CN104151179B - A kind of dication type asphalt emulsifier and preparation method thereof - Google Patents
A kind of dication type asphalt emulsifier and preparation method thereof Download PDFInfo
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- CN104151179B CN104151179B CN201410387152.1A CN201410387152A CN104151179B CN 104151179 B CN104151179 B CN 104151179B CN 201410387152 A CN201410387152 A CN 201410387152A CN 104151179 B CN104151179 B CN 104151179B
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Abstract
The invention discloses a kind of dication type asphalt emulsifier, the molecular structure of this dication type asphalt emulsifier is:
Description
Technical field
The present invention relates to a kind of dication type asphalt emulsifier and preparation method thereof, belong to fine chemical technology field.
Background technology
Emulsified asphalt especially cationic emulsified bitumen, owing to having energy-conserving and environment-protective, can improve execution conditions, and can effectively reduce dropMany good application characteristics such as blue or green overaging, and be widely used in road construction and pavement preservation.
The most critical factor that affects emulsified asphalt pavement performance is exactly asphalt emulsifier, at present domestic and international cationic asphalt emulsifierPrincipal item has organic amine, quaternary ammonium salt, imidazolines, amide-type etc., and wherein quaternary ammonium salt emulsifying agent is most widely used general.Along with the application of cationic emulsified bitumen, the kind of asphalt emulsifier is also abundant gradually.
US Patent No. P4338136 is with C12-18Long carbon chain fatty acid reacts under certain condition and prepares pitch breast with diethylenetriamineAgent. The shortcoming of the method is that the asphalt emulsifier of preparation is expensive, and while construction for slurry seal, the breakdown of emulsion time is long, becomesThe type time is slow, and the open to traffic time is long. Chinese patent CN1096714 utilizes oil plant by-product aphthenic acids to react with alkenyl polyamine,Prepare asphalt emulsifier. The shortcoming of the method is that the raw material supply of emulsifying agent is subject to severely restricts, is unfavorable for applying. ChinaPatent CN1861721A relates to a kind of rosin cation asphalt emulgent. This emulsifying agent is to be reacted by rosin and alkenyl polyamine, obtainsRosin intermediate, then, the quaternary ammonium salt intermediate condensation with dissimilar, makes the rosin cation asphalt emulsification of function admirableAgent. The shortcoming of this method is that reactions steps is loaded down with trivial details, needs pyroreaction. Chinese patent CN101712625A relates to a kind of both sexesSlowly split quick-setting asphalt emulsifying agent synthetic method, adopt oleic acid to react with polyamines and generate polyamide-polyamino, then add monoxone generation halogenGeneration reaction, makes asphalt emulsifier. The shortcoming of the method needs pyroreaction while being preparation. Chinese patent CN101745340A relates toAnd a kind of cation asphalt emulgent preparation method, host obtains intermediate by mixed organic acid and organic amine reaction, then carries out seasonAmmoniumization reaction makes, and assistant agent is non-ionic surface active agent and modified additive. The shortcoming of the method is that preparation process is loaded down with trivial details, costHigher, need pyroreaction.
The ubiquitous deficiency of above-mentioned cationic asphalt emulsifier and preparation method thereof is: the cost of material of preparing emulsifying agent is higher,Source is restricted, and needs pyroreaction when preparation, higher to productive experiment equipment requirement.
Summary of the invention
For the deficiencies in the prior art, the object of the present invention is to provide that a kind of production cost is low, technique simply, do not needWant dication type asphalt emulsifier of pyroreaction and preparation method thereof.
For achieving the above object, the present invention adopts following technical scheme:
A kind of dication type asphalt emulsifier, is prepared from by the raw material of following mole of proportioning:
N-hydrogenated-tallow group-1,3-trimethylene diamines: alcohols solvent: methyl acrylate: sodium chloroacetate=1mol:(6.00-13.00)mol：(1.02-3.05)mol：(2.02-2.10)mol；
Described alcohols solvent is ethanol, methyl alcohol or isopropyl alcohol.
The molecular structure of described dication type asphalt emulsifier is:
Wherein, in the time of x=1, y=1, z=1, i=0; In the time of x=2, y=0, z=1 or 0, i+z=1.
The preparation method of this dication type asphalt emulsifier, comprises the following steps:
(1), by N-hydrogenated-tallow group-1,3-trimethylene diamines joins in reaction vessel, adds alcohols solvent, heating stirring and dissolving,Add again methyl acrylate, at 60-80 DEG C of stirring reaction 2-6h, obtain reaction intermediate;
(2) be the 25-35% sodium chloroacetate aqueous solution to adding mass concentration in the reactant liquor of step (1), 60-80 DEG C of stirringReaction 2-7h, obtains dication type asphalt emulsifier;
In step (1), (2), N-hydrogenated-tallow group-1,3-trimethylene diamines, alcohols solvent, methyl acrylate, sodium chloroacetateMol ratio is 1:(6.00-13.00): (1.02-3.05): (2.02-2.10);
In step (1), described alcohols solvent is ethanol, methyl alcohol or isopropyl alcohol;
In step (2), sodium chloroacetate is made by monoxone and NaOH reaction.
Preferably, in step (1), reaction temperature is 65-75 DEG C;
Preferably, in step (2), reaction temperature is 65-75 DEG C.
Dication type asphalt emulsifier prepared by the present invention is in the application of preparing in emulsified asphalt, and application process is by dicationType asphalt emulsifier is mixed with the aqueous solution that mass concentration is 1.0-3.0%, to 2-3, is heated to 65 DEG C with salt acid for adjusting pH value,Make soap lye; Pitch and emulsifying agent soap lye are prepared to cationic emulsified asphalt by colloid mill emulsification.
The present invention has following beneficial effect with respect to prior art:
(1) raw material N-hydrogenated-tallow group-1 of dication type asphalt emulsifier of the present invention, 3-trimethylene diamines is with respect to currentCationic asphalt emulsifier raw material used is cheap, wide material sources, and asphalt emulsifier production cost is low.
(2) preparation method's technique of dication type asphalt emulsifier of the present invention simply, does not need pyroreaction.
(3) the dication type asphalt emulsifier that prepared by the present invention can the multiple different model of emulsification pitch, the emulsified asphalt of preparationEvenly fine and smooth, storage stability is good, is applicable to spread and slurry seal and micro-table place of highway priming oil or sticking layer oil, hasIn split and split slowly the characteristic of asphalt emulsifier. The emulsified asphalt properties making all can meet the cation that Chinese transportation portion works outEmulsified asphalt standard (JTJ052-2000).
(4) in raw material of the present invention by adding sodium chloroacetate, make preparation asphalt emulsification agent molecule there is dication type,Strengthen the electric charge intensity of asphalt emulsification agent molecule.
Detailed description of the invention
The present invention is further illustrated in conjunction with the embodiments, should be noted that following explanation is only in order to explain the present invention,Its content is not limited.
In the embodiment of the present invention, raw material used, reagent are conventional chemical product, all can be bought and be obtained by market.
Embodiment 1
(1) preparation of dication type asphalt emulsifier:
1) in reactor, add 326gN-hydrogenated-tallow group-1,3-trimethylene diamines, 400g isopropyl alcohol, heating stirring and dissolving.Then drip 90.3g methyl acrylate, 70 DEG C of stirring reaction 4h, obtain reaction intermediate.
The reaction intermediate obtaining is carried out to FTIR detection after recrystallization separating-purifying, and result is as follows: 3275cm-1For N-HStretching vibration absworption peak, 2917cm-1And 2854cm-1The asymmetric stretching vibration and the symmetrical stretching vibration that are respectively methylene absorbPeak, 1735cm-1For ester group C=O stretching vibration absworption peak, 1569cm-1For the flexural vibrations absworption peak of N-H, 1470cm-1For methylene scissoring vibration absworption peak, 1376cm-1For methyl symmetric curvature vibration absorption peak, 1207cm-1For C-N stretching vibrationAbsworption peak, 1125cm-1For C-O-C stretching vibration absworption peak, 724cm-1For methylene rocking vibration absworption peak.
2) 83.2g NaOH is dissolved in 160.0g water and obtains sodium hydrate aqueous solution, 196.6g monoxone is dissolved in 400.0gIn water, obtain the monoxone aqueous solution; Sodium hydrate aqueous solution is added drop-wise to and in the monoxone aqueous solution, obtains the sodium chloroacetate aqueous solution. WillThe sodium chloroacetate aqueous solution of preparation is added drop-wise to above-mentioned steps 1) in synthetic product, 65 DEG C of stirring reaction 5h. Obtain dication typeAsphalt emulsifier, gives over to emulsified asphalt test.
Synthetic product through recrystallization carry out after separating-purifying FTIR and1HNMR detects, and result is as follows: FTIR:3250-3500cm-1For stretching vibration and the N-H stretching vibration of O-H absorb stack peak, 2918cm-1And 2846cm-1Be respectively the asymmetric of methyleneStretching vibration and symmetrical stretching vibration absworption peak, 1737cm-1For C=O stretching vibration absworption peak in carboxylic acid, 1634cm-1For carboxylic acidC=O stretching vibration absworption peak in salt, 1470cm-1For methylene scissoring vibration absworption peak, 1395cm-1For methyl symmetric curvature is shakenMoving absworption peak, 1207cm-1For C-N stretching vibration absworption peak, 1068cm-1For C-OH stretching vibration absworption peak, 926cm-1For the wagging vibration absworption peak of O-H in carboxylic acid, 717cm-1For methylene rocking vibration absworption peak.1HNMR(300MHz,D2O),δ:0.81(t,3H,-CH3),1.22(s,30H,-CH2-),1.66(s,2H,CH3(CH2)15CH 2-),2.16(s,2H,-NH+CH2CH 2CH2NH+-),2.59(m,2H,-NH+CH2CH 2COOH),3.12-3.67(m,8H,-CH 2NH+CH 2CH2CH 2NH+CH 2CH2COOH),3.73-4.24(m,4H,-CH 2COONa)ppm。
Reaction equation is as follows:
C18H37NH(CH2)3NH2+CH2＝CHCOOCH3→C18H37NH(CH2)3NH(CH2)2COOCH3(1)
(2) preparation of emulsified asphalt:
Get AH-90# pitch 300g, be heated to 125 DEG C, asphalt emulsifier prepared by 12.5g the present embodiment joins 200gIn water, to 2-3, be heated to 65 DEG C by technical hydrochloric acid adjusting pH value, make soap lye. Pitch and emulsifying agent soap lye are passed through to colloidCationic emulsified asphalt is prepared in mill emulsification.
(3) emulsified asphalt Performance Detection:
The cationic emulsified bitumen standard (JTJ052-2000) that the emulsified asphalt making is worked out by Chinese transportation portion detects, resultAs follows: emulsified asphalt prepared by the present embodiment is even, fine and smooth, and bitumen content is 59%, on sieve, surplus is 0.02%, with mineral aggregateWrap area and be greater than 2/3, storage stability (5d) is 3.5%; In de-emulsification speed test, adopt category-B material, can the mixing timeIt is 12 seconds. Show that asphalt emulsion prepared by this emulsifying agent splits type cationic emulsified bitumen in being, properties all can meetThe requirement of JTJ052-2000 standard.
Embodiment 2
(1) preparation of dication type asphalt emulsifier:
1) in reactor, add 326gN-hydrogenated-tallow group-1,3-trimethylene diamines, 400g isopropyl alcohol, heating stirring and dissolving.Then drip 175.5g methyl acrylate, 75 DEG C of stirring reaction 3h, obtain reaction intermediate.
2) 83.2g NaOH is dissolved in 160.0g water and obtains sodium hydrate aqueous solution, 196.6g monoxone is dissolved in 400.0gIn water, obtain the monoxone aqueous solution; Sodium hydrate aqueous solution is added drop-wise to and in the monoxone aqueous solution, obtains the sodium chloroacetate aqueous solution. WillThe sodium chloroacetate aqueous solution of preparation is added drop-wise to above-mentioned steps 1) in synthetic product, 75 DEG C of stirring reaction 3h. Obtain dication typeAsphalt emulsifier, gives over to emulsified asphalt test.
Synthetic product through recrystallization carry out after separating-purifying FTIR and1HNMR detects, and result is as follows: FTIR:3250-3500cm-1For stretching vibration and the N-H stretching vibration of O-H absorb stack peak, 2925cm-1And 2850cm-1Be respectively the asymmetric of methyleneStretching vibration and symmetrical stretching vibration absworption peak, 1735cm-1For C=O stretching vibration absworption peak in carboxylic acid, 1605cm-1For carboxylic acidC=O stretching vibration absworption peak in salt, 1470cm-1For methylene scissoring vibration absworption peak, 1395cm-1For methyl symmetric curvature is shakenMoving absworption peak, 1254cm-1For C-N stretching vibration absworption peak, 1068cm-1For C-OH stretching vibration absworption peak, 917cm-1For the wagging vibration absworption peak of O-H in carboxylic acid, 701cm-1For methylene rocking vibration absworption peak.1HNMR(300MHz,D2O),δ:0.85(t,3H,-CH3),1.26(s,30H,-CH2-),1.70(s,2H,CH3(CH2)15CH 2-),2.24(s,2H,-NH+CH2CH 2CH2N+-),2.57-2.64(m,4H,-CH2CH 2COOH),3.01-3.58(m,10H,-CH 2NH+CH 2CH2CH 2N+(CH 2CH2COOH)2),3.83-4.28(s,4H,-CH 2COONa)ppm。
Reaction equation is as follows:
C18H37NH(CH2)3NH2+2CH2＝CHCOOCH3→C18H37NH(CH2)3N(CH2CH2COOCH3)2(3)
(2) preparation of emulsified asphalt:
Get AH-90# pitch 300g, be heated to 125 DEG C, asphalt emulsifier prepared by 12.5g the present embodiment joins 200g waterIn, to 2-3, be heated to 65 DEG C by technical hydrochloric acid adjusting pH value, make soap lye. Pitch and emulsifying agent soap lye are passed through to colloid millCationic emulsified asphalt is prepared in emulsification.
(3) emulsified asphalt Performance Detection:
Detection method is with embodiment 1, and testing result is: emulsified asphalt is even, fine and smooth, and bitumen content is 60%, surplus on sieveBe 0.03%, wrap area be greater than 2/3 with mineral aggregate, storage stability (5d) is 3.4%; In de-emulsification speed test, adopt BClass material can be 47 seconds the mixing time. Show that asphalt emulsion prepared by this emulsifying agent is for splitting slowly type cationic emulsified bitumen, Ge XiangxingCan all can meet the requirement of JTJ052-2000 standard.
Embodiment 3
(1) preparation of dication type asphalt emulsifier:
1) in reactor, add 326gN-hydrogenated-tallow group-1,3-trimethylene diamines, 400g isopropyl alcohol, heating stirring and dissolving.Then drip 261.6g methyl acrylate, 70 DEG C of stirring reaction 4h, obtain reaction intermediate.
2) 83.2g NaOH is dissolved in 160.0g water and obtains sodium hydrate aqueous solution, 196.6g monoxone is dissolved in 400.0gIn water, obtain the monoxone aqueous solution; Sodium hydrate aqueous solution is added drop-wise to and in the monoxone aqueous solution, obtains the sodium chloroacetate aqueous solution. WillThe sodium chloroacetate aqueous solution of preparation is added drop-wise to above-mentioned steps 1) in synthetic product, 60 DEG C of stirring reaction 7h. Obtain dication typeAsphalt emulsifier, gives over to emulsified asphalt test.
Synthetic product through recrystallization carry out after separating-purifying FTIR and1HNMR detects, and result is as follows: FTIR:3427cm-1ForThe stretching vibration absworption peak of O-H, 2925cm-1And 2854cm-1Be respectively asymmetric stretching vibration and symmetrical flexible the shaking of methyleneMoving absworption peak, 1733cm-1For C=O stretching vibration absworption peak in carboxylic acid, 1606cm-1For C=O stretching vibration in carboxylate absorbsPeak, 1463cm-1For methylene scissoring vibration absworption peak, 1395cm-1For methyl symmetric curvature vibration absorption peak, 1261cm-1And 1197cm-1For C-N stretching vibration absworption peak, 1072cm-1For C-OH stretching vibration absworption peak, 930cm-1In carboxylic acidThe wagging vibration absworption peak of O-H, 772cm-1For methylene rocking vibration absworption peak.1HNMR(300MHz,D2O),δ:0.85(t,3H,-CH3),1.25(s,30H,-CH2-),1.70(s,2H,CH3(CH2)15CH 2-),2.24(s,2H,-N+CH2CH 2CH2N+-),2.63-2.85(m,6H,-CH2CH 2COOH),2.93-3.51(m,12H,-CH 2N+(CH 2CH2COOH)-CH 2CH2CH 2N+(CH 2CH2COOH)2),3.89-4.25(s,4H,-CH 2COONa)ppm。
Reaction equation is as follows:
(2) preparation of emulsified asphalt:
Get AH-90# pitch 300g, be heated to 125 DEG C, asphalt emulsifier prepared by 12.5g the present embodiment joins 200g waterIn, to 2-3, be heated to 65 DEG C by technical hydrochloric acid adjusting pH value, make soap lye. Pitch and emulsifying agent soap lye are passed through to colloid millCationic emulsified asphalt is prepared in emulsification.
(3) emulsified asphalt Performance Detection:
Detection method is with embodiment 1, and testing result is: emulsified asphalt is even, fine and smooth, and bitumen content is 59%, surplus on sieveBe 0.03%, wrap area be greater than 2/3 with mineral aggregate, storage stability (5d) is 4.1%; In de-emulsification speed test, adopt BClass material can be 14 seconds the mixing time. Show that asphalt emulsion prepared by this emulsifying agent splits type cationic emulsified bitumen, Ge Xiangxing in beingCan all can meet the requirement of JTJ052-2000 standard.
Above-described embodiment is preferably embodiment of the present invention, but embodiments of the present invention are not restricted to the described embodiments,One of ordinary skill in the art should be understood that, on the basis of technical scheme of the present invention, those skilled in the art do not need to pay woundThe property made is worked the various amendments that can make or distortion still in protection scope of the present invention.
Claims (7)
1. a preparation method for dication type asphalt emulsifier, is characterized in that, described dication type asphalt emulsifierMolecular structure is:
Wherein, in the time of x=1, y=1, z=1, i=0; In the time of x=2, y=0, z=1 or 0, i+z=1;
Preparation method comprises the steps:
(1) by N-hydrogenated-tallow group-1,3-trimethylene diamines joins in reaction vessel, adds alcohols solvent, dissolves, then addsMethyl acrylate, at 60-80 DEG C of reaction 2-6h, obtains reaction intermediate;
(2) be the 25-35% sodium chloroacetate aqueous solution to adding mass concentration in the reactant liquor of step (1), 60-80 DEG C of reaction2-7h, obtains dication type asphalt emulsifier;
In step (1), (2), N-hydrogenated-tallow group-1,3-trimethylene diamines, alcohols solvent, methyl acrylate, sodium chloroacetateMol ratio is 1:(6.00-13.00): (1.02-3.05): (2.02-2.10);
Described alcohols solvent is ethanol, methyl alcohol or isopropyl alcohol.
2. the preparation method of dication type asphalt emulsifier as claimed in claim 1, is characterized in that, in step (1),Reaction temperature is 65-75 DEG C.
3. the preparation method of dication type asphalt emulsifier as claimed in claim 1, is characterized in that, in step (2),Reaction temperature is 65-75 DEG C.
4. the preparation method of dication type asphalt emulsifier as claimed in claim 1, is characterized in that, in step (2),Sodium chloroacetate is made by monoxone and NaOH reaction.
5. the preparation method of dication type asphalt emulsifier as claimed in claim 1, is characterized in that, concrete steps are as follows:
(1) by 326gN-hydrogenated-tallow group-1,3-trimethylene diamines, 400g isopropyl alcohol, heating stirring and dissolving, then drips 90.3gMethyl acrylate, 70 DEG C of stirring reaction 4h, obtain reaction intermediate;
(2) 83.2g NaOH is dissolved in 160.0g water and obtains sodium hydrate aqueous solution, 196.6g monoxone is dissolved in 400.0gIn water, obtain the monoxone aqueous solution; Sodium hydrate aqueous solution is added drop-wise to and in the monoxone aqueous solution, obtains the sodium chloroacetate aqueous solution; WillThe sodium chloroacetate aqueous solution of preparation is added drop-wise in above-mentioned steps (1) synthetic product, and 65 DEG C of stirring reaction 5h, obtain dicationType asphalt emulsifier.
6. the preparation method of dication type asphalt emulsifier as claimed in claim 1, is characterized in that, concrete steps are as follows:
(1) by 326gN-hydrogenated-tallow group-1,3-trimethylene diamines, 400g isopropyl alcohol, heating stirring and dissolving, then drips175.5g methyl acrylate, 75 DEG C of stirring reaction 3h, obtain reaction intermediate;
(2) 83.2g NaOH is dissolved in 160.0g water and obtains sodium hydrate aqueous solution, 196.6g monoxone is dissolved in 400.0gIn water, obtain the monoxone aqueous solution; Sodium hydrate aqueous solution is added drop-wise in the monoxone aqueous solution and obtains the sodium chloroacetate aqueous solution, willThe sodium chloroacetate aqueous solution of preparation is added drop-wise in above-mentioned steps (1) synthetic product, and 75 DEG C of stirring reaction 3h, obtain dicationType asphalt emulsifier.
7. the preparation method of dication type asphalt emulsifier as claimed in claim 1, is characterized in that, concrete steps are as follows:
(1) by 326gN-hydrogenated-tallow group-1,3-trimethylene diamines, 400g isopropyl alcohol, heating stirring and dissolving, then drips 261.6gMethyl acrylate, 70 DEG C of stirring reaction 4h, obtain reaction intermediate;
(2) 83.2g NaOH is dissolved in 160.0g water and obtains sodium hydrate aqueous solution, 196.6g monoxone is dissolved in 400.0gIn water, obtain the monoxone aqueous solution; Sodium hydrate aqueous solution is added drop-wise in the monoxone aqueous solution and obtains the sodium chloroacetate aqueous solution, willThe sodium chloroacetate aqueous solution of preparation is added drop-wise in above-mentioned steps (1) synthetic product, and 60 DEG C of stirring reaction 7h, obtain dication typeAsphalt emulsifier.
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| CN105418942B (en) * | 2015-12-21 | 2017-12-19 | 山东大学 | A kind of dication acid amide type asphalt emulsifier and preparation method thereof |
| CN105384948B (en) * | 2015-12-21 | 2017-10-24 | 山东大学 | A kind of dication dual anion type asphalt emulsifier and preparation method thereof |
| CN107383391B (en) * | 2017-04-13 | 2019-05-24 | 山东大学 | A kind of secondary amide double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier and preparation method thereof |
| CN106946747B (en) * | 2017-04-13 | 2018-07-10 | 山东大学 | A kind of carboxylic acid double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier and preparation method thereof |
| CN106995393B (en) * | 2017-04-13 | 2018-07-10 | 山东大学 | A kind of double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier and preparation method thereof |
| CN108047269B (en) * | 2018-01-05 | 2019-08-13 | 山东大学 | A kind of quaternary Hydroxypropyl phosphate ester sodium splits type asphalt emulsifier and preparation method thereof fastly |
| CN113750906B (en) * | 2021-03-17 | 2022-06-17 | 山东大学 | Amphoteric surfactant and preparation method and application thereof |
| CN114907224B (en) * | 2022-07-19 | 2022-09-23 | 华巍博大(北京)科技有限公司 | Acid-resistant NEDTA complexing agent and synthesis method and application thereof |
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