CN105968386B - A kind of cation containing steric hindrance splits solidifying type asphalt emulsifier soon slowly - Google Patents
A kind of cation containing steric hindrance splits solidifying type asphalt emulsifier soon slowly Download PDFInfo
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- CN105968386B CN105968386B CN201610379555.0A CN201610379555A CN105968386B CN 105968386 B CN105968386 B CN 105968386B CN 201610379555 A CN201610379555 A CN 201610379555A CN 105968386 B CN105968386 B CN 105968386B
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- steric hindrance
- asphalt
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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
Abstract
The present invention is a kind of cation asphalt emulgent containing steric hindrance, and the structure of the emulsifying agent is as follows.The emulsifying agent, with reference to quaterisation, obtains cation, directly adds steric hindrance on the hydrophilic group nitrogen-atoms of asphalt emulsifier, i.e., added a ring around N atoms, it is had an inhibition when being contacted with stone surface by introducing nafoxidine ring.The Emulsifying Effect of Asphalt Emulsifying Agents that the present invention obtains is good, and the emulsified asphalt of preparation is uniform, stable, and synthesis condition is gentle, and technique is simple.
Description
Technical field
The present invention relates to a kind of asphalt emulsifier and its synthetic method and application, be specially a kind of sun containing steric hindrance from
Sub slow split coagulates type asphalt emulsifier and its synthetic method and application soon.
Technical background
In recent years, with economic rapid development, the requirement to communications and transportation also improves therewith, especially to making
The maintenance and maintenance on road surface.In order to repair the damage on road surface, road is set to be open to traffic as early as possible, it is necessary to which study slow split coagulates type pitch soon
Emulsifying agent, for slurry seal.In numerous emulsifying agents, the application of quaternary ammonium salt emulsifying agent is especially prominent, because whether
Stronger adsorption capacity is respectively provided with for acid stone or alkaline building stones, nitrogen-atoms, pitch and building stones is had stronger adhesion
Property.The cation asphalt emulgent used at present split soon and in split it is more, it is difficult to meet that slurry seal splits soon solidifying requirement slowly,
So the hot spot that fast solidifying type asphalt emulsifier is always asphalt emulsifier research is split slowly.
At present, the report in relation to splitting fast solidifying type cation asphalt emulgent slowly mainly has：Chinese patent CN104693450A
A kind of slow breaking asphalt emulsifier has been invented, has been synthesized with alkali lignin, tetraethylenepentamine, formaldehyde through single step reaction a kind of new
Asphalt emulsifier tetraethylenepentamine/formaldehyde modified lignin amine, is slow breaking asphalt emulsifier, but due to the introducing of lignin,
Make accessory substance more, and the structure of accessory substance and content have a certain impact emulsifying effectiveness, are difficult to control.Chinese patent
CN104941509A has invented a kind of micro-surface area and has split solidifying type asphalt emulsifier soon with slow, passes through amidatioon, cyclization and addition
Reaction obtains the asphalt emulsifier, but condition is not gentle, it is necessary to high temperature and vacuum condition enough.Chinese patent CN102492136A
Invented the slow of seriation and split solidifying type cation asphalt emulgent soon, base stock is cheap and easy to get, but need with auxiliary material with
Different component carries out compatibility and timesharing in mass ratio feeds intake, and technique is more complicated.
The content of the invention
The purpose of the present invention is for insufficient existing for current techniques, there is provided a kind of cation containing steric hindrance is split soon slowly
Solidifying type asphalt emulsifier and preparation method thereof.The emulsifying agent is by introducing nafoxidine ring, with reference to quaterisation, obtain sun from
Son, directly adds steric hindrance on the hydrophilic group nitrogen-atoms of asphalt emulsifier, i.e., has added a ring around N atoms, made
There is an inhibition when it is contacted with stone surface.The Emulsifying Effect of Asphalt Emulsifying Agents that the present invention obtains is good, the emulsification of preparation
Pitch is uniform, stablizes, and synthesis condition is gentle, and technique is simple.
The technical scheme is that：
A kind of cation asphalt emulgent containing steric hindrance, the structure of the emulsifying agent are as follows：
Wherein n=12,14,16 or 18.
The cation containing steric hindrance splits the preparation method of fast solidifying type asphalt emulsifier slowly, includes the following steps：
(1) long-chain alkyl halide is dissolved in organic solvent, adds catalyst solution, react 10~30min, then in nitrogen
Protection is lower to be added dropwise nafoxidine solution, and after 10~30min is added dropwise, magnetic agitation reacts 4~10h at 50~60 DEG C, so
After steam solvent, wash, filter, vacuum drying, obtain intermediate B；Wherein, material proportion is molar ratio long-chain alkyl halide：Four
Hydrogen pyrroles：Catalyst=1：1.0-1.5：0.001-1.0；
(2) intermediate B is dissolved in organic solvent, epoxychloropropane is added dropwise, 10~20min is added dropwise, 60~90
Magnetic agitation reacts 8~14h at DEG C, steams solvent, is cooled to room temperature, washs, and filters, vacuum drying, finally obtains described
Cation containing steric hindrance splits solidifying type asphalt emulsifier soon slowly；Wherein material proportion is molar ratio intermediate B：Epoxychloropropane
=1：1.0-3.0；
The long-chain alkyl halide is bromododecane, bromotetradecane, bromohexadecane, bromo-octadecane, chloro ten
Dioxane, chloro-tetradecane, chloro-hexadecane or chlorooctadecane.
The solvent of the nafoxidine solution is ethyl acetate.
The catalyst is sodium hydroxide or potassium hydroxide.
The concentration range of the catalyst solution is 0.5~1.5mol/L.
Organic solvent in the step (1) is ethyl acetate, ethanol, normal propyl alcohol or isopropanol.
The organic solvent of the step (2) is ethanol, normal propyl alcohol or isopropanol.
The cation containing steric hindrance splits the application of fast solidifying type asphalt emulsifier slowly, comprises the following steps:
By the cation obtained above containing steric hindrance split slowly solidifying type asphalt emulsifier soon be configured to mass fraction for 1~
4% aqueous solution, with dilute hydrochloric acid tune pH value to 2~6, after being heated to 50~80 DEG C, adds 120~140 DEG C of pitch and carries out
Mixing, obtains emulsified asphalt；
Wherein, the quality of pitch is the 50~65% of emulsifier aqueous solution and pitch gross mass.
The substantive distinguishing features of the present invention in emulsifier molecules in introducing heterocycle --- nafoxidine ring, so as to directly increase
Add the steric hindrance of hydrophilic group nitrogen-atoms, made positively charged hydrophilic radical be not easy to contact quickly with stone surface, and must
It must can be just set to reach the surface of building stones by the action of forced stirring of the strength for public use of certain time, so as to ensure that what is split slowly wants
Ask, while hydrophilic group is nitrogenous quaternary ammonium structure, reaches the effect coagulated soon by Electrostatic Absorption.With this seminar patent
CN103920415A is compared, and the present invention has obvious difference at following three aspects and CN103920415A：When
Heterocycle used in CN103920415A is piperazine, and containing 2 N atoms, the present invention only has 1 N atom；Second is not both,
CN103920415A introduces two long oil chains by two N atoms, belongs to bi-quaternary ammonium salt structure, and the present invention is a N atom
An oily chain is introduced, is mono-quaternaries；It is not both thirdly that piperazine ring belongs to rigid radical so that two hydrophobic chain bendings are tired
Difficulty, and then prevent two long-chains closer to each other, surfactant cannot be in oil/water interface aligned transfer, so that emulsifying effectiveness is not
It is good.The present invention is single long-chain using using nafoxidine ring increase steric hindrance, can in oil/water interface aligned transfer,
Coagulate to obtain effect soon with preferably splitting slowly.
It is larger to be connected to a volume from the point of view of MOLECULE DESIGN on emulsifying agent hydrophilic group nitrogen-atoms by the present invention
Pyrrole ring, so when electronegative building stones are attempted with the N atomic contacts of positively charged in emulsifying agent, pyrrole ring just plays space
The effect of stop, add the difficulty that emulsifying agent hydrophilic radical is contacted with building stones, it is necessary to by the strength for public use of certain time
Action of forced stirring, can just make it reach the surface of building stones, so that ensure that the requirement split slowly, while hydrophilic group is nitrogenous quaternary ammonium knot
Structure, reaches the effect coagulated soon by Electrostatic Absorption.The present invention is using long-chain alkyl halide, nafoxidine and epoxychloropropane to be main former
Material, the cation asphalt emulgent containing steric hindrance is obtained by two-step reaction.Wherein, using long-chain alkyl halide and nafoxidine as
Raw material synthesizes first step intermediate under catalyst action；This intermediate obtains again with epoxychloropropane by quaterisation
Cation containing steric hindrance splits solidifying type asphalt emulsifier soon slowly.The core innovative point of the present invention is exactly to use nafoxidine, with
The difference of other quaternary ammonium salt asphalt emulsifier maximums is exactly the pyrroles's five-membered ring for having a volume larger on N atoms, this is it
Not available for its quaternary ammonium salt asphalt emulsifier.
The present invention has following positive beneficial effect：
(1) on Molecular Design, pyrrole ring directly increases the steric hindrance of hydrophilic radical, makes it have what is split slowly
Effect, while hydrophilic group is nitrogenous quaternary ammonium structure, reaches the effect coagulated soon by Electrostatic Absorption, splitting effect solidifying soon slowly makes it
It can be applied to slurry seal.
(2) asphalt emulsifier of the invention, process route is simple, and cost of material is cheap and readily available, and reaction condition is gentle, instead
Temperature is answered at 50 DEG C to 90 DEG C, and is produced without waste liquid, is an environmentally protective asphalt emulsifier.
(3) general asphalt emulsifier energy storage-stable 5 days, with this emulsifier pitch, can storage-stable more than 7 days,
Resting period is more than 100 days, there is more preferable stability, and demulsification experimental result is shown as obvious slow breaking.The drip of the present invention
Blue or green emulsifying agent (such as embodiment 1) presetting period is 106min, and evaporation residual quantity is 60.3%, and surplus is 0.04% on sieve,
Meet《Highway asphalt construction technique normalizing》It is required that.
Embodiment
Split fast solidifying type asphalt emulsifier slowly to a kind of cation containing steric hindrance of the present invention with reference to embodiment
Synthetic method and application are described in detail, but do not limit the scope of the invention.
Embodiment 1
First, the preparation of intermediate B
4.66g (0.014mol) bromo-octadecane is dissolved in 15ml ethyl acetate to (ethyl acetate amount is can be by bromo ten
Eight alkane dissolve), 0.40g (0.01mol) NaOH is dissolved in (ethanol in the aqueous solution of 10ml ethanol：Distilled water=4:1 volume
Than), two parts solution is placed in 100ml there-necked flasks, reacts 20min in 30 DEG C under magnetic agitation, under nitrogen protection, will
1.5ml (0.015mol) nafoxidine is dissolved in 5ml ethyl acetate (ethyl acetate amount can dissolve nafoxidine), is placed in
It is slowly dropped into constant pressure funnel in there-necked flask, 15min is added dropwise, then magnetic agitation reaction 6h at 55 DEG C, 50 DEG C of rotations
Steam, steam solvent, with 40 DEG C of distilled water washed products, filter, be dried in vacuo at 40 DEG C, obtain intermediate B.
The structural characterization of intermediate B：
This research analyzes intermediate B using infra-red sepectrometry, and target product is made with KBr tablettings.
IR(cm-1)：2914,2841,1577,1473,1119,719
Wherein wave number 2914cm-1, 2841cm-1The respectively antisymmetric stretching vibration of methylene c h bond and symmetrical stretch is shaken
It is dynamic, 1577cm-1The stretching vibration of pyrrole ring, 1473cm-1For the deformation vibration of methyl C-H, 1119cm-1Flexible for C-N keys shakes
It is dynamic, 719cm-1For the deformation vibration (being waved during n >=4 in face) of methylene.Secondary amine is in 3350cm-1Nearby there is the flexible of c h bond to shake
Dynamic peak, bromoalkane is in 700cm-1-500cm-1Also there should be the stretching vibration peak of C-Br keys, and this peak is had no in infared spectrum, explanation
Reacted, generate tertiary amine, obtained intermediate B.
2nd, the preparation of product A
3.23g (0.01mol) intermediate B is dissolved in 20ml ethanol, is added in 100ml there-necked flasks, 1.80g is added dropwise
(0.02mol) epoxychloropropane, 10min are added dropwise, and 12h are reacted under 60 DEG C of magnetic agitations, 60 DEG C of revolvings, steam solvent, cold
But room temperature is arrived, with acetone washed product, is filtered, 40 DEG C of vacuum drying, obtain product A.Wherein n is 18.
Product A structural characterizations：
This research analyzes target product A using infra-red sepectrometry, and target product is made with KBr tablettings.
IR(cm-1)：2914,2841,1630,1473,1263,1106,719
Wherein wave number 2914cm-1, 2841cm-1The respectively antisymmetric stretching vibration of methylene c h bond and symmetrical stretch is shaken
It is dynamic, 1630cm-1The stretching vibration of pyrrole ring, 1473cm-1For the deformation vibration of methyl C-H, 1263cm-1For the flexible of epoxy group
Vibration peak, 1106cm-1The stretching vibration of C-N keys, 719cm-1For the deformation vibration (being waved during n >=4 in face) of methylene.These
As shown by data has obtained target product A.
Bromophenol blue experimental result：1% (wt) product solution A is added, bromophenol blue solution is changed into navy blue from red, illustrates production
Thing is cationic compound.
3rd, the preparation of emulsified asphalt：
Asphalt emulsifier 1.0g obtained above (for the 2.85% of asphalt quality) is taken, 24ml water is added, is configured to emulsify
Agent aqueous solution, with hydrochloric acid, (36% concentrated hydrochloric acid and the volume ratio of water are 1:1) pH value is adjusted to 2~3, and heating, keeps temperature 70
~80 DEG C.No. 90 pitch 35g of CNOOC that the company of emulsified asphalt provides are weighed, 120~130 DEG C is heated to, opens homogenizer,
Heated bitumen is poured slowly into the emulsifier aqueous solution of stirring, is sufficiently stirred 1min, you can obtains uniform asphalt emulsion.
The performance of emulsified asphalt sees attached list 1.
Embodiment 2
First, the preparation of intermediate B
8.33g (0.025mol) bromo-octadecane is dissolved in 25ml ethyl acetate, 0.60g (0.015mol) NaOH is molten
(the absolute ethyl alcohol in the aqueous solution of 15ml alcohol：Distilled water=4:1), two parts solution is placed in 100ml there-necked flasks, magnetic force stirs
Mix down and react 20min in 30 DEG C, under nitrogen protection, 3ml (0.03mol) nafoxidine is dissolved in 10ml ethyl acetate, is put
It is slowly dropped into constant pressure funnel in there-necked flask, 20min is added dropwise, and magnetic agitation reacts 6h at 55 DEG C, and 50 DEG C rotate,
Solvent is steamed, with 40 DEG C of distilled water washed products, is filtered, is dried in vacuo at 40 DEG C, obtains intermediate B.
2nd, the preparation of product A
6.46g (0.02mol) intermediate B is dissolved in 30ml absolute ethyl alcohols, is added in 100ml there-necked flasks, is added dropwise
3.70g (0.04mol) epoxychloropropane, 15min are added dropwise, and 12h are reacted under 60 DEG C of magnetic agitations, 60 DEG C of revolvings, steam molten
Agent, is cooled to room temperature, and with acetone washed product, filters, and 40 DEG C of vacuum drying, obtain product A.
3rd, 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
First, the preparation of the cation asphalt emulgent containing steric hindrance
Except the time is changed to 8h in the preparation intermediate B, it is spare to obtain asphalt emulsifier with embodiment 2 for other.
2nd, 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
First, the preparation of the cation asphalt emulgent containing steric hindrance
Except temperature in the preparation of product A is changed to 70 DEG C, it is spare to obtain asphalt emulsifier with embodiment 2 for other.
2nd, 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
First, the preparation of the cation asphalt emulgent containing steric hindrance
In addition to the dosage of epoxychloropropane is changed to 0.06mol, it is spare to obtain asphalt emulsifier with embodiment 2 for other.
2nd, 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
First, the preparation of the cation asphalt emulgent containing steric hindrance
Except replacing bromo-octadecane with chlorooctadecane, it is spare to obtain asphalt emulsifier with embodiment 2 for other.
2nd, 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
First, the preparation of the cation asphalt emulgent containing steric hindrance
Except replacing bromo-octadecane with bromohexadecane, with embodiment 2, other obtain pitch breast with embodiment 2 for other
Agent is spare.
2nd, 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
First, the preparation of the cation asphalt emulgent containing steric hindrance
Except replacing bromo-octadecane with chloro-hexadecane, it is spare to obtain asphalt emulsifier with embodiment 2 for other.
2nd, 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
Each embodiment asphalt emulsion the performance test results of table 1
The asphalt emulsifier that it can be seen from subordinate list 1 prepared by the present invention has the feature of cation, is 2~3 in pH value
Under the conditions of, the emulsified asphalt of preparation has good storage performance.De-emulsification speed result of the test shows, breast prepared by the present invention
Agent coagulates type asphalt emulsifier soon for slow split, and surplus and evaporation residual quantity test result reach on sieve《Asphalt highway
Construction technique normalizing》It is required that.
Unaccomplished matter of the present invention is known technology.
Claims (8)
- A kind of 1. cation asphalt emulgent containing steric hindrance, it is characterized in that the structural formula of the emulsifying agent is as follows：Wherein n=12,14,16 or 18.
- 2. the preparation method of the cation asphalt emulgent containing steric hindrance as claimed in claim 1, it is characterized in that including such as Lower step：(1) long-chain alkyl halide is dissolved in organic solvent, adds catalyst solution, react 10~30min, then protect in nitrogen Lower dropwise addition nafoxidine solution, after 10~30min is added dropwise, magnetic agitation reacts 4~10h, Ran Houzheng at 50~60 DEG C Go out solvent, wash, filter, vacuum drying, obtains intermediate B；Wherein, material proportion is molar ratio long-chain alkyl halide：Tetrahydrochysene pyrrole Cough up：Catalyst=1：1.0-1.5：0.001-1.0；(2) intermediate B is dissolved in organic solvent, epoxychloropropane is added dropwise, 10~20min is added dropwise, at 60~90 DEG C Magnetic agitation reacts 8~14h, steams solvent, is cooled to room temperature, and washs, and filters, vacuum drying, finally obtains described containing sky Between the cation of steric hindrance split solidifying type asphalt emulsifier soon slowly；Wherein material proportion is molar ratio intermediate B：Epoxychloropropane=1： 1.0-3.0；The long-chain alkyl halide for bromododecane, bromotetradecane, bromohexadecane, bromo-octadecane, chlorinated dodecane, Chloro-tetradecane, chloro-hexadecane or chlorooctadecane.
- 3. the preparation method of the cation asphalt emulgent containing steric hindrance as claimed in claim 2, it is characterized in that described The solvent of nafoxidine solution is ethyl acetate.
- 4. the preparation method of the cation asphalt emulgent containing steric hindrance as claimed in claim 2, it is characterized in that described Catalyst is sodium hydroxide or potassium hydroxide.
- 5. the preparation method of the cation asphalt emulgent containing steric hindrance as claimed in claim 2, it is characterized in that described The concentration range of catalyst solution is 0.5~1.5mol/L.
- 6. the preparation method of the cation asphalt emulgent containing steric hindrance as claimed in claim 2, it is characterized in that described Organic solvent in step (1) is ethyl acetate, ethanol, normal propyl alcohol or isopropanol.
- 7. the preparation method of the cation asphalt emulgent containing steric hindrance as claimed in claim 2, it is characterized in that described The organic solvent of step (2) is ethanol, normal propyl alcohol or isopropanol.
- 8. the application process of the cation asphalt emulgent containing steric hindrance as claimed in claim 1, it is characterized in that including with Lower step:The cation containing steric hindrance is split into fast solidifying type asphalt emulsifier slowly and is configured to the water that mass fraction is 1~4% Solution, with dilute hydrochloric acid tune pH value to 2~6, after being heated to 50~80 DEG C, adds 120~140 DEG C of pitch and is mixed, obtained To emulsified asphalt；Wherein, the quality of pitch is the 50~65% of emulsifier aqueous solution and pitch gross mass.
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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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