CN101712625A - Method for synthesizing amphoteric slow-breaking quick-setting asphalt emulsifier - Google Patents
Method for synthesizing amphoteric slow-breaking quick-setting asphalt emulsifier Download PDFInfo
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- CN101712625A CN101712625A CN200910065764A CN200910065764A CN101712625A CN 101712625 A CN101712625 A CN 101712625A CN 200910065764 A CN200910065764 A CN 200910065764A CN 200910065764 A CN200910065764 A CN 200910065764A CN 101712625 A CN101712625 A CN 101712625A
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Abstract
The invention discloses a method for synthesizing a novel amphoteric slow-breaking quick-setting asphalt emulsifier, belonging to the technical field of organic chemical synthesis. The method comprises the following steps of: reacting oleic acid with polyamine to generate acid amide polyamine, and then adding chloroactic acid to generate halogenating reaction to prepare the asphalt emulsifier, wherein the polyamine is the mixture of diethylenetriamine and triethylene tetramine. The water solubility of the hydrophilic radical of the emulsifier synthesized by the process is stronger than those of like emulsifiers, thereby obviously lowering the critical micelle concentration (CMC) value, and the particles of the produced asphalt emulsion are finer, smoother and evener. The emulsifier can effectively prevent asphalt from settling, increases the storage stability of the asphalt emulsion, reasonably regulates the charge ratio, widens the selectivity on stone materials in the application of slurry seal construction, enables the mixing time to be sufficient, and has obvious quick-setting effect and improved project quality.
Description
Technical field
The present invention relates to a kind of asphalt emulsifier synthetic method, belong to the organic chemistry synthesis technical field.
Background technology
Development along with the highway industry, the application of emulsified bitumen relates to a plurality of fields, seriation and diversified kind have also appearred in emulsifying agent, and nowadays motorway slurry seal and little table are in popularizing of highway industry, split the fast emulsifying agent that coagulates slowly and also are widely used.The emulsified bitumen of this type of emulsifying agent production requires and will be arranged the sufficient mixing time with building stones, and the rapid-curing effect is arranged again.Slurry seal and the more use fatty amide of little table place using emulsion agent polyamines class emulsifying agent are strong to the building stones selectivity in construction in the market.Reason is an electric charge insufficient strength on the hydrophilic group of fatty amide, the diffusion double layer of formation a little less than, influence the stability in storage of bitumen emulsion, cause the bitumen emulsion segregation, cause road surface bitumen aggregate ratio difference in the construction, influence construction quality; And use the fatty amide cost higher merely, influence the rapid-curing effect during emulsifying agents such as composite other nonionics again, therefore apply being subjected to very big obstruction.Existing market is badly in need of a kind of amphoteric slow-breaking quick-setting asphalt emulsifier.
Summary of the invention
For meeting the need of market, the object of the invention is to provide a kind of new type amphoteric to split quick-setting asphalt emulsifying agent synthetic method slowly.
For realizing the object of the invention, deficiency at present asphalt emulsifier, the present invention is split the fast molecular structure that coagulates emulsifying agent slowly to tradition and is improved, synthesized new type amphoteric by the following technical solutions and split the fast emulsifying agent that coagulates slowly: oleic acid and polyamines reaction have been generated polyamide-polyamino, add Mono Chloro Acetic Acid generation halogenating reaction then, make emulsifier production of the present invention.Described polyamines is diethylenetriamine and triethylene tetramine mixture.Described polyamines is diethylenetriamine and triethylene tetramine mixture, and both mix with weight ratio 1: 1.4-2.0.The weight ratio of oleic acid and polyamines is 1.5-2.2: 1; Oleic acid is 2.5-2.7 times of Mono Chloro Acetic Acid dripping quantity.
Innovative point of the present invention is: the fatty amide emulsifying agent is improved since fatty amide emulsifying agent electric charge a little less than, make its hydrophilic-lipophilic balance (HLB) value not reach the used ratio of desirable emulsified bitumen.The present invention introduces Mono Chloro Acetic Acid reagent, and halogenating reaction takes place, and can strengthen electric charge; And introduced carboxylic acid ion again, made that existing cation group has anionic group again on the emulsifying agent molecule, formed stronger diffusion double layer, impelled emulsified bitumen more stable.Owing to introduce the effect of negative ions on the emulsifying agent molecule, in the slurry seal construction, various building stones had selectivity and adaptability widely.Consider production cost simultaneously, adopt diethylenetriamine and the compound use of triethylene tetramine, reduced production cost to a great extent, be convenient to industrialization promotion.
The invention has the advantages that: raw materials used wide material sources, cost is low.By the emulsified bitumen performance that generates in the reaction process is detected contrast, industrialization, preferable processing condition have been determined to be suitable for, make synthetic emulsifying agent molecule not only contain cation group but also contain anionic group, increased the emulsifying capacity of product, its hydrophilic group is water-soluble water-soluble better than similar emulsifying agent, can obviously reduce micelle-forming concentration (CMC) value, make the bitumen emulsion particle fine and smooth more and even; Can effectively prevent the pitch sedimentation, improve the bitumen emulsion stability in storage, and can reasonably regulate the electric charge ratio, enlarge the selectivity to building stones in the slurry seal construction application, can make the mixing time abundant, effect is obvious with fixed attention soon, has improved construction quality.All be up to state standards by detecting every performance index.
Embodiment
For the present invention is illustrated better, as follows for embodiment:
Embodiment 1
Get oleic acid 68.3g, diethylenetriamine 13.2g, triethylene tetramine 18.7g adds in the reactor, is warming up to 160 ℃ of reactions 5 hours.Be cooled to 55 ℃ and add 95% ethanol 25g, stir.Get the 27.5g Mono Chloro Acetic Acid and be dissolved to slowly dropping in the 50% content aqueous solution, dropwise the maintenance temperature and be not higher than 60 ℃ of reactions 3 hours.With 72 ℃ of reactions of 22.3g chloroethanol temperature 2 hours, obtain the 202.5g product again, stay and do the emulsified bitumen test.
Get 70# pitch 1000g, be heated to 130 ℃.Emulsifier aqueous solution 800g, emulsifying agent 27g wherein, the adjusting pH value is 2-3, is heated to 55 ℃, prepares bitumen emulsion by colloidal mill.Obtain even, fine and smooth positively charged ion and split rapid-setting emulsified asphalt slowly.
The emulsified bitumen performance index are as follows:
| Sample number into spectrum | Fatty acid type | Emulsified bitumen stability | Bonding force | But duration of mixing |
| Embodiment 1 | Oleic acid | Stable | Qualified | ??＞2min |
Discover by experiment and can improve the workability that different building stones mix and stir, make emulsified bitumen and the slurry seal mixture performance index are as shown in the table by regulating the ratio of hydroxy-acid group and cation group:
Little table place and slurry seal emulsified bitumen technical indicator:
Little table place and slurry seal mixture technical indicator
| Project | Standard value | Measured result | Test method |
| But the mixing time (25 ℃) | Be not less than 120s | ??300 | ??ISSA?TB-113 |
| Project | Standard value | Measured result | Test method |
| Cohesion 30min 60min | Be not less than 1.2N.m and be not less than 2.0N.m | ??1..4??2.3 | ??ISSA?TB-139 |
| Adhere to the sand amount | Be not more than 538g/m 2 | ??480 | ??ISSA?TB-109 |
| Bath is peeled off | Be not more than 90% | ??60 | ??ISSA?TB-114 |
| Wet wheel abrasion loss immersion 1h immersion 6d | Be not more than 538g/m 2Be not more than 807g/m 2 | ??475??702 | ??ISSA?TB-100 |
Learn by experiment, all reach and exceed with the emulsified bitumen of this technology synthetic emulsifying agent production and the every index of compound and meet every standard that country formulates.
Comparative Examples 1
Get mixed fatty acid 57.7g, triethylene tetramine 31.9g adds in the reactor, is warming up to 160 ℃ of reactions 5 hours.Be cooled to 55 ℃ and add 95% ethanol 25g, stir.Get the 43.2g Mono Chloro Acetic Acid and be dissolved to slowly dropping in the 50% content aqueous solution, dropwise the maintenance temperature and be not higher than 60 ℃ of reactions 3 hours, with 72 ℃ of reactions of 17.2g chloropropane temperature 2 hours, obtain the 218g product again, stay and do the emulsified bitumen test.
Get 70# pitch 1000g, be heated to 130 ℃.Emulsifier aqueous solution 800g, emulsifying agent 27g wherein, the adjusting pH value is 2-3, is heated to 55 ℃, prepares bitumen emulsion by colloidal mill.Obtain even, fine and smooth positively charged ion and split rapid-setting emulsified asphalt slowly.
Actual measurement emulsified bitumen performance index are as follows:
Comparative Examples 2
Get stearic acid 60.3g, triethylene tetramine 31g adds in the reactor, is warming up to 160 ℃ of reactions 5 hours.Be cooled to 55 ℃ and add 95% ethanol 25g, stir.Get the 42g Mono Chloro Acetic Acid and be dissolved to slowly dropping in the 50% content aqueous solution, dropwise the maintenance temperature and be not higher than 60 ℃ of reactions 3 hours, with 72 ℃ of reactions of 16.7g chloropropane temperature 2 hours, obtain the 217g product again, stay and do the emulsified bitumen test.
Get 70# pitch 1000g, be heated to 130 ℃.Emulsifier aqueous solution 800g, emulsifying agent 27g wherein, the adjusting pH value is 2-3, is heated to 55 ℃, prepares bitumen emulsion by colloidal mill.Obtain even, fine and smooth positively charged ion and split rapid-setting emulsified asphalt slowly.
Actual measurement emulsified bitumen performance index are as follows:
Comparative Examples 3
Get oleic acid acid 59.9g, triethylene tetramine 31g adds in the reactor, is warming up to 160 ℃ of reactions 5 hours.Be cooled to 55 ℃ and add 95% ethanol 25g, stir.Get the 42g Mono Chloro Acetic Acid and be dissolved to slowly dropping in the 50% content aqueous solution, dropwise the maintenance temperature and be not higher than 60 ℃ of reactions 3 hours.With 72 ℃ of reactions of 17.1g chloroethanol temperature 2 hours, obtain the 217g product again, stay and do the emulsified bitumen test.
Get 70# pitch 1000g, be heated to 130 ℃.Emulsifier aqueous solution 800g, emulsifying agent 27g wherein, the adjusting pH value is 2-3, is heated to 55 ℃, prepares bitumen emulsion by colloidal mill.Obtain even, fine and smooth positively charged ion and split rapid-setting emulsified asphalt slowly.
Actual measurement emulsified bitumen performance index are as follows:
Comparative Examples 4
Get naphthenic acid 46.8g, diethylenetriamine 37.6g adds in the reactor, is warming up to 160 ℃ of reactions 5 hours.Be cooled to 55 ℃ and add 95% ethanol 25g, stir.Get the 36.2g Mono Chloro Acetic Acid and be dissolved to slowly dropping in the 50% content aqueous solution, dropwise the maintenance temperature and be not higher than 60 ℃ of reactions 3 hours.With 72 ℃ of reactions of 29.4g chloroethanol temperature 2 hours, obtain the 211.2g product again, stay and do the emulsified bitumen test.
Get 70# pitch 1000g, be heated to 130 ℃.Emulsifier aqueous solution 800g, emulsifying agent 27g wherein, the adjusting pH value is 2-3, is heated to 55 ℃, prepares bitumen emulsion by colloidal mill.Obtain even, fine and smooth positively charged ion and split rapid-setting emulsified asphalt slowly.
Actual measurement emulsified bitumen performance index are as follows:
By the campaign identical with embodiment 1, the emulsifying agent that Comparative Examples is made is used for bituminous emulsification, its performance test such as following table:
| Sample number into spectrum | Fatty acid type | Emulsified bitumen stability | Bonding force | But duration of mixing |
| Comparative Examples 1 | Mixed fatty acid | Unstable | Defective | ??＞2min |
| Comparative Examples 2 | Stearic acid | Stable | Defective | Defective |
| Comparative Examples 3 | Oleic acid | Stable | Qualified | ??＞2min |
| Comparative Examples 4 | Naphthenic acid | Unstable | Defective | ??＞2min |
As seen from the above table: the present invention has obtained the asphalt emulsifier than good quality by changing starting material and feed ratio.
Claims (3)
1. the synthetic method of amphoteric slow-breaking quick-setting asphalt emulsifier is characterized in that, contains following synthesis step: oleic acid and polyamines reacting by heating are generated polyamide-polyamino, add Mono Chloro Acetic Acid generation halogenating reaction then, make asphalt emulsifier.
2. the synthetic method of amphoteric slow-breaking quick-setting asphalt emulsifier as claimed in claim 1 is characterized in that, described polyamines is diethylenetriamine and triethylene tetramine mixture, and both mix with weight ratio 1: 1.4-2.0.
3. the synthetic method of amphoteric slow-breaking quick-setting asphalt emulsifier as claimed in claim 1 or 2 is characterized in that, the weight ratio of oleic acid and polyamines is 1.5-2.2: 1; Oleic acid is 2.5-2.7 times of Mono Chloro Acetic Acid dripping quantity.
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| CN200910065764A CN101712625B (en) | 2009-08-13 | 2009-08-13 | Method for synthesizing amphoteric slow-breaking quick-setting asphalt emulsifier |
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| CN200910065764A CN101712625B (en) | 2009-08-13 | 2009-08-13 | Method for synthesizing amphoteric slow-breaking quick-setting asphalt emulsifier |
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| CN101712625B CN101712625B (en) | 2012-10-03 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102698649A (en) * | 2012-05-17 | 2012-10-03 | 郑州轻工业学院 | Acyl-containing complexing surface active agent and synthesis method thereof |
| CN103709764A (en) * | 2013-11-01 | 2014-04-09 | 西安近代化学研究所 | Method using high boiling point by-products in ethylenediamine production for preparation of asphalt emulsifier |
| CN104893401A (en) * | 2015-06-11 | 2015-09-09 | 江苏金阳新材料科技有限公司 | Anion asphalt emulsifier for spraying rapid-hardening rubber asphalt waterproof paint and preparation method of anion asphalt emulsifier |
| CN107099041A (en) * | 2017-04-28 | 2017-08-29 | 江南大学 | A kind of high-performance asphalt emulsifier and preparation method thereof |
| CN112920311A (en) * | 2021-01-27 | 2021-06-08 | 山东交通学院 | High-molecular asphalt emulsifier and preparation method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2364952A1 (en) * | 1976-09-16 | 1978-04-14 | Azote & Prod Chim | PROCESS FOR THE PREPARATION OF QUICK-BREAKING BITUMINOUS EMULSIONS |
| 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 |
-
2009
- 2009-08-13 CN CN200910065764A patent/CN101712625B/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102698649A (en) * | 2012-05-17 | 2012-10-03 | 郑州轻工业学院 | Acyl-containing complexing surface active agent and synthesis method thereof |
| CN103709764A (en) * | 2013-11-01 | 2014-04-09 | 西安近代化学研究所 | Method using high boiling point by-products in ethylenediamine production for preparation of asphalt emulsifier |
| CN103709764B (en) * | 2013-11-01 | 2015-12-09 | 西安近代化学研究所 | The high boiling point by-products produced method preparing asphalt emulsifier in utilizing ethyleneamines to produce |
| CN104893401A (en) * | 2015-06-11 | 2015-09-09 | 江苏金阳新材料科技有限公司 | Anion asphalt emulsifier for spraying rapid-hardening rubber asphalt waterproof paint and preparation method of anion asphalt emulsifier |
| CN107099041A (en) * | 2017-04-28 | 2017-08-29 | 江南大学 | A kind of high-performance asphalt emulsifier and preparation method thereof |
| CN112920311A (en) * | 2021-01-27 | 2021-06-08 | 山东交通学院 | High-molecular asphalt emulsifier and preparation method and application thereof |
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| CN101712625B (en) | 2012-10-03 |
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