CN105968386A - Positive ion slow-breaking quick-setting type asphalt emulsifier containing steric hindrance - Google Patents
Positive ion slow-breaking quick-setting type asphalt emulsifier containing steric hindrance Download PDFInfo
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- CN105968386A CN105968386A CN201610379555.0A CN201610379555A CN105968386A CN 105968386 A CN105968386 A CN 105968386A CN 201610379555 A CN201610379555 A CN 201610379555A CN 105968386 A CN105968386 A CN 105968386A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/27—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/36—Compounds containing oxirane rings with hydrocarbon radicals, substituted by nitrogen atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2395/00—Bituminous materials, e.g. asphalt, tar or pitch
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- Chemical Kinetics & Catalysis (AREA)
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- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
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Abstract
The invention provides positive ion slow-breaking quick-setting type asphalt emulsifier containing steric hindrance. The structure of the emulsifier is shown as follows. According to the emulsifier, a tetrahydropyrrole ring is introduced, a quaternization reaction is conducted, positive ions are obtained, and steric hindrance is added to hydrophilic nitrogen atoms of asphalt emulsifier, that is, a ring is added around the N atoms, so that a blocking function is achieved when the ring makes contact with the surface of stone. The obtained asphalt emulsifier is good in emulsification effect, prepared emulsified asphalt is uniform and stable, synthesis conditions are mild, and the process is simple. Please see the structure in the description, wherein n is equal to 12 or 14 or 16 or 18.
Description
Technical field
The present invention relates to a kind of asphalt emulsifier and synthetic method thereof and application, be specially one and split slowly containing sterically hindered cation
Coagulate type asphalt emulsifier and synthetic method thereof and application soon.
Technical background
In the last few years, along with economic develops rapidly, the requirement to transportation improves the most therewith, especially to being currently in use
The maintenance on road surface and maintenance.In order to repair the damage on road surface, make road be open to traffic as early as possible, need research to split fast solidifying type asphalt emulsification slowly
Agent, for slurry seal.In numerous emulsifying agents, the application of quaternary ammonium salt emulsifying agent is the most prominent, because whether for
Acid stone or alkalescence building stones, nitrogen-atoms is respectively provided with stronger absorbability, makes Colophonium and building stones have stronger adhesiveness.Mesh
The cation asphalt emulgent of front use split soon and in split more, be difficult to meet slurry seal and split fast solidifying requirement slowly, so slowly
Split fast solidifying type asphalt emulsifier and be always the focus of asphalt emulsifier research.
At present, mainly have about splitting the report of fast solidifying type cation asphalt emulgent slowly: Chinese patent CN104693450A invents
A kind of slow breaking asphalt emulsifier, synthesizes a kind of novel asphalt breast with alkali lignin, TEPA, formaldehyde through single step reaction
Agent TEPA/formaldehyde modified lignin amine, for slow breaking asphalt emulsifier, but due to the introducing of lignin, makes by-product
More, and emulsifying effectiveness has a certain impact by the structure of by-product and content, wayward.Chinese patent CN104941509A
Invent a kind of micro-surface area with splitting fast solidifying type asphalt emulsifier slowly, obtain described drip by amidatioon, cyclization and additive reaction
Blue or green emulsifying agent, but condition is the gentleest, needs high temperature and vacuum condition.Chinese patent CN102492136A has invented seriation
Slowly splitting fast solidifying type cation asphalt emulgent, base stock is cheap and easy to get, but needs to carry out compatibility with auxiliary material with different component
And timesharing feeds intake in mass ratio, technique is more complicated.
Summary of the invention
The purpose of the present invention is the deficiency existed for current techniques, it is provided that a kind of splitting slowly containing sterically hindered cation coagulates type drip soon
Blue or green emulsifying agent and preparation method thereof.This emulsifying agent, by introducing nafoxidine ring, in conjunction with quaterisation, obtains cation, directly
It is connected on and adds sterically hindered on the hydrophilic group nitrogen-atoms of asphalt emulsifier, around atom N, i.e. added a ring so that it is with stone
An inhibition is had during the contact of material surface.The Emulsifying Effect of Asphalt Emulsifying Agents that the present invention obtains is good, the emulsified asphalt of preparation uniformly,
Stable, and synthesis condition is gentle, and technique is simple.
The technical scheme is that
A kind of containing sterically hindered cation asphalt emulgent, the structure of this emulsifying agent is as follows:
Wherein n=12,14,16 or 18.
The described preparation method splitting fast solidifying type asphalt emulsifier containing sterically hindered cation slowly, comprises the steps:
(1) long-chain alkyl halide is dissolved in organic solvent, adds catalyst solution, react 10～30min, then protect at nitrogen
Protect lower dropping nafoxidine solution, after 10～30min droppings, magnetic agitation reaction 4～10h at 50～60 DEG C, then
Steam solvent, washing, filter, vacuum drying, obtain intermediate B；Wherein, material proportion is mol ratio long-chain alkyl halide:
Nafoxidine: catalyst=1:1.0-1.5:0.001-1.0；
(2) intermediate B being dissolved in organic solvent, drip epoxychloropropane, 10～20min droppings are complete, at 60～90 DEG C
Lower magnetic agitation reaction 8～14h, steams solvent, is cooled to room temperature, and washing is filtered, vacuum drying, finally obtains described
Slowly fast solidifying type asphalt emulsifier is split containing sterically hindered cation；Wherein material proportion is mol ratio intermediate B: epoxychloropropane
=1:1.0-3.0；
Described long-chain alkyl halide be bromododecane, bromotetradecane, bromohexadecane, bromo-octadecane, chlorinated dodecane,
Chloro-tetradecane, chloro-hexadecane or chlorooctadecane.
The solvent of described nafoxidine solution is ethyl acetate.
Described catalyst is sodium hydroxide or potassium hydroxide.
The concentration range of described catalyst solution is 0.5～1.5mol/L.
The described organic solvent in step (1) is ethyl acetate, ethanol, normal propyl alcohol or isopropanol.
The organic solvent of described step (2) is ethanol, normal propyl alcohol or isopropanol.
The described application splitting fast solidifying type asphalt emulsifier containing sterically hindered cation slowly, comprises the following steps:
Slowly split fast solidifying type asphalt emulsifier containing sterically hindered cation and be configured to, by obtained above, the water that mass fraction is 1～4%
Solution, adjusts pH value to 2～6 with dilute hydrochloric acid, and after being heated to 50～80 DEG C, the Colophonium adding 120～140 DEG C mixes,
Obtain emulsified asphalt；
Wherein, the quality of Colophonium is the 50～65% of emulsifier aqueous solution and Colophonium gross mass.
The substantive distinguishing features of the present invention is in emulsifier molecules to introduce heterocycle nafoxidine ring, thus directly increases parent
Water base nitrogen-atoms sterically hindered, makes positively charged hydrophilic group be not easy with stone surface and quickly contacts, and have to pass through one
The action of forced stirring of the strength for public use fixed time, just can make it arrive the surface of building stones, thus ensure that the requirement split slowly, simultaneously parent
Water base for nitrogenous quaternary ammonium structure, reach fast solidifying effect by Electrostatic Absorption.Compared with this seminar patent CN103920415A,
There is significantly difference at following three aspects and CN103920415A in the present invention: one be the heterocycle used by CN103920415A be piperazine
Piperazine, containing 2 atom N, the present invention only has 1 atom N；Second is not both, and CN103920415A is former by two N
Son introduces two long oil chains, belongs to bi-quaternary ammonium salt structure, and the present invention is that an atom N introduces an oily chain, for mono-quaternaries；
Not being both, piperazine ring belongs to rigid radical so that two hydrophobic chain bending difficulties, and then prevents two long-chains to connect each other
Closely, surfactant can not be at oil/water interface aligned transfer, thus emulsifying effectiveness is the best.The present invention uses nafoxidine ring
Increase sterically hindered, and be single long-chain, can have preferably to split slowly fast solidifying to obtain effect at oil/water interface aligned transfer.
The present invention, from the point of view of MOLECULE DESIGN, is connected to a bigger pyrrole ring of volume on emulsifying agent hydrophilic group nitrogen-atoms,
So attempting with when in emulsifying agent, the atom N of positively charged contacts when electronegative building stones, pyrrole ring just serves the work that space stops
With, add the difficulty that emulsifying agent hydrophilic group contacts with building stones, it is necessary to through the action of forced stirring of the strength for public use of certain time,
It just can be made to arrive the surface of building stones, thus ensure that the requirement split slowly, hydrophilic group is nitrogenous quaternary ammonium structure simultaneously, by quiet
Electro-adsorption reaches fast solidifying effect.The present invention is with long-chain alkyl halide, nafoxidine and epoxychloropropane as primary raw material, through two
Step reaction obtains containing sterically hindered cation asphalt emulgent.Wherein, it is being catalyzed with long-chain alkyl halide and nafoxidine for raw material
First step intermediate is synthesized under agent effect；This intermediate passes through quaterisation with epoxychloropropane again, obtains containing sterically hindered
Cation splits fast solidifying type asphalt emulsifier slowly.The core innovative point of the present invention uses nafoxidine exactly, drips with other quaternary ammonium salt
The difference of blue or green emulsifying agent maximum is exactly the pyrroles's five-membered ring having a volume bigger in atom N, and this is other quaternary ammonium salt Colophonium breast
Not available for agent.
The present invention has a following positive beneficial effect:
(1) on Molecular Design, pyrrole ring directly increases the sterically hindered of hydrophilic group so that it is have the effect split slowly,
Hydrophilic group is nitrogenous quaternary ammonium structure simultaneously, reaches fast solidifying effect by Electrostatic Absorption, splits fast solidifying effect slowly and makes it to answer
For slurry seal.
(2) asphalt emulsifier of the present invention, process route is simple, and cost of material is cheap and readily available, and reaction condition is gentle, reaction
Temperature is at 50 DEG C to 90 DEG C, and produces without waste liquid, is the asphalt emulsifier of an environmental protection.
(3) general asphalt emulsifier energy storage-stable 5 days, by this emulsifier Colophonium, energy storage-stable more than 7 days, deposit
The time of putting is more than 100 days, has more preferable stability, breakdown of emulsion experimental result to be shown as obvious slow breaking.The Colophonium of the present invention
Emulsifying agent (such as the embodiment 1) presetting period is 106min, and evaporation residual quantity is 60.3%, and on sieve, surplus is 0.04%,
All meet " highway asphalt construction technique normalizing " requirement.
Detailed description of the invention
Below in conjunction with the embodiment a kind of synthetic method splitting fast solidifying type asphalt emulsifier containing sterically hindered cation slowly to the present invention
And application is described in detail, but it not to limit the scope of the present invention.
Embodiment 1
One, the preparation of intermediate B
4.66g (0.014mol) bromo-octadecane is dissolved in 15ml ethyl acetate that (ethyl acetate amount is for can be by bromo-octadecane
Dissolve), 0.40g (0.01mol) NaOH is dissolved in the aqueous solution of 10ml ethanol (ethanol: distilled water=4:1 volume
Than), two parts solution is placed in 100ml there-necked flask, in 30 DEG C of reaction 20min under magnetic agitation, under nitrogen protection,
1.5ml (0.015mol) nafoxidine is dissolved in 5ml ethyl acetate (nafoxidine can be dissolved by ethyl acetate amount),
Being placed in constant pressure funnel and be slowly dropped in there-necked flask, 15min dropping is complete, then magnetic agitation reaction 6h at 55 DEG C, 50 DEG C
Rotation is steamed, and steams solvent, with 40 DEG C of distilled water wash products, sucking filtration, is vacuum dried, obtains intermediate B at 40 DEG C.
The structural characterization of intermediate B:
This research uses infrared spectrometry to be analyzed intermediate B, and target product prepares with KBr tabletting.
IR(cm-1): 2914,2841,1577,1473,1119,719
Wherein wave number 2914cm-1, 2841cm-1It is respectively antisymmetric stretching vibration and the symmetrical stretching vibration of methylene c h bond,
1577cm-1The stretching vibration of pyrrole ring, 1473cm-1For the deformation vibration of methyl C-H, 1119cm-1For the stretching vibration of C-N key,
719cm-1Deformation vibration (waving in face during n >=4) for methylene.Secondary amine is at 3350cm-1Near have the stretching vibration of c h bond
Peak, bromoalkane is at 700cm-1-500cm-1Also should there is the stretching vibration peak of C-Br key, and infared spectrum there is no this peak, illustrate to send out
Give birth to reaction, generated tertiary amine, obtain intermediate B.
Two, the preparation of product A
3.23g (0.01mol) intermediate B is dissolved in 20ml ethanol, joins in 100ml there-necked flask, drip 1.80g
(0.02mol) epoxychloropropane, 10min dropping is complete, reacts 12h under 60 DEG C of magnetic agitation, and 60 DEG C of rotations are steamed, and steam solvent,
It is cooled to room temperature, uses washing with acetone product, sucking filtration, 40 DEG C of vacuum drying, obtain product A.Wherein n is 18.
Product A structural characterization:
This research uses infrared spectrometry to be analyzed target product A, and target product prepares with KBr tabletting.
IR(cm-1): 2914,2841,1630,1473,1263,1106,719
Wherein wave number 2914cm-1, 2841cm-1It is respectively antisymmetric stretching vibration and the symmetrical stretching vibration of methylene c h bond,
1630cm-1The stretching vibration of pyrrole ring, 1473cm-1For the deformation vibration of methyl C-H, 1263cm-1Stretching vibration for epoxy radicals
Peak, 1106cm-1The stretching vibration of C-N key, 719cm-1Deformation vibration (waving in face during n >=4) for methylene.These data
Show to have obtained target product A.
Bromophenol blue experimental result: adding 1% (wt) product solution A, bromophenol blue solution is become navy blue from redness, product is described
For cationic compound.
Three, the preparation of emulsified asphalt:
Take asphalt emulsifier 1.0g obtained above (for the 2.85% of asphalt quality), add 24ml water, be configured to emulsifying agent
Aqueous solution, with hydrochloric acid (concentrated hydrochloric acid of 36% with the volume ratio of water be 1:1) regulation pH value to 2～3, heating, keep temperature 70～
80℃.Weigh No. 90 Colophonium 35g of CNOOC that the company of emulsified asphalt provides, be heated to 120～130 DEG C, open homogenizer,
Heated bitumen is poured slowly in the emulsifier aqueous solution of stirring, is sufficiently stirred for 1min, i.e. can get uniform asphalt emulsion.
The performance of emulsified asphalt sees attached list 1.
Embodiment 2
One, the preparation of intermediate B
8.33g (0.025mol) bromo-octadecane is dissolved in 25ml ethyl acetate, by molten for 0.60g (0.015mol) NaOH
In the aqueous solution of 15ml alcohol (dehydrated alcohol: distilled water=4:1), two parts solution is placed in 100ml there-necked flask, magnetic force
React 20min in 30 DEG C under stirring, under nitrogen protection, 3ml (0.03mol) nafoxidine is dissolved in 10ml ethyl acetate
In, it being placed in constant pressure funnel and be slowly dropped in there-necked flask, 20min dropping is complete, magnetic agitation reaction 6h at 55 DEG C, 50 DEG C
Rotation is steamed, and steams solvent, with 40 DEG C of distilled water wash products, sucking filtration, is vacuum dried, obtains intermediate B at 40 DEG C.
Two, the preparation of product A
6.46g (0.02mol) intermediate B is dissolved in 30ml dehydrated alcohol, joins in 100ml there-necked flask, drip 3.70g
(0.04mol) epoxychloropropane, 15min dropping is complete, reacts 12h under 60 DEG C of magnetic agitation, and 60 DEG C of rotations are steamed, and steam solvent,
It is cooled to room temperature, uses washing with acetone product, sucking filtration, 40 DEG C of vacuum drying, obtain product A.
Three, the preparation of emulsified asphalt:
According to the method for embodiment 1, emulsifying agent obtained above is used for emulsified asphalt.
The performance of emulsified asphalt sees attached list 1.
Embodiment 3
One, containing the preparation of sterically hindered cation asphalt emulgent
Except the time in the preparation of intermediate B is changed into 8h, other, with embodiment 2, obtain asphalt emulsifier standby.
Two, the preparation of emulsified asphalt:
According to the method for embodiment 1, emulsifying agent obtained above is used for emulsified asphalt.
The performance of emulsified asphalt sees attached list 1.
Embodiment 4
One, containing the preparation of sterically hindered cation asphalt emulgent
Except temperature in the preparation of product A is changed into 70 DEG C, other, with embodiment 2, obtain asphalt emulsifier standby.
Two, the preparation of emulsified asphalt:
According to the method for embodiment 1, emulsifying agent obtained above is used for emulsified asphalt.
The performance of emulsified asphalt sees attached list 1.
Embodiment 5
One, containing the preparation of sterically hindered cation asphalt emulgent
In addition to changing the consumption of epoxychloropropane into 0.06mol, other, with embodiment 2, obtain asphalt emulsifier standby.
Two, the preparation of emulsified asphalt
According to the method for embodiment 1, emulsifying agent obtained above is used for emulsified asphalt.
The performance of emulsified asphalt sees attached list 1.
Embodiment 6
One, containing the preparation of sterically hindered cation asphalt emulgent
Except replacing bromo-octadecane with chlorooctadecane, other, with embodiment 2, obtain asphalt emulsifier standby.
Two, the preparation of emulsified asphalt:
According to the method for embodiment 1, emulsifying agent obtained above is used for emulsified asphalt.
The performance of emulsified asphalt sees attached list 1.
Embodiment 7
One, containing the preparation of sterically hindered cation asphalt emulgent
Except replacing bromo-octadecane with bromohexadecane, other are with embodiment 2, and other, with embodiment 2, obtain asphalt emulsifier
Standby.
Two, the preparation of emulsified asphalt:
According to the method for embodiment 1, emulsifying agent obtained above is used for emulsified asphalt.
The performance of emulsified asphalt sees attached list 1.
Embodiment 8
One, containing the preparation of sterically hindered cation asphalt emulgent
Except replacing bromo-octadecane with chloro-hexadecane, other, with embodiment 2, obtain asphalt emulsifier standby.
Two, the preparation of emulsified asphalt:
According to the method for embodiment 1, emulsifying agent obtained above is used for emulsified asphalt.
The performance of emulsified asphalt sees attached list 1.
Subordinate list 1
Table 1 each embodiment asphalt emulsion the performance test results
By subordinate list 1 it can be seen that asphalt emulsifier prepared by the present invention has the feature of cation, at the bar that pH value is 2～3
Under part, the emulsified asphalt of preparation has good storage performance.De-emulsification speed result of the test shows, emulsifying prepared by the present invention
Agent is for splitting fast solidifying type asphalt emulsifier slowly, and on sieve, surplus and evaporation residual quantity test result all reach " asphalt highway construction
Technical specification " requirement.
Unaccomplished matter of the present invention is known technology.
Claims (8)
1., containing a sterically hindered cation asphalt emulgent, it is characterized by that the structural formula of this emulsifying agent is as follows:
Wherein n=12,14,16 or 18.
2. the preparation method containing sterically hindered cation asphalt emulgent as claimed in claim 1, is characterized by comprise the steps:
(1) long-chain alkyl halide is dissolved in organic solvent; add catalyst solution; reaction 10～30min, then dropping nafoxidine solution under nitrogen protection, after 10～30min droppings; magnetic agitation reaction 4～10h at 50～60 DEG C; then solvent is steamed, washing, filter; vacuum drying, obtains intermediate B；Wherein, material proportion is mol ratio long-chain alkyl halide: nafoxidine: catalyst=1:1.0-1.5:0.001-1.0；
(2) intermediate B is dissolved in organic solvent, dropping epoxychloropropane, 10～20min droppings are complete, at 60～90 DEG C, magnetic agitation reaction 8～14h, steams solvent, is cooled to room temperature, washing, filter, vacuum drying, finally obtain described splitting slowly containing sterically hindered cation and coagulate type asphalt emulsifier soon；Wherein material proportion is mol ratio intermediate B: epoxychloropropane=1:1.0-3.0；
Described long-chain alkyl halide is bromododecane, bromotetradecane, bromohexadecane, bromo-octadecane, chlorinated dodecane, chloro-tetradecane, chloro-hexadecane or chlorooctadecane.
3. the preparation method containing sterically hindered cation asphalt emulgent as claimed in claim 2, is characterized by that the solvent of described nafoxidine solution is ethyl acetate.
4. the preparation method containing sterically hindered cation asphalt emulgent as claimed in claim 2, is characterized by that described catalyst is sodium hydroxide or potassium hydroxide.
5. the preparation method containing sterically hindered cation asphalt emulgent as claimed in claim 2, is characterized by that the concentration range of described catalyst solution is 0.5～1.5mol/L.
6. the preparation method containing sterically hindered cation asphalt emulgent as claimed in claim 2, is characterized by that the organic solvent in described step (1) is ethyl acetate, ethanol, normal propyl alcohol or isopropanol.
7. the preparation method containing sterically hindered cation asphalt emulgent as claimed in claim 2, is characterized by that the organic solvent of described step (2) is ethanol, normal propyl alcohol or isopropanol.
8. the application process containing sterically hindered cation asphalt emulgent as claimed in claim 1, is characterized by comprise the following steps:
Slowly split fast solidifying type asphalt emulsifier containing sterically hindered cation and be configured to, by obtained above, the aqueous solution that mass fraction is 1～4%, adjust pH value to 2～6 with dilute hydrochloric acid, after being heated to 50～80 DEG C, the Colophonium adding 120～140 DEG C mixes, and obtains emulsified asphalt；
Wherein, the quality of Colophonium is the 50～65% of emulsifier aqueous solution and Colophonium gross mass.
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| CN201610379555.0A CN105968386B (en) | 2016-06-01 | 2016-06-01 | A kind of cation containing steric hindrance splits solidifying type asphalt emulsifier soon slowly |
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| CN201610379555.0A CN105968386B (en) | 2016-06-01 | 2016-06-01 | A kind of cation containing steric hindrance splits solidifying type asphalt emulsifier soon slowly |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102604125A (en) * | 2012-03-16 | 2012-07-25 | 河北工业大学 | Slow-breaking quick-setting asphalt emulsifier, preparation method and application thereof |
| CN102719106A (en) * | 2012-06-21 | 2012-10-10 | 河北工业大学 | Polyamine slow-breaking quick-setting asphalt emulsifier and preparation method and application thereof |
| CN103920415A (en) * | 2014-04-30 | 2014-07-16 | 河北工业大学 | Novel dimeric cationic surfactant and preparation method thereof |
| CN104607094A (en) * | 2015-02-03 | 2015-05-13 | 上海发凯化工有限公司 | Dissymmetric cationic Gemini surfactant and preparation method thereof |
-
2016
- 2016-06-01 CN CN201610379555.0A patent/CN105968386B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102604125A (en) * | 2012-03-16 | 2012-07-25 | 河北工业大学 | Slow-breaking quick-setting asphalt emulsifier, preparation method and application thereof |
| CN102719106A (en) * | 2012-06-21 | 2012-10-10 | 河北工业大学 | Polyamine slow-breaking quick-setting asphalt emulsifier and preparation method and application thereof |
| CN103920415A (en) * | 2014-04-30 | 2014-07-16 | 河北工业大学 | Novel dimeric cationic surfactant and preparation method thereof |
| CN104607094A (en) * | 2015-02-03 | 2015-05-13 | 上海发凯化工有限公司 | Dissymmetric cationic Gemini surfactant and preparation method thereof |
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