CN104693041A - Diester-based cationic Gemini surfactant synthesis - Google Patents
Diester-based cationic Gemini surfactant synthesis Download PDFInfo
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- CN104693041A CN104693041A CN201310647112.1A CN201310647112A CN104693041A CN 104693041 A CN104693041 A CN 104693041A CN 201310647112 A CN201310647112 A CN 201310647112A CN 104693041 A CN104693041 A CN 104693041A
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Abstract
Lauric acid propyl (2-hydroxy-3-chloro) ester intermediate (CHPL) is synthesized from epoxy chloropropane and lauric acid as raw materials, then lauric acid propyl (2-hydroxy-3-chloro) ester intermediate (CHPL) is further reacted with tetramethylethylenediamine for synthesis of title compound (CEGs). The influence of reaction time, reaction temperature and reactant dosage molar ratio on CEGs yield can be researched, the determined optimum reaction conditions for the synthesis of the target product are as follows: isopropyl alcohol is used as a reaction medium, the molar ratio of intermediate CHPL to tetramethylethylenediamine (TMED) is 2.2:1, the reaction is performed for30h at isopropyl alcohol reflux temperature, and the recovery rate is 82.2%. The performance test shows that the newly synthesized emulsifier has good emulsifying ability, the various performances of the emulsified asphalt are completely in accordance with the national standard, and the asphalt emulsifier belongs to a medium-cracking asphalt emulsifier.
Description
Technical field
The present invention relates to the synthesis of Organic chemical products and the practical application of building field at asphalt roads, belong to fine chemistry industry and building material field.
Background technology
Emulsified bitumen be pitch and emulsifying agent under certain process acts, generate the liquid bitumen of oil-in-water or water-in-oil (specifically who wraps the kind who will see emulsifying agent).Emulsified bitumen is by the road bitumen of usual applied at elevated temperature, through mechanical stirring and chemically stable method (emulsification), is diffused in water and is liquefied as that viscosity under normal temperature is very low, the good a kind of pavement construction material of mobility.Can use by normal temperature, and can use together with the building stones of humidity with cold.Emulsified bitumen is divided into cationic emulsified bitumen, anionic emulsified bitumen and non ionic emulsified bitumen.The bitumen particle of cationic emulsified bitumen is positively charged, and anionic emulsified bitumen particulate is electronegative.When cationic emulsified bitumen contacts with aggregate surface, due to electrically charged difference, there is a natural attraction between the sexes in generation, and both can make bitumen particle wrap at aggregate surface when there being moisture film, still can adsorb combination very well.Thus under dark and damp, low temperature condition, (more than 5 DEG C) still can construct.But anionic emulsified bitumen is just in time contrary, it and moist aggregate surface are all electronegative, it is made to produce two like magnetic poles repel each other, bitumen particle can not stick on aggregate surface very soon, wrap at aggregate surface to make bitumen particle, must in liquid to be emulsified after moisture evaporation, so be just difficult to construction when meeting dark and damp or low temperature season.When emulsified bitumen breakdown of emulsion solidifies--be reduced to continuous print pitch and moisture excludes completely, the final strength of pavement material could be formed.Modified emulsifying asphalt is pitch and emulsifying agent, with latex under certain process acts, the liquid bitumen of generation.Modified emulsifying asphalt and emulsified bitumen add when being just different from generation and do not add latex.Bitumen particle is dispersed in the aqueous solution containing emulsifying agent the stable emulsion obtained.
1991, Menger etc. synthesized the two alkyl chain surfactants connected by rigid radical, and by tensio-active agent called after Shuangzi (Gemini) tensio-active agent of this type.Compared with corresponding conventional surfactant, Gemini surface active agent has the surface tension that efficiently can reduce water, lower micelle-forming concentration (CMC), the special performances such as special rheological property, but recently find, two long chain alkyl dimethyl quaternary cationicses are difficult to biological degradation under common river, river and sewage work's condition, therefore develop readily biodegradable, namely environmentally acceptable Novel Cationic Surfactants is subject to extensive concern.Gemini type cationic ester based surfactants not only has the interfacial characteristics of general cats product, and its maximum advantage is its biodegradability, is eco-friendly tensio-active agent.
Summary of the invention
The present invention relates to a kind of synthesis preparation method of di-ester-base Cationic Gemini Surfactant.The emulsifying agent of synthesis is that one splits type asphalt emulsifier slowly.Adhesion coating, mist sealing and solvent-free cold mixing can be widely used in and be recycled for pitch and Asphalt Pavement Base stablize.
Technical scheme of the present invention is as follows:
A kind of preparation method of novel cation asphalt emulsifier, adopt one pot process, with epoxy chloropropane, lauric acid for Material synthesis lauric acid third (2-hydroxyl-3-chlorine) ester intermediate (CHPL), then with Tetramethyl Ethylene Diamine further Reactive Synthesis di-ester-base Cationic Gemini Surfactant (CEGS).Instead determine best synthetic technological condition, step is as follows:
(1) synthetic intermediate CHPL:
In the 250mL there-necked flask with agitator and prolong, add 40mL (1.0mol) epoxy chloropropane (ECH), add lauric acid, after stirring makes it fully dissolving, add the appropriate anhydrous acetic acid chromium (III) of the total amount of substance of reactant 0.1% again as catalyzer, raised temperature, reacts 10 ~ 12h (when product acid number is lower than 5mg/g (in KOH), termination reaction) at 80 ~ 90 DEG C.Reclaim unnecessary epoxy chloropropane, mixture is dissolved in ether, filter 23 ~ 4 time, reclaims ether with Rotary Evaporators, obtains micro-yellow liquid, i.e. lauric acid third (2-hydroxyl-3-chlorine) ester (CHPL), yield 92.5%.
(2) synthesis of target product CEGS
In the 100mL round-bottomed flask with agitator and prolong, intermediate CHPL and Tetramethyl Ethylene Diamine (TMED) are dropped into the amount of substance of 2:2.1 ratio, take Virahol as solvent, reflux stirs, by measuring the concentration determination reaction end of chlorion.About 30h reacts end, vacuum rotary steam, obtain di-ester-base Geminini quaternary ammonium salt crude product, with the mixing solutions recrystallization 3 times of y (acetone): V (ethyl acetate)=5:1, through washed with diethylether 2-3 times, drying under reduced pressure 6-8h at 50-60 DEG C, obtains White waxy sterling CEGS, yield 82.2%.
Preferred according to the present invention, described amine is triethylamine, Trimethylamine 99 etc.
Preferred according to the present invention, the material amount of substance ratio of step (1), nonyl phenol: epoxy chloropropane=1:2;
Preferred according to the present invention, the optimal reaction temperature of step (1) is react 10 ~ 12h at 80 ~ 90 DEG C;
Preferred according to the present invention, in step (2), the consumption amount of substance of material is than being 2:2.1 for intermediate CHPL and Tetramethyl Ethylene Diamine (TMED), take Virahol as solvent.
Preferred according to the present invention, crude product in step (2), with the mixing solutions recrystallization 3 times of y (acetone): V (ethyl acetate)=5:1.
Asphalt emulsifier prepared by the present invention, without the need to carrying out separation and purification, being directly used in and preparing emulsified bitumen with oil mix.
Asphalt emulsifier prepared by the present invention, principal product is long phenol quaternary ammonium salt, and by product is amino ester, carboxylic acid amide esters etc., also containing the unreacted nonyl phenol of part.Described principal product accounts for 75-85wt%, by product accounts for 15-20wt%, and all the other are unreacted fatty primary secondary amine, tertiary amine amine and impurity completely.Described principal product, by product and unreacted reactant form compound synergic system naturally.It is under low concentration (product total concn can be less than 0.3wt%), do not need to add alkali and other cosurfactant, under wide temperature (20 DEG C ~ 40 DEG C) condition, all can reach ultra low interfacial tension with the pitch of Different sources, the i.e. 10-3mN/m order of magnitude, minimumly reaches 10-5mN/m.Reach desirable emulsifying effectiveness.
Result of study of the present invention shows, the by product of suitable configurations has raising interfacial activity and the adaptive outstanding effect of oil phase when content is suitable, ultralow oil water interfacial tension can be reached in very low concentrations, and it is fast to reduce interfacial tension, adsorption losses is low, emulsified bitumen ability is strong, improves emulsifying effectiveness remarkable.Therefore, the present invention adopts simple one pot process to prepare quaternary cationics, by the reactant conditions of specified proportion, without the need to using analytically pure material, all can use Industrial products, and not need to add neutralizing agent, by product and unreacted reactant can as effective constituents, without the need to purifying, product has higher interfacial activity and oil phase adaptability, is applicable to the preparation of emulsified bitumen for building.
Embodiment
By GB50092-96 test method, gained bitumen emulsion is analyzed (emulsifier is 1.0%).
Embodiment 1: get 5g emulsifying agent; add 200ml water, be heated to 60 ~ 70 DEG C, be dissolved into solution; take common No. 100 pitches of 300g again; be heated to 120 DEG C, start colloidal mill, emulsifying agent hydrothermal solution is added in colloidal mill; slow being poured into by heated bitumen carries out emulsification again; shut down after 1min, emulsion loads in mineral water bottle, for analysis.
Take 100g building stones, get a certain amount of water and auxiliary agent, join in iron bowl, mix, then take a certain amount of emulsified bitumen, pour in iron bowl, fully stir rapidly, and start timing, start-of-record Mixable time and molding time.
Emulsification condition: No. 100, bi tumenf orr oad, pH=2 ~ 3, emulsification dosage is 1% ~ 2%.
Emulsifying effectiveness: emulsification is complete, respond well.
Package stability: long storage periods, without Precipitation and demulsifying phenomenon, has good stability.
Mix condition: be 18 DEG C at temperature, adds 100g building stones, 1% ~ 5% cement, 8g water, 2% ~ 5% emulsified bitumen.
Mix result: can duration of mixing be 605s, for splitting type asphalt emulsifier slowly.
Table 1 emulsified bitumen performance table
Emulsifying agent has good emulsifying capacity to pitch, and the emulsified bitumen of preparation has good stability in storage.Place and aqueous phase does not occur after 6 days and pitch is separated.
Embodiment 2: take a certain amount of emulsifying agent in beaker, adds 200ml water, is heated to 50 ~ 60 DEG C, stirs, make it dissolve with glass stick, regulates pH to 2 ~ 3 with technical hydrochloric acid.Take 300AH-90 pitch again, be heated to 120 DEG C and make it melt.Start colloidal mill (first using 60 DEG C of hot water preheatings before startup), emulsifier aqueous solution is injected colloidal mill, more slowly pitch is poured in colloidal mill and carry out emulsification, in colloidal mill about one minute, emulsion is loaded in mineral water bottle, close colloidal mill.
Take 100g building stones, get a certain amount of water and auxiliary agent, join in iron bowl, mix, then take a certain amount of emulsified bitumen, pour in iron bowl, fully stir rapidly, and start timing, start-of-record Mixable time and molding time.
Emulsification condition: 300AH-90 pitch, pH=2, emulsification dosage is 1% ~ 2%.
Emulsifying effectiveness: emulsification is complete, respond well.
Package stability: long storage periods, without Precipitation and demulsifying phenomenon, has good stability.
Mix condition: be 18 DEG C at temperature, adds 100g building stones, 1% ~ 5% cement, 8g water, 2% ~ 5% emulsified bitumen.
Mix result: can duration of mixing be 500s, for splitting type asphalt emulsifier slowly.
Emulsifying agent has good emulsifying capacity to pitch, and the emulsified bitumen of preparation has good stability in storage.Place and aqueous phase does not occur after 8 days and pitch is separated.
Table 2 emulsified bitumen performance table
Embodiment 3: get 5g emulsifying agent; add 200ml water, be heated to 60 ~ 70 DEG C, be dissolved into solution; take common No. 100 pitches of 300g again; be heated to 120 DEG C, start colloidal mill, emulsifying agent hydrothermal solution is added in colloidal mill; slow being poured into by heated bitumen carries out emulsification again; shut down after 1min, emulsion loads in mineral water bottle, for analysis.
Take 100g building stones, get a certain amount of water and auxiliary agent, join in iron bowl, mix, then take a certain amount of emulsified bitumen, pour in iron bowl, fully stir rapidly, and start timing, start-of-record Mixable time and molding time.
Emulsification condition: No. 180, bi tumenf orr oad, pH=2, emulsification dosage is 1% ~ 2%.
Emulsifying effectiveness: emulsification is complete, respond well.
Package stability: long storage periods, without Precipitation and demulsifying phenomenon, has good stability.
Mix condition: be 18 DEG C at temperature, adds 100g building stones, 1 ~ 5% cement, 8g water, 2% ~ 5% emulsified bitumen.
Mix result: can duration of mixing be 578s, for splitting type asphalt emulsifier slowly.
Emulsifying agent (b) has good emulsifying capacity to pitch, and the emulsified bitumen of preparation has good stability in storage.Place and aqueous phase does not occur after 16 days and pitch is separated.
Table 3 emulsified bitumen performance table
Above-described embodiment is only for the invention example is clearly described, and the restriction not to the invention embodiment.For those of ordinary skill in the field, other multi-form change and variations can also be made on the basis of the above description.Here exhaustive without the need to also giving all embodiments.
Claims (2)
1. can the interfacial tension of common building pitch be down to ultralow, and there is the tensio-active agent asphalt emulsifier of certain stability, this Novel Cationic Surfactants optimum process condition: nonyl phenol: the mixed in molar ratio of 1:2 pressed by epoxy chloropropane, the appropriate anhydrous acetic acid chromium (III) of total amount of substance 0.1% is as catalyzer, and temperature is react 10 ~ 12h at 80 ~ 90 DEG C.Intermediate CHPL and Tetramethyl Ethylene Diamine (TMED) are dropped into the amount of substance of 2:2.1 ratio, take Virahol as the mixing solutions recrystallization 3 times of solvent y (acetone): V (ethyl acetate)=5:1, through washed with diethylether 2-3 times, drying under reduced pressure 6-8h at 50-60 DEG C, obtains White waxy sterling CEGS.
2. optimum process condition according to claim 1, solvent is Virahol.Catalyzer is anhydrous acetic acid chromium (III).
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| CN201310647112.1A CN104693041A (en) | 2013-12-04 | 2013-12-04 | Diester-based cationic Gemini surfactant synthesis |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105669449A (en) * | 2016-02-29 | 2016-06-15 | 诺泰生物科技(合肥)有限公司 | Chlorine hydroxyl ester synthesis method and application of chlorine hydroxyl ester in special oil |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105669449A (en) * | 2016-02-29 | 2016-06-15 | 诺泰生物科技(合肥)有限公司 | Chlorine hydroxyl ester synthesis method and application of chlorine hydroxyl ester in special oil |
| CN105669449B (en) * | 2016-02-29 | 2018-04-06 | 诺泰生物科技(合肥)有限公司 | A kind of synthetic method of chlorine hydroxyl ester and its application in extraordinary oil |
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Application publication date: 20150610 |