CN102516093B - Gemini type asphalt emulsifier and preparation method thereof - Google Patents
Gemini type asphalt emulsifier and preparation method thereof Download PDFInfo
- Publication number
- CN102516093B CN102516093B CN201110404128.0A CN201110404128A CN102516093B CN 102516093 B CN102516093 B CN 102516093B CN 201110404128 A CN201110404128 A CN 201110404128A CN 102516093 B CN102516093 B CN 102516093B
- Authority
- CN
- China
- Prior art keywords
- structural formula
- gemini type
- type asphalt
- asphalt emulsifier
- amine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
The invention relates to a Gemini type asphalt emulsifier and a preparation method thereof. The obtained Gemini type asphalt emulsifier can be used for effectively enhancing the stability and permeability of emulsified asphalt. The preparation method of the Gemini type asphalt emulsifier comprises the following steps of: reacting fatty amine shown as a structural formula (II) with epoxy chloropropane to obtain an intermediate; reacting the intermediate with amine shown as a structural formula (IV) to obtain the Gemini type asphalt emulsifier, wherein R1 is dodecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl or nonadecyl; R2=R3=R4=CH3, or R2=R3=R4=Et, or R2=R3=CH3 and R4=H, or R2=R3=H and R4=CH3, or R2=R3=Et and R4=H, or R2=R3=Buty and R4=H, or R2=R3=CH2CH2OH and R4=H, or R2=octadecylamino, R3=CH3 and R4=H.
Description
Technical field
The present invention relates to a kind of Gemini type asphalt emulsifier and preparation method thereof.
Background technology
Petroleum pitch is the indispensable construction material of transportation industry.Can find out from the petroleum pitch consumption of various countries: road pitch used accounts for total 70%～85%.And in the use procedure of road bitumen, for keeping the mobility of pitch, need to consume a large amount of fuel, produce the problems such as a large amount of pollutions.Therefore the mobility that how to solve pitch, economizes on resources, and reduces energy consumption, and protection of the environment is a main direction of petroleum pitch research in recent years.And succeeding in developing of the asphalt emulsifier of dissimilar and kind makes emulsified bitumen emulsion obtain using widely in highway making.
Gemini emulsifying agent is called as third generation tensio-active agent.The special structure of Gemini emulsifying agent makes itself and the conventional surfactant character that only contains a hydrophobic grouping and hydrophilic radical have very big difference.Gemini type emulsifying agent has following characteristics: it is strong that (1) forms micella ability, and cmc value is low; (2) ability that is adsorbed on interface exceedes the ability that forms micella, reduces surface tension efficiency high; (3) the clumsy point of Kr is low, good water solubility, and have the excellent hydrotropy and lyotropy, contribute to formulating of recipe; (4) good with the compatibleness of other tensio-active agents.At present, this type of emulsifying agent research report seldom.Therefore, exploitation excellent property, Gemini type asphalt emulsifier with low cost will be one of developing direction of asphalt emulsifier.
Summary of the invention
The invention provides a kind of preparation method of Gemini type asphalt emulsifier, technique is simple, reaction conditions is gentle, productive rate is higher, is easy to realize industrialization.
The Gemini type asphalt emulsifier that the present invention also provides above-mentioned preparation method to obtain, can effectively improve stability and the perviousness of emulsified bitumen.
The preparation method of described Gemini type asphalt emulsifier is: long-chain fat amine and epoxy chloropropane shown in structural formula (II) are carried out to ring-opening reaction, obtain the intermediate shown in formula (III), then make intermediate react with the amine shown in structural formula (IV), obtain the Gemini type asphalt emulsifier shown in structural formula (I)
R
1-NH
2(II)
Wherein, R
1for dodecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl or nonadecyl; R
2=R
3=R
4=CH
3, or R
2=R
3=R
4=Et or R
2=R
3=CH
3, R
4=H or R
2=R
3=H, R
4=CH
3, or R
2=R
3=Et, R
4=H or R
2=R
3=Buty, R
4=H or R
2=R
3=CH
2cH
2oH, R
4=H or R
2=stearylamine base, R
3=CH
3, R
4=H.What the amine shown in structural formula (IV) was concrete is: methylamine, dimethylamine, Trimethylamine 99, diethylamine, triethylamine, dibutylamine, N-methyl stearylamine or diethanolamine, preferably methylamine, dimethylamine, Trimethylamine 99, triethylamine, N-methyl stearylamine or diethanolamine.
Preferably, the mol ratio of the amine shown in long-chain fat amine, epoxy chloropropane and the structural formula (IV) shown in structural formula (II) is 1: (2～3): (2～3), long-chain fat amine and epoxy chloropropane shown in structural formula (II) are carried out to ring-opening reaction, obtain the intermediate shown in formula (III), productive rate is 100%; Then make intermediate react with the amine shown in structural formula (IV), obtain the Gemini type asphalt emulsifier shown in structural formula (I), productive rate is 75%-97%.The condition that long-chain fat amine shown in further preferred structure formula (II) and epoxy chloropropane carry out ring-opening reaction is: at 30～70 DEG C, react 4～9 hours; Intermediate with the condition that the amine shown in structural formula (IV) reacts is: at 20～90 DEG C, react 5～10 hours.
Preferably, long-chain fat amine shown in structural formula (II) and epoxy chloropropane carry out ring-opening reaction and intermediate reacts all and carries out in solvent with the amine shown in structural formula (IV), described solvent is dimethyl sulfoxide (DMSO), DMF, dioxane, acetonitrile, octane, ethanol, toluene, methyl alcohol, THF, ethyl acetate, normal hexane, hexanaphthene, chloroform, methylene dichloride, water or pyridine.
The structural formula of gained Gemini type asphalt emulsifier is as shown in (I).
The preparation method of Gemini type asphalt emulsifier of the present invention, technique is simple, reaction conditions is gentle, productive rate is higher, is easy to realize industrialization, and gained Gemini type asphalt emulsifier can effectively improve stability and the perviousness of emulsified bitumen.
Embodiment
In following examples, through post decouples computation productive rate.
The condition of post isolation of intermediate products is:
Adopt the silica gel chromatographic column of medium model, weighting agent is 20～25 centimetres, 200-400 object silica gel, and moving phase is chloroform/ethyl acetate=3/1～1/2 (moving phase is determined according to the polarity of intermediate product).R
f＝0.2～0.5。
The condition that post separates final product is:
Adopt the silica gel chromatographic column of medium model, weighting agent is 20～25 centimetres, 200-400 object silica gel, and moving phase is that methanol/ethyl acetate is 2/1～1/3 (moving phase is determined according to the polarity of final product).R
f＝0.1～0.4。
The Performance Detection of coating emulsified asphalt is with reference to " standard specification for construction and acceptance of highway asphalt pavement " (People's Republic of China's industry standard, JTG F40-2004) thoroughly.
Embodiment 1
In there-necked flask, add the stearylamine of 27.0g (0.1mol), the epoxy chloropropane of the ethanol of 50ml and 19.4g (0.21mol), being heated to 40 DEG C of reaction 3h, to obtain productive rate be 100% intermediate product.At 40 DEG C to the triethylamine that drips 22.3g (0.22mol) in there-necked flask.After dripping, be warmed up to 90 DEG C of reaction 10h, steam ethanol.Obtain crude product and carried out post and separate, obtain productive rate and be 92.1% pure emulsifying agent.
Intermediate product carries out after post separating-purifying
1h-NMR and IR detect, and result is as follows:
1H-NMR(400MHz，CDCl
3，δppm)δ3.84(d，J＝8.0Hz，4H)，3.75(m，2H)，2.58(d，J＝7.6Hz，4H)，2.42(t，J＝15.2Hz，J＝7.6Hz，2H)，2.24(s，2H)，1.26-1.33(m，32H)，0.93(t，J＝16.0Hz，J＝8.0Hz，3H).
IR(neat)：3408cm
-1，1459cm
-1，1221cm
-1，1026cm
-1，1103cm
-1，745cm
-1，716cm
-1.
The finished product carry out after post separating-purifying
1h-NMR and IR detect, and result is as follows:
1H-NMR(400MHz，CDCl
3，δppm)δ4.17(m，2H)，3.48(d，J＝7.2Hz，4H)，3.21(m，12H)，2.61(d，J＝8.0Hz，4H)，2.36(t，J＝16.02Hz，J＝8.0Hz，2H)，2.31(s，2H)，1.25(t，J＝8.4Hz，J＝16.0Hz，J＝7.6Hz，18H)，1.28-1.36(m，32H)，0.96(t，J＝7.6Hz，J＝16.0Hz，J＝8.4Hz，3H).
IR(neat)：3419cm
-1，1460cm
-1，1227cm
-1，1130cm
-1，1052cm
-1，780cm
-1，725cm
-1.
Get bi tumenf orr oad 600g No. 70, be heated to 140 DEG C.Emulsifier aqueous solution 400g, wherein emulsifying agent 4g, is heated to 60 DEG C, prepares bitumen emulsion by colloidal mill.Obtain even, fine and smooth positively charged ion slow-breaking emulsified asphalt.The emulsified bitumen that employing makes is prepared asphalt of penetrate layer compound, and its performance is as shown in the table.
The performance of asphalt of penetrate layer compound
Embodiment 2
In there-necked flask, add the stearylamine of 27.0g (0.1mol), the epoxy chloropropane of the chloroform of 50ml and 22.2g (0.24mol), being heated to 30 DEG C of reaction 4h, to obtain productive rate be 100% intermediate product.At 30 DEG C to the Trimethylamine 99 that drips 39.1g (0.23mol) in there-necked flask.After dripping, be warmed up to 80 DEG C of reaction 5h, steam chloroform.Obtain crude product and carried out post and separate, obtain productive rate and be 87.6% pure emulsifying agent.
Intermediate product carries out after post separating-purifying
1h-NMR and IR detect, and result is as follows:
1H-NMR(400MHz，CDCl
3，δppm)δ3.84(d，J＝8.0Hz，4H)，3.75(m，2H)，2.58(d，J＝7.6Hz，4H)，2.42(t，J＝15.2Hz，J＝7.6Hz，2H)，2.24(s，2H)，1.26-1.33(m，32H)，0.93(t，J＝16.0Hz，J＝8.0Hz，3H).
IR(neat)：3408cm
-1，1459cm
-1，1221cm
-1，1026cm
-1，1103cm
-1，745cm
-1，716cm
-1.
The finished product carry out after post separating-purifying
1h-NMR and IR detect, and result is as follows:
1H-NMR(400MHz，CDCl
3，δppm)δ4.12(m，2H)，3.45(d，J＝8.0Hz，4H)，3.25(s，18H)，2.63(d，J＝8.4Hz，4H)，2.38(t，J＝15.2Hz，J＝7.6Hz，2H)，2.31(s，2H)，1.26-1.33(m，32H)，0.88(t，J＝7.6Hz，J＝16.0Hz，J＝8.4Hz，3H).
IR(neat)：3408cm
-1，1465cm
-1，1227cm
-1，1038cm
-1，1082cm
-1，751cm
-1，715cm
-1.
Get bi tumenf orr oad 600g No. 90, be heated to 140 DEG C.Emulsifier aqueous solution 400g, wherein emulsifying agent 3.5g, is heated to 60 DEG C, prepares bitumen emulsion by colloidal mill.Obtain even, fine and smooth positively charged ion slow-breaking emulsified asphalt.The emulsified bitumen that employing makes is prepared asphalt of penetrate layer compound, and its performance is as shown in the table.
The performance of asphalt of penetrate layer compound
Embodiment 3
In there-necked flask, add the stearylamine of 27.0g (0.1mol), the epoxy chloropropane of the water of 50ml and 23.1g (0.25mol), being heated to 20 DEG C of reaction 5h, to obtain productive rate be 100% intermediate product.At 35 DEG C to the dimethylamine that drips 35.5g (0.26mol) in there-necked flask.After dripping, be warmed up to 90 DEG C of reaction 8h, steam water.Obtain crude product and carried out post and separate, obtain productive rate and be 90.6% pure emulsifying agent.
Intermediate product carries out after post separating-purifying
1h-NMR and IR detect, and result is as follows:
1H-NMR(400MHz，CDCl
3，δppm)δ3.84(d，J＝8.0Hz，4H)，3.75(m，2H)，2.58(d，J＝7.6Hz，4H)，2.42(t，J＝15.2Hz，J＝7.6Hz，2H)，2.24(s，2H)，1.26-1.33(m，32H)，0.93(t，J＝16.0Hz，J＝8.0Hz，3H).
IR(neat)：3408cm
-1，1459cm
-1，1221cm
-1，1026cm
-1，1103cm
-1，745cm
-1，716cm
-1.
The finished product carry out after post separating-purifying
1h-NMR and IR detect, and result is as follows:
1H-NMR(400MHz，CDCl
3，δ，ppm)δ7.15(s，2H)，4.18(m，2H)，3.23(d，J＝8.4Hz，4H)，2.95(s，12H)，2.55(d，J＝7.6Hz，4H)，2.33(t，J＝7.6Hz，J＝14.8Hz，J＝7.2Hz，2H)，2.21(s，2H)，1.28-1.36(m，32H)，0.91(t，J＝7.6Hz，J＝14.8Hz，J＝7.2Hz，3H).
IR(neat)：3442cm
-1，2718cm
-1，1459cm
-1，1217cm
-1，1132cm
-1，1097cm
-1，734cm
-1，718cm
-1.
Get bi tumenf orr oad 600g No. 70, be heated to 150 DEG C.Emulsifier aqueous solution 400g, wherein emulsifying agent 2.5g, is heated to 60 DEG C, prepares bitumen emulsion by colloidal mill.Obtain even, fine and smooth positively charged ion slow-breaking emulsified asphalt.The emulsified bitumen that employing makes is prepared asphalt of penetrate layer compound, and its performance is as shown in the table.
The performance of asphalt of penetrate layer compound
Embodiment 4
In there-necked flask, add the stearylamine of 27.0g (0.1mol), the epoxy chloropropane of the octane of 50ml and 19.4g (0.21mol), being heated to 70 DEG C of reaction 7.5h, to obtain productive rate be 100% intermediate product.At 70 DEG C to the methylamine that drips 28.3g (0.30mol) in there-necked flask.After dripping, be warmed up to 90 DEG C of reaction 6.5h, steam octane.Obtain crude product and carried out post and separate, obtain productive rate and be 80.2% pure emulsifying agent.
Intermediate product carries out after post separating-purifying
1h-NMR and IR detect, and result is as follows:
1H-NMR(400MHz，CDCl
3，δppm)δ3.84(d，J＝8.0Hz，4H)，3.75(m，2H)，2.58(d，J＝7.6Hz，4H)，2.42(t，J＝15.2Hz，J＝7.6Hz，2H)，2.24(s，2H)，1.26-1.33(m，32H)，0.93(t，J＝16.0Hz，J＝8.0Hz，3H).
IR(neat)：3408cm
-1，1459cm
-1，1221cm
-1，1026cm
-1，1103cm
-1，745cm
-1，716cm
-1.
The finished product carry out after post separating-purifying
1h-NMR and IR detect, and result is as follows:
1H-NMR(400MHz，CDCl
3，δ，ppm)δ6.81(s，4H)，4.06(m，2H)，3.47(d，J＝8.0Hz，4H)，2.90(s，6H)，2.51(d，J＝8.4Hz，4H)，2.36(t，J＝15.2Hz，J＝7.6Hz，2H)，2.23(s，2H)，1.31-1.39(m，32H)，0.93(t，J＝8.0Hz，J＝15.6Hz，J＝7.6Hz，3H).
IR(neat)：3457cm
-1，2959cm
-1，1463cm
-1，1228cm
-1，1124cm
-1，1105cm
-1，762cm
-1，718cm
-1.
Get bi tumenf orr oad 600g No. 90, be heated to 140 DEG C.Emulsifier aqueous solution 400g, wherein emulsifying agent 2.0g, is heated to 60 DEG C, prepares bitumen emulsion by colloidal mill.Obtain even, fine and smooth positively charged ion slow-breaking emulsified asphalt.The emulsified bitumen that employing makes is prepared asphalt of penetrate layer compound, and it is as shown in the table for its performance.
The performance of asphalt of penetrate layer compound
Embodiment 5
In there-necked flask, add the cetylamine of 24.1g (0.1mol), the epoxy chloropropane of the DMF of 50ml and 21.3g (0.23mol), being heated to 45 DEG C of reaction 3h, to obtain productive rate be 100% intermediate product.At 45 DEG C to the triethylamine that drips 22.3g (0.22mol) in there-necked flask.After dripping, be warmed up to 85 DEG C of reaction 5h.Obtain crude product and carried out post and separate, obtain productive rate and be 94.5% pure emulsifying agent.
Intermediate product carries out after post separating-purifying
1h-NMR and IR detect, and result is as follows:
1H-NMR(400MHz，CDCl
3，δppm)δ3.75(d，J＝7.6Hz，4H)，3.68(m，2H)，2.51(d，J＝8.4Hz，4H)，2.40(t，J＝8.4Hz，J＝16.0Hz，J＝7.6Hz，2H)，2.18(s，2H)，1.25-1.31(m，28H)，0.96(t，J＝16.0Hz，J＝8.0Hz，3H).
IR(neat)：3411cm
-1，1462cm
-1，1229cm
-1，1030cm
-1，1096cm
-1，753cm
-1，718cm
-1.
The finished product carry out after post separating-purifying
1h-NMR and IR detect, and result is as follows:
1H-NMR(400MHz，CDCl
3，δppm)δ4.16(m，2H)，3.54(d，J＝7.6Hz，4H)，3.31(s，18H)，2.58(d，J＝8.0Hz，4H)，2.39(t，J＝7.6，J＝14.8Hz，J＝7.2Hz，2H)，2.07(s，2H)，1.28-1.33(m，28H)，0.81(t，J＝8.4Hz，J＝16.0Hz，J＝7.6Hz，3H).
IR(neat)：3447cm
-1，1460cm
-1，1235cm
-1，1131cm
-1，1097cm
-1，736cm
-1，720cm
-1.
Get bi tumenf orr oad 600g No. 90, be heated to 140 DEG C.Emulsifier aqueous solution 400g, wherein emulsifying agent 5g, AlCl
32g, regulates pH value to 2-3, is heated to 60 DEG C, prepares bitumen emulsion by colloidal mill.Obtain even, fine and smooth positively charged ion slow-breaking emulsified asphalt.The emulsified bitumen that employing makes is prepared asphalt of penetrate layer compound, and it is as shown in the table for its performance.
The performance of asphalt of penetrate layer compound
Embodiment 6
In there-necked flask, add the tetradecy lamine of 21.3g (0.1mol), the epoxy chloropropane of the dioxane of 50ml and 23.1g (0.25mol), being heated to 70 DEG C of reaction 9h, to obtain productive rate be 100% intermediate product.At 70 DEG C to the diethanolamine that drips 30.5g (0.29mol) in there-necked flask.After dripping, be warmed up to 90 DEG C of reaction 8h, steam dioxane.Obtain crude product and carried out post and separate, obtain productive rate and be 87.3% pure emulsifying agent.
Intermediate product carries out after post separating-purifying
1h-NMR and IR detect, and result is as follows:
1H-NMR(400MHz，CDCl
3，δppm)δ3.91(d，J＝8.0Hz，4H)，3.72(m，2H)，2.62(d，J＝8.0Hz，4H)，2.35(t，J＝16.0Hz，J＝8.0Hz，2H)，2.21(s，2H)，1.23-1.29(m，24H)，0.83(t，J＝7.6Hz，J＝15.6Hz，J＝8.0Hz，3H).
IR(neat)：3428cm
-1，1458cm
-1，1220cm
-1，1018cm
-1，1086cm
-1，748cm
-1，725cm
-1.
The finished product carry out after post separating-purifying
1h-NMR and IR detect, and result is as follows:
1H-NMR(400MHz，CDCl
3，δppm)δ4.33(m，2H)，4.08(t，J＝16.0Hz，J＝8.0Hz，4H)3.39(d，J＝8.0Hz，8H)，3.21(t，J＝7.6Hz，J＝15.6Hz，J＝8.0Hz，8H)，2.57(d，J＝8.0Hz，4H)，2.31(t，J＝8.0Hz，J＝15.6Hz，J＝7.6Hz，2H)，2.14(s，2H)2.11(s，2H)，1.27-1.32(m，24H)，0.92(t，J＝16.0Hz，J＝8.0Hz，3H).
IR(neat)：3418cm
-1，1460cm
-1，1231cm
-1，1112cm
-1，1102cm
-1，734cm
-1，724cm
-1.
Get bi tumenf orr oad 600g No. 70, be heated to 150 DEG C.Emulsifier aqueous solution 400g, wherein emulsifying agent 4.5g, regulates pH value to 2-3, is heated to 60 DEG C, prepares bitumen emulsion by colloidal mill.Obtain even, fine and smooth positively charged ion slow-breaking emulsified asphalt.The emulsified bitumen that employing makes is prepared asphalt of penetrate layer compound, and it is as shown in the table for its performance.
The performance of asphalt of penetrate layer compound
Embodiment 7
In there-necked flask, add the amino dodecane of 18.5g (0.1mol), the epoxy chloropropane of the THF of 50ml and 27.8g (0.3mol), being heated to 65 DEG C of reaction 5.5h, to obtain productive rate be 100% intermediate product.At 40 DEG C to the N-methyl stearylamine that drips 85.1g (0.30mol) in there-necked flask.After dripping, be warmed up to 75 DEG C of reaction 8h, obtain crude product and carried out post and separate, obtain productive rate and be 76.3% pure emulsifying agent.
Intermediate product carries out after post separating-purifying
1h-NMR and IR detect, and result is as follows:
Intermediate product carries out after post separating-purifying
1h-NMR and IR detect, and result is as follows:
1H-NMR(400MHz，CDCl
3，δppm)δ3.78(d，J＝7.6Hz，4H)，3.72(m，2H)，2.51(d，J＝8.0Hz，4H)，2.46(t，＝8.0Hz，J＝15.6Hz，J＝7.6Hz，2H)，2.29(s，2H)，1.21-1.37(m，20H)，0.85(t，J＝16.0Hz，J＝8.0Hz，3H).
IR(neat)：3422cm
-1，1453cm
-1，1231cm
-1，1035cm
-1，1112cm
-1，772cm
-1，714cm
-1.
The finished product after post separating-purifying, carry out 1H-NMR and IR detects, and result is as follows:
1H-NMR(400MHz，CDCl
3，δppm)δ4.43(m，2H)，3.31(d，J＝8.0Hz，4H)，3.14(d，J＝7.6Hz，4H)，2.67(s，3H)，2.32(t，J＝16.0Hz，J＝8.0Hz，2H)，2.32(t，J＝7.6Hz，J＝15.6Hz，J＝8.0Hz，2H)，2.01(s，2H)，1.21-1.37(m，52H)，0.96(t，J＝15.2Hz，J＝7.6Hz，3H)，0.89(t，J＝8.0Hz，J＝15.6Hz，J＝7.6Hz，3H).
IR(neat)：3459cm
-1，1485cm
-1，1231cm
-1，1124cm
-1，1097cm
-1，771cm
-1，721cm
-1.
Get bi tumenf orr oad 600g No. 90, be heated to 140 DEG C.Emulsifier aqueous solution 400g, wherein emulsifying agent 2.0g, CaCl
22g, regulates pH value to 2-3, is heated to 60 DEG C, prepares bitumen emulsion by colloidal mill.Obtain even, fine and smooth positively charged ion slow-breaking emulsified asphalt.The emulsified bitumen that employing makes is prepared asphalt of penetrate layer compound, and it is as shown in the table for its performance.
The performance of asphalt of penetrate layer compound
Claims (3)
1. the preparation method of a Gemini type asphalt emulsifier, it is characterized in that, long-chain fat amine and epoxy chloropropane shown in structural formula (II) are carried out to ring-opening reaction, obtain the intermediate shown in formula (III), then make intermediate react with the amine shown in structural formula (IV), obtain the Gemini type asphalt emulsifier shown in structural formula (I)
R
1-NH
2(II)
Wherein, R
1for dodecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl or nonadecyl; R
2=R
3=R
4=CH
3, or R
2=R
3=R
4=Et or R
2=R
3=CH
3, R
4=H or R
2=R
3=H, R
4=CH
3, or R
2=R
3=Et, R
4=H or R
2=R
3=Buty, R
4=H or R
2=R
3=CH
2cH
2oH, R
4=H;
The mol ratio of the amine shown in long-chain fat amine, epoxy chloropropane and the structural formula (IV) shown in structural formula (II) is 1: (2～3): (2～3), long-chain fat amine and epoxy chloropropane shown in structural formula (II) are carried out to ring-opening reaction, obtain the intermediate shown in formula (III), productive rate is 100%; Then make intermediate react with the amine shown in structural formula (IV), obtain the Gemini type asphalt emulsifier shown in structural formula (I), productive rate is 75%-97%;
The condition that long-chain fat amine shown in structural formula (II) and epoxy chloropropane carry out ring-opening reaction is: at 30～70 DEG C, react 4～9 hours; Intermediate with the condition that the amine shown in structural formula (IV) reacts is: at 20～90 DEG C, react 5～10 hours;
Long-chain fat amine shown in structural formula (II) and epoxy chloropropane carry out ring-opening reaction and intermediate reacts all and carries out in solvent with the amine shown in structural formula (IV), described solvent is dimethyl sulfoxide (DMSO), DMF, dioxane, acetonitrile, octane, ethanol, toluene, methyl alcohol, tetrahydrofuran (THF), ethyl acetate, normal hexane, hexanaphthene, chloroform, methylene dichloride, water or pyridine.
2. the preparation method of Gemini type asphalt emulsifier as described in claim 1, is characterized in that R2=R
3=R
4=CH
3, or R
2=R
3=R
4=Et or R
2=R
3=CH
3, R
4=H or R
2=R
3=H, R
4=CH
3, or R
2=R
3=CH
2cH
2oH, R
4=H.
3. a Gemini type asphalt emulsifier, is characterized in that its structural formula is as shown in (I).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110404128.0A CN102516093B (en) | 2011-12-08 | 2011-12-08 | Gemini type asphalt emulsifier and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110404128.0A CN102516093B (en) | 2011-12-08 | 2011-12-08 | Gemini type asphalt emulsifier and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102516093A CN102516093A (en) | 2012-06-27 |
| CN102516093B true CN102516093B (en) | 2014-10-08 |
Family
ID=46287231
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110404128.0A Active CN102516093B (en) | 2011-12-08 | 2011-12-08 | Gemini type asphalt emulsifier and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102516093B (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103525099B (en) * | 2012-07-03 | 2015-10-28 | 华东理工大学 | Compound asphalt emulsifier containing Gemini surface active agent |
| CN102924299B (en) * | 2012-08-24 | 2014-08-13 | 武汉理工大学 | Preparation method of novel slow-crack slow-coagulation asphalt emulsifier |
| CN103113618B (en) * | 2012-12-25 | 2014-10-29 | 江苏苏博特新材料股份有限公司 | Method for preparing cold-recycling asphalt emulsification additive |
| CN103613941B (en) * | 2013-12-09 | 2016-07-06 | 江苏苏博特新材料股份有限公司 | The preparation method of amphoteric ion type asphalt warm-mix agent and the application in warm-mixed asphalt thereof |
| CN104609771B (en) * | 2015-01-14 | 2017-04-12 | 江苏苏博特新材料股份有限公司 | Warm-mixing reclaiming agent and preparation method thereof |
| 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 |
| CN106422962A (en) * | 2016-10-31 | 2017-02-22 | 四川理工学院 | Synthesis method and application of 2-chloride, 3-poly hydroxypropyl dodecylamine quaternary ammonium salt surfactant |
| CN106832166B (en) * | 2016-12-31 | 2019-03-12 | 山西省交通科学研究院 | A kind of coemulsifier and preparation method thereof applied to emulsified asphalt cold in place recycling mixture |
| CN107162918A (en) * | 2017-05-09 | 2017-09-15 | 中国民航大学 | 2 chlorinations, the synthetic method of 3 poly- hydroxypropyl isopropylamine quaternary surfactants |
| CN108041035A (en) * | 2017-12-12 | 2018-05-18 | 中海油天津化工研究设计院有限公司 | A kind of dication epoxy type fungicide and preparation method thereof |
| CN108409586A (en) * | 2018-02-05 | 2018-08-17 | 苏州拓博琳新材料科技有限公司 | Antistripping agent, preparation method and liquid asphalt |
| CN112029302A (en) * | 2018-04-05 | 2020-12-04 | 湖南辰砾新材料有限公司 | Zwitterionic Gemini emulsifier and application thereof in asphalt |
| CN108586773A (en) * | 2018-05-15 | 2018-09-28 | 苏州太星新材料科技有限公司 | A kind of aliphatic chain graphene oxide nonionic asphalt emulsifier and preparation method thereof |
| CN111349347A (en) * | 2020-05-14 | 2020-06-30 | 海娇 | Modified emulsified asphalt and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1096714A (en) * | 1993-06-24 | 1994-12-28 | 中国石油化工总公司抚顺石油化工研究院 | Cation asphalt emulgent |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4927515A (en) * | 1972-07-10 | 1974-03-12 | ||
| JPH0927515A (en) * | 1995-07-12 | 1997-01-28 | Nitto Denko Corp | Semiconductor mounting method |
-
2011
- 2011-12-08 CN CN201110404128.0A patent/CN102516093B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1096714A (en) * | 1993-06-24 | 1994-12-28 | 中国石油化工总公司抚顺石油化工研究院 | Cation asphalt emulgent |
Non-Patent Citations (3)
| Title |
|---|
| Gemini型阳离子沥青乳化剂的合成与性能测试;施来顺 等;《石油沥青》;20101231;第24卷(第6期);第67页1.3，1.5 * |
| JP特开昭49-27515A 1974.03.12 |
| 施来顺 等.Gemini型阳离子沥青乳化剂的合成与性能测试.《石油沥青》.2010,第24卷(第6期),第67页1.3十八烷基-双(3-十八烷基二甲基氯化铵-2-羟基丙基)叔胺的合成，1.5十八烷基-双叔胺的合成. |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102516093A (en) | 2012-06-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102516093B (en) | Gemini type asphalt emulsifier and preparation method thereof | |
| CN102531931B (en) | Phenol quaternary ammonium salt emulsifier and preparation method thereof | |
| CN103406063B (en) | Cationic gemini surfactant preparation method | |
| CN105384948A (en) | Dication and dianion type asphalt emulsifier and preparation method thereof | |
| CN104169265B (en) | Use acetate alkyl ammonium to prepare the new method of AcHMF | |
| CN103721584B (en) | A kind of preparation method of silicone oil pickering emulsion | |
| CN103274972B (en) | Synthesis method of zwitterion type modified asphalt emulsifier and modified emulsified asphalt containing emulsifier | |
| Gao et al. | Synthesis and surface activity of biquaternary ammonium salt gemini surfactants with ester bond | |
| CN104437238A (en) | Amide-type bis-hydroxypropyl sulphobetaine surfactant as well as preparation method and application thereof | |
| CN103864637B (en) | A kind of N-(β-4-nitro alkyl) preparation method of amides | |
| CN103585925A (en) | Preparation method of double-end based amide type glycine betaine surfactant and application thereof | |
| CN109096313A (en) | A kind of trimeric indenyl click coughs up-preparation method of porphyrin-fullerene star-like compound | |
| CN104403653B (en) | A kind of environment-friendly type Flooding Agent for EOR based on biosurfactant | |
| CN105523949A (en) | Method for preparing triethanolamine acrylate compound | |
| CN103387238B (en) | Preparation technology of Ethyl-bridged functionalized ordered mesoporous PMO | |
| CA2555777A1 (en) | Dehydrating condensation agent having property of accumulating at interface with water | |
| CN111088011B (en) | Composite surfactant for improving crude oil recovery ratio and preparation method and application thereof | |
| CN102659681B (en) | For the preparation method of the imidazolines cation asphalt emulgent of micro-surface area | |
| CN106588708B (en) | The synthetic method of Gemini surface active agent | |
| CN109593043A (en) | A kind of benzenediol cationoid asphalt emulsifier and preparation method | |
| CN111378151B (en) | Bisphenol A type gemini asphalt emulsifier and preparation method thereof | |
| CN102093258B (en) | Aromatic diamidine compound and synthesis method thereof | |
| CN103849370B (en) | A kind of fracturing propping agents and preparation method thereof | |
| CN104001449A (en) | Quaternary ammonium salt type Gemini surfactant containing biphenyl group, and preparation method thereof | |
| CN108727231A (en) | A kind of ester crosslinking anacardol sulfonate anionic asphalt emulsifier and preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: JIANGSU SUBOTE NEW MATERIAL CO., LTD. Free format text: FORMER OWNER: BOTE NEW MATERIAL CO., LTD., JIANGSU Effective date: 20150212 Free format text: FORMER OWNER: JIANGSU SUBOTE NEW MATERIAL CO., LTD. JAINGSU ACADEMY OF BUILDING RESEARCH CO., LTD. Effective date: 20150212 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 210008 NANJING, JIANGSU PROVINCE TO: 211103 NANJING, JIANGSU PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20150212 Address after: Jiangning District of Nanjing City, Jiangsu province 211103 Li Quan Lu No. 118 Patentee after: Jiangsu Subute New Materials Co., Ltd. Address before: 210008 No. 12 West Beijing Road, Jiangsu, Nanjing Patentee before: Jiangsu Bote New Materials Co., Ltd. Patentee before: Jiangsu Subute New Materials Co., Ltd. Patentee before: Jiangsu Provincial Architectural Science Institute Ltd. |