CN104693043A - An improvement in a synthesis process for a saturated aliphatic amine cation asphalt emulsifier - Google Patents
An improvement in a synthesis process for a saturated aliphatic amine cation asphalt emulsifier Download PDFInfo
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- CN104693043A CN104693043A CN201310655765.4A CN201310655765A CN104693043A CN 104693043 A CN104693043 A CN 104693043A CN 201310655765 A CN201310655765 A CN 201310655765A CN 104693043 A CN104693043 A CN 104693043A
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- emulsifier
- asphalt
- asphalt emulsifier
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- emulsified bitumen
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Abstract
The invention synthesizes a novel cation asphalt emulsifier by utilization of N,N-dimethyl octadecylamine, epichlorohydrin and an aqueous dimethylamine solution through two-step reactions and obtains the optimum reaction process conditions for synthesis of N,N-dimethyl-N-(ethylene oxide-2-methylene)octadecyl-1-ammonium chloride. By-products of the first step of reaction are detected by an online infrared spectrum technique. Base on experiment data, a reasonable reaction mechanism is provided. The CMC value of the target compound is 4.35*10<-4> mol/L and is relatively low, and the surface tension at the critical micelle concentration is 28.51 mN/m. The synthesized emulsifier is a medium-splitting-speed type asphalt emulsifier, and can be widely used for adhesion layers, fog sealing layers, solvent-free cold mixing, recovery and reutilization of asphalt, and stabilization of asphalt pavement bases.
Description
Technical field
The present invention relates to chemical industry organic synthesis, belong to field of fine chemical.
Background technology
Emulsified bitumen refers to asphalt heating melting, and through mechanical effect, pitch forms the bitumen emulsion of oil-in-water (O/W) shape in containing the aqueous solution of emulsifying agent with tiny graininess stable dispersion.Compared with heated bitumen, emulsified bitumen can be applied at normal temperatures, has the advantages such as better adhesive capacity, less energy-consumption and environmental pollution with building stones be little, is widely used in highway and water-proof material.
Emulsified bitumen is emulsion oil-in-water, and asphalt emulsifier can be divided into cationic, anionic, amphoteric and non-ionic type.The mainly anionic emulsifier that the research initial stage uses, as an alkali metal salt of long-chain sulfonate salt, xylogen and carboxylate salt etc.Cationic emulsifier development in recent years is rapid, and cation asphalt emulgent has good emulsifying property and the bonding strength stronger to building stones.Most of building stones have negative charge, cationic emulsified bitumen can rapid adsorption and be bonded in its surface.Main cationic emulsifier is nitrogenous organic amine derivatives.Honma have studied a kind of positively charged ion of temperature and building stones characteristics influence that is subject to hardly and splits type asphalt emulsifier slowly.Gemini emulsifying agent is a kind of tensio-active agent containing two or more hydrophilic groups and oleophilic group, has very strong surfactivity.Rist utilizes corresponding alkyl alcohol and 2-chloro-N, N-dimethyl amine under alkaline environment, have synthesized linear Gemini type quaternary surfactant.
Zwitter-ion emulsifying agent is also an active research direction, is mainly divided into betaine type and amino acid pattern etc.In this kind of emulsifier molecules structure, hydrophilic group has acidity and basic group simultaneously, and amphoteric emulsifier is applicable to different pH environment.Zwitter-ion emulsifying agent has good emulsifying performance, all has good consistency with positively charged ion, negatively charged ion and nonionic emulsifier.The research field of betaine type emulsifying agent is very wide.The people such as Martin utilize betaine type emulsifying agent to prepare emulsified bitumen, and for the laying of sub-surface.Non-ionic type asphalt emulsifier has good chemical stability.Usual a kind of nonionogenic tenside obtains by following steps: joined by oxyethane and have in the alcohol of long-chain, then joined in obtained compound by propylene oxide again.The emulsified bitumen prepared by nonionic emulsifier under static state has good preservation stability.
The present invention has synthesized a kind of cationic asphalt emulsifier with fine emulsifying property, and is optimized synthetic route.
Summary of the invention
The present invention relates to a kind of preparation method of novel cation asphalt emulsifier.The emulsifying agent of synthesis splits type asphalt emulsifier in one.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 long-chain fat tertiary amine, epoxy chloropropane, dimethylamine agueous solution through two-step reaction synthesize a kind of novel cation asphalt emulsifier N-(3-(N ', N '-dimethylamino)-2-hydroxypropyl)-N, N-dimethyl stearyl-1-ammonium chloride is reactant, react under the basic catalyst effect of specified proportion, directly obtained asphalt emulsifier, step is as follows:
(1) long-chain alkyl tertiary amine of certain mass is dissolved in a certain amount of dehydrated alcohol
(2) then dropwise add amount of substance than being the epoxy chloropropane within the scope of 1:1.2, under 50 DEG C of stirring in water bath, react 5h, recrystallization obtains product.
(3) dimethylamine agueous solution of appropriate 30% ~ 40% is dropwise joined the N of above synthesis, in N-dimethyl-N-(oxyethane-2-methylene radical) octadecyl-1-ammonium chloride, 45 ~ 65 DEG C of stirring in water bath reaction 3 ~ 5h.
(4) aqueous phase separating funnel separates, and oil phase removes desolventizing through underpressure distillation
(5) then use ethyl acetate and sherwood oil mixed solution recrystallization, be dried to constant weight under obtaining product vacuum condition, yield 69.9%.
Scheme1 is the synthetic route of asphalt emulsifier.
Preferred according to the present invention, described aliphatic amide is octadecyl tertiary amine, dodecyl tertiary amine, hexadecyl tertiary amine etc.
Preferred according to the present invention, the material amount of substance of step (1) compares 1:1.2;
Preferred according to the present invention, the temperature of reaction of step (2) 40 ~ 50 DEG C, the reaction times is 3 ~ 5h;
Preferred according to the present invention, in step (2) recrystallization solvent for use be purity higher than 99% ethyl acetate;
Preferred according to the present invention, temperature of reaction 40 ~ 65 DEG C in step (3), the reaction times is 3 ~ 5h.
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 chain alkyl ammonium salt, and by product is amino ester, carboxylic acid amide esters etc., also containing the unreacted fatty acid ester of part, tertiary amine.Described principal product accounts for 65-75wt%, 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 does not need to add alkali and other cosurfactant under low concentration (product total concn can be less than 0.3wt%), under wide temperature (20 DEG C ~ 40 DEG C) condition, all can reach ultra low interfacial tension with the pitch of Different sources, and namely 10
-3the mN/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, appropriate catalytic dosage, without the need to vacuumizing, and does 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.
Accompanying drawing explanation
The logarithmic relationship figure of surface tension (σ) and production concentration when Fig. 1 is 298K.Sharply reduce when surface tension starts, then basic maintenance is constant.At curve break place, its concentration is CMC, and its value is 4.35 × 10
-4mol/L, this numerical value is less.Be 28.51mN/m at micelle-forming concentration lower surface tension force.
Embodiment
Embodiment 1: take 12.5g in beaker, adds 200mL water, is heated to 40 ~ 60 DEG C, with glass stick stir make it dissolve, with salt acid for adjusting pH to 2.0 ~ 3.0. by 300g AH-90 asphalt heating to 120 DEG C.Emulsifier aqueous solution is injected colloidal mill, slowly adds pitch and carry out emulsification, emulsification times is 0.5min.
Join in the iron hand of 500mL by 300g building stones, 3g cement and 15g water, add 30 ~ 40g emulsified bitumen, compound is pressed 60r/min and is stirred, and observes mixed state, and records the mixing time.Room temperature is 34.4 DEG C.
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 5 days and pitch is separated.
Embodiment 2: take 12.5g product in beaker, adds 200mL water, is heated to 50 ~ 70 DEG C, with glass stick stir make it dissolve, with salt acid for adjusting pH to 2.0 ~ 3.5. by 300g road bitumen 100 first asphalt heating to 110 ~ 120 DEG C.Emulsifier aqueous solution is injected colloidal mill, slowly adds pitch and carry out emulsification, emulsification times is 1min.
Join in the iron hand of 500mL by 300g building stones, 3g cement and 15g water, add 20 ~ 40g emulsified bitumen, compound is pressed 60r/min and is stirred, and observes mixed state, and records the mixing time.Room temperature is 28.8 DEG C.
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 7 days and pitch is separated.
Embodiment 3: take 12.5g end product in beaker, adds 200mL water, is heated to 50 ~ 60 DEG C, stirs and makes it dissolve, with salt acid for adjusting pH to 2.0 ~ 3.0., No. 30,300g building petroleum asphalt is heated to 100 ~ 125 DEG C with glass stick.Emulsifier aqueous solution is injected colloidal mill, slowly adds pitch and carry out emulsification, emulsification times is 2min.
Join in the iron hand of 500mL by 300g building stones, 3g cement and 15g water, add 20 ~ 40g emulsified bitumen, compound is pressed 60r/min and is stirred, and observes mixed state, and records the mixing time.Room temperature is 30.1 DEG C.
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 15 days and pitch is separated.
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 (3)
1. an energy is by near ultralow for the chance of winning circle tension force of common building pitch, and has the tensio-active agent asphalt emulsifier of certain stability, it is characterized in that kind of a novel cation surfactivity composition, wherein, amido is from being octadecyl tertiary amine, dodecyl tertiary amine, hexadecyl tertiary amine.
2. emulsified bitumen according to claim 1 take petroleum pitch as optimum feed stock, petroleum pitch 8% ~ 10%, wherein surfactant concentration 0.1% ~ 2%.
3. emulsified bitumen according to claim 1 take petroleum pitch as optimum feed stock, surfactant concentration 0.3%.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105330552A (en) * | 2015-10-10 | 2016-02-17 | 上海森锐道路工程技术有限公司 | New cationic asphalt emulsifier preparation method and application |
| CN105418942A (en) * | 2015-12-21 | 2016-03-23 | 山东大学 | Dicationic amide type asphalt emulsifier and preparation method therefor |
| CN106279680A (en) * | 2016-08-12 | 2017-01-04 | 贯硕磉 | Quaternary cationics and preparation method thereof |
| CN110591395A (en) * | 2019-08-23 | 2019-12-20 | 湖北大学 | Warm-mixing modifier for oily asphalt mixture and preparation method of warm-mixing modifier |
| CN113549225A (en) * | 2021-09-03 | 2021-10-26 | 天津康泽威科技有限公司 | Composite spraying quick-setting emulsifier and preparation method thereof, preparation method of anionic emulsified asphalt and waterproof coating |
-
2013
- 2013-12-04 CN CN201310655765.4A patent/CN104693043A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105330552A (en) * | 2015-10-10 | 2016-02-17 | 上海森锐道路工程技术有限公司 | New cationic asphalt emulsifier preparation method and application |
| CN105418942A (en) * | 2015-12-21 | 2016-03-23 | 山东大学 | Dicationic amide type asphalt emulsifier and preparation method therefor |
| 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 |
| CN106279680A (en) * | 2016-08-12 | 2017-01-04 | 贯硕磉 | Quaternary cationics and preparation method thereof |
| CN110591395A (en) * | 2019-08-23 | 2019-12-20 | 湖北大学 | Warm-mixing modifier for oily asphalt mixture and preparation method of warm-mixing modifier |
| CN110591395B (en) * | 2019-08-23 | 2022-05-24 | 武汉市市政路桥有限公司 | Warm-mixing modifier for oily asphalt mixture and preparation method of warm-mixing modifier |
| CN113549225A (en) * | 2021-09-03 | 2021-10-26 | 天津康泽威科技有限公司 | Composite spraying quick-setting emulsifier and preparation method thereof, preparation method of anionic emulsified asphalt and waterproof coating |
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Application publication date: 20150610 |