.02%, wraps area more than 2/3 with mineral aggregate, charge is cation；It is mixed and stirred using material is mixed and stirred, it can the mixing time
It is 5 seconds.Show that asphalt emulsion prepared by the emulsifier is to split type cationic emulsified bitumen soon, properties can meet standard will
It asks.
Embodiment 3：
(1) preparation of carboxylic acid double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier：
1) addition 326.0g N- hydrogenated-tallow group -1,3- trimethylene diamines, 330g methanol, heating stirring are molten in the reactor
Solution.Then 219.8g acrylic acid is gradually added into, 63 DEG C are stirred to react 4h.
2) 245.2g sodium hydrogensulfites and 785.4g water, stirring and dissolving are added in another reactor, is heated to 75 DEG C.Again
197.8g epoxychloropropane is added dropwise, 75 DEG C are stirred to react 3.5h, obtain 3- chlorine-2-hydroxyl propyl sulfonic acid sodium water solutions.
3) 3- chlorine-2-hydroxyl propyl sulfonic acid sodium water solutions prepared by step 2) are added drop-wise to above-mentioned steps 1) synthetic product
In, 60 DEG C are stirred to react 6h.Carboxylic acid double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier is obtained, 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 57%, is remained on sieve
Surplus is 0.02%, wraps area more than 2/3 with mineral aggregate, charge is cation；It is mixed and stirred using material is mixed and stirred, it can the mixing time
It is 4 seconds.Show that asphalt emulsion prepared by the emulsifier is to split type cationic emulsified bitumen soon, properties can meet standard will
It asks.
Comparative example 1：
(1) preparation of carboxylic acid quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium emulsifier：
1) 269.5g octadecylamines, 260g isopropanols, heating stirring dissolving are added in the reactor.Then it is gradually added into
147.7g acrylic acid, 70 DEG C are stirred to react 3h.
2) 122.6g sodium hydrogensulfites and 392.7g water, stirring and dissolving are added in another reactor, is heated to 75 DEG C.Again
98.9g epoxychloropropane is added dropwise, 75 DEG C are stirred to react 3.5h, obtain 3- chlorine-2-hydroxyl propyl sulfonic acid sodium water solutions.
3) 3- chlorine-2-hydroxyl propyl sulfonic acid sodium water solutions prepared by step 2) are added drop-wise to above-mentioned steps 1) synthetic product
In, 65 DEG C are stirred to react 4h.Carboxylic acid quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium emulsifier is obtained, gives over to emulsified asphalt experiment.
Synthetic product carries out FTIR detections after recrystallizing separating-purifying, as a result as follows：3430cm-1For O-H stretching vibrations
Absorption peak, 2920cm-1For the asymmetric stretching vibration absworption peak of methylene, 2853cm-1Symmetrical stretching vibration for methylene is received
Peak, 1740cm-1For C=O stretching vibration absworption peaks, 1615cm in carboxyl-1For C-O asymmetric stretching vibrations absorption peak in carboxyl,
1474cm-1Asymmetric curvature for methylene is vibrated, 1398cm-1Asymmetric curvature for methyl is vibrated, 1305cm-1It is stretched for C-N
Contracting vibration absorption peak, 1180cm-1For sulfonate S=O stretching vibration absworption peaks, 1040cm-1For sulfonate RSO3Asymmetric stretch
Vibration absorption peak, 723cm-1For methylene rocking vibration absorption peak.
Reaction equation is as follows：
C18H37NH2+2CH2=CHCOOH → C18H37N(CH2CH2COOH)2 (4)
(2) preparation of emulsified asphalt：
AH-90# pitch 300g are taken, are heated to 125 DEG C, emulsifier prepared by 12.5g comparative examples 1 is added to 200g water
In, pH value is adjusted to 2-3 with technical hydrochloric acid, is heated to 65 DEG C, soap lye is made.Pitch and emulsifier soap lye are passed through into colloid mill breast
Cationic emulsified asphalt is prepared in change.As a result：It cannot emulsify.
Comparative example 2：
(1) preparation of quaternary hydroxypropyl azochlorosulfonate acid sodium emulsifier：
1) 269.5g octadecylamines, 260g isopropanols, heating stirring dissolving are added in the reactor.Then it is gradually added into
122.0g propylene oxide, 70 DEG C are stirred to react 3h.
2) 122.6g sodium hydrogensulfites and 392.7g water, stirring and dissolving are added in another reactor, is heated to 75 DEG C.Again
98.9g epoxychloropropane is added dropwise, 75 DEG C are stirred to react 3.5h, obtain 3- chlorine-2-hydroxyl propyl sulfonic acid sodium water solutions.
3) 3- chlorine-2-hydroxyl propyl sulfonic acid sodium water solutions prepared by step 2) are added drop-wise to above-mentioned steps 1) synthetic product
In, 65 DEG C are stirred to react 4h.Quaternary hydroxypropyl azochlorosulfonate acid sodium emulsifier is obtained, gives over to emulsified asphalt experiment.
Synthetic product carries out FTIR detections after recrystallizing separating-purifying, as a result as follows：3434cm-1For O-H stretching vibrations
Absorption peak, 2916cm-1For the asymmetric stretching vibration absworption peak of methylene, 2849cm-1Symmetrical stretching vibration for methylene is received
Peak, 1652cm-1For C-O asymmetric stretching vibration absorption peaks, 1464cm-1Asymmetric curvature for methylene is vibrated, 1407cm-1
Asymmetric curvature for methyl is vibrated, 1208cm-1For sulfonate S=O stretching vibration absworption peaks, 1040cm-1For sulfonate RSO3
Asymmetric stretching vibration absorption peak, 785cm-1For C-H out-of-plane bending vibration absorption peaks, 728cm-1It shakes to be waved in methylene basal plane
Dynamic absorption peak, 624cm-1And 535cm-1For O-H out-of-plane bending vibration absorption peaks.
Reaction equation is as follows：
(2) preparation of emulsified asphalt：
AH-90# pitch 300g are taken, are heated to 125 DEG C, emulsifier prepared by 12.5g comparative examples 2 is added to 200g water
In, pH value is adjusted to 2-3 with technical hydrochloric acid, is heated to 65 DEG C, soap lye is made.Pitch and emulsifier soap lye are passed through into colloid mill breast
Cationic emulsified asphalt is prepared in change.As a result：It cannot emulsify.
Comparative example 3：
(1) preparation of quaternary hydroxypropyl azochlorosulfonate acid sodium emulsifier：
1) 269.5g octadecylamines, 260g isopropanols, heating stirring dissolving are added in the reactor.Then it is gradually added into
238.1g propylene oxide, 70 DEG C are stirred to react 3h.
2) 122.6g sodium hydrogensulfites and 392.7g water, stirring and dissolving are added in another reactor, is heated to 75 DEG C.Again
98.9g epoxychloropropane is added dropwise, 75 DEG C are stirred to react 3.5h, obtain 3- chlorine-2-hydroxyl propyl sulfonic acid sodium water solutions.
3) 3- chlorine-2-hydroxyl propyl sulfonic acid sodium water solutions prepared by step 2) are added drop-wise to above-mentioned steps 1) synthetic product
In, 65 DEG C are stirred to react 4h.Quaternary hydroxypropyl azochlorosulfonate acid sodium emulsifier is obtained, gives over to emulsified asphalt experiment.
Synthetic product carries out FTIR detections after recrystallizing separating-purifying, as a result as follows：3445cm-1For O-H stretching vibrations
Absorption peak, 2924cm-1For the asymmetric stretching vibration absworption peak of methylene, 2851cm-1Symmetrical stretching vibration for methylene is received
Peak, 1643cm-1For C-O asymmetric stretching vibration absorption peaks, 1551cm-1Asymmetric curvature for methylene is vibrated, 1469cm-1
Asymmetric curvature for methyl is vibrated, 1195cm-1For sulfonate S=O stretching vibration absworption peaks, 1039cm-1For sulfonate RSO3
Asymmetric stretching vibration absorption peak, 783cm-1For C-H out-of-plane bending vibration absorption peaks, 720cm-1It shakes to be waved in methylene basal plane
Dynamic absorption peak, 627cm-1And 527cm-1For O-H out-of-plane bending vibration absorption peaks.
Reaction equation is as follows：
(2) preparation of emulsified asphalt：
AH-90# pitch 300g are taken, are heated to 125 DEG C, emulsifier prepared by 12.5g comparative examples 3 is added to 200g water
In, pH value is adjusted to 2-3 with technical hydrochloric acid, is heated to 65 DEG C, soap lye is made.Pitch and emulsifier soap lye are passed through into colloid mill breast
Cationic emulsified asphalt is prepared in change.As a result：It cannot emulsify.
Comparative example 4：
(1) preparation of quaternary hydroxypropyl azochlorosulfonate acid sodium emulsifier：
1) 269.5g octadecylamines, 260g isopropanols, heating stirring dissolving are added in the reactor.Then it is gradually added into
354.3g propylene oxide, 70 DEG C are stirred to react 3h.
2) 122.6g sodium hydrogensulfites and 392.7g water, stirring and dissolving are added in another reactor, is heated to 75 DEG C.Again
98.9g epoxychloropropane is added dropwise, 75 DEG C are stirred to react 3.5h, obtain 3- chlorine-2-hydroxyl propyl sulfonic acid sodium water solutions.
3) 3- chlorine-2-hydroxyl propyl sulfonic acid sodium water solutions prepared by step 2) are added drop-wise to above-mentioned steps 1) synthetic product
In, 65 DEG C are stirred to react 4h.Quaternary hydroxypropyl azochlorosulfonate acid sodium emulsifier is obtained, gives over to emulsified asphalt experiment.
Synthetic product carries out FTIR detections after recrystallizing separating-purifying, as a result as follows：3427cm-1For O-H stretching vibrations
Absorption peak, 2933cm-1For the asymmetric stretching vibration absworption peak of methylene, 2851cm-1Symmetrical stretching vibration for methylene is received
Peak, 1652cm-1For C-O asymmetric stretching vibration absorption peaks, 1542cm-1Asymmetric curvature for methylene is vibrated, 1469cm-1
Asymmetric curvature for methyl is vibrated, 1205cm-1For sulfonate S=O stretching vibration absworption peaks, 1039cm-1For sulfonate RSO3
Asymmetric stretching vibration absorption peak, 791cm-1For C-H out-of-plane bending vibration absorption peaks, 718cm-1It shakes to be waved in methylene basal plane
Dynamic absorption peak, 618cm-1And 527cm-1For O-H out-of-plane bending vibration absorption peaks.
Reaction equation is as follows：
(2) preparation of emulsified asphalt：
AH-90# pitch 300g are taken, are heated to 125 DEG C, emulsifier prepared by 12.5g comparative examples 4 is added to 200g water
In, pH value is adjusted to 2-3 with technical hydrochloric acid, is heated to 65 DEG C, soap lye is made.Pitch and emulsifier soap lye are passed through into colloid mill breast
Cationic emulsified asphalt is prepared in change.As a result：It cannot emulsify.
Conclusion：Based on above example and comparative example can be seen that the present invention using filter out excellent asphalt emulsifier as
Starting point reasonably selects reaction raw materials, and properties, which are prepared, can meet the cation emulsified of standard requirement
Pitch.It is specific anti-so as to be formed that the present invention selects specific raw material (N- hydrogenated-tallow groups -1,3- trimethylene diamines and acrylic acid)
Intermediate compound I is answered, (reaction intermediate II, also can be directly as reaction with reaction intermediate I and 3- chlorine-2-hydroxyl propyl sulfonic acid sodium
Raw material) it is the carboxylic acid double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier that raw material can just obtain new structure, in experimental study
In the process, inventors have surprisingly discovered that the asphalt emulsifier has excellent emulsifiability, and by others in comparative example 1~4
The emulsifier that reaction intermediate I is obtained is unable to emulsified asphalt.
The foregoing is merely the preferred embodiments of the application, are not limited to the application, for the skill of this field
For art personnel, the application can have various modifications and variations.It is all within spirit herein and principle, made any repair
Change, equivalent replacement, improvement etc., should be included within the protection domain of the application.
Claims (13)
1. a kind of carboxylic acid double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier, which is characterized in that its molecular structure is：
2. carboxylic acid double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier as described in claim 1, which is characterized in that by following
The raw material of mol ratio is prepared：
N- hydrogenated-tallow group -1,3- trimethylene diamines, alcohols solvent, acrylic acid, epoxychloropropane, sodium hydrogensulfite molar ratio be
1mol：(5.00-11.00)mol：(3.00-3.10)mol：(2.00-2.30)mol：(2.10-2.50)mol.
3. carboxylic acid double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier as claimed in claim 2, which is characterized in that the alcohol
Class solvent is ethyl alcohol, methanol or isopropanol.
4. the preparation method of claim 1-3 any one of them carboxylic acid double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifiers,
It is characterized by comprising the following steps：
(1) by N- hydrogenated-tallow group -1,3- trimethylene diamines, alcohols solvent and acrylic acid hybrid reaction, reaction intermediate I is obtained,
The structural formula of the reaction intermediate I is：
(2) it is sodium hydrogensulfite is soluble in water, heating stirring dissolving, then epoxychloropropane is gradually added into, hybrid reaction obtains anti-
Intermediate II is answered, the structural formula of the reaction intermediate II is：
(3) reaction intermediate II is added drop-wise in reaction intermediate I, reacted to get to carboxylic acid double quaternary ammonium salt type hydroxypropyl sulfonic acid
Sodium asphalt emulsifier.
5. preparation method as claimed in claim 4, which is characterized in that N- hydrogenated-tallow group -1,3- trimethylene diamines, alcohols are molten
Agent, acrylic acid, epoxychloropropane, sodium hydrogensulfite molar ratio be 1mol：(5.00-11.00)mol：(3.00-3.10)mol：
(2.00-2.30)mol：(2.10-2.50)mol.
6. preparation method as claimed in claim 4, which is characterized in that in step (1), the temperature of reaction is 60-80 DEG C, reaction
Time be 2-4h.
7. preparation method as claimed in claim 6, which is characterized in that in step (1), the temperature of reaction is 65-75 DEG C.
8. preparation method as claimed in claim 4, which is characterized in that in step (2), the temperature of reaction is 40-85 DEG C, reaction
Time be 3-6h.
9. preparation method as claimed in claim 8, which is characterized in that in step (2), the temperature of reaction is 55-75 DEG C.
10. preparation method as claimed in claim 4, which is characterized in that in step (3), the temperature of reaction is 60-80 DEG C, instead
The time answered is 3-6h.
11. preparation method as claimed in claim 10, which is characterized in that in step (3), the temperature of reaction is 65-75 DEG C.
12. claim 1-3 any one of them carboxylic acid double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifiers are split soon in preparation
Application in type cationic emulsified bitumen.
13. 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 water claim 1-3 any one of them carboxylic acid double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifiers
Solution adjusts pH to 2-3 with technical hydrochloric acid, is heated to 60-70 DEG C, soap lye is made；By the pitch after heating and emulsifier soap lye
Cationic emulsified bitumen is prepared by colloid mill emulsification；
The dosage of the carboxylic acid double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier is the emulsified asphalt gross mass prepared
1.0-3.0%.
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| CN109694481B (en) * | 2017-10-20 | 2020-03-10 | 山东大学 | Carboxylic acid bis-quaternary ammonium salt type sodium hydroxypropyl phosphate asphalt emulsifier and preparation method thereof |
| CN107903194B (en) * | 2017-11-20 | 2019-09-06 | 山东大学 | A kind of amidoquat salt form hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier and preparation method thereof |
| CN113105373B (en) * | 2021-04-14 | 2022-07-26 | 山东大学 | Tertiary amine sulfonic acid surfactant, and preparation method and application thereof |
| CN113083152B (en) * | 2021-04-20 | 2022-02-08 | 山东大学 | Carboxylic acid sulfonic acid type surfactant, and preparation method and application thereof |
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| CN115368915B (en) * | 2021-07-22 | 2024-05-24 | 山东大学 | Quaternary ammonium salt sodium carboxylate sulfonate surfactant, and preparation method and application thereof |
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