CN106008996A - Lignin polyamine cation type asphalt emulsifier as well as preparation method and application thereof - Google Patents
Lignin polyamine cation type asphalt emulsifier as well as preparation method and application thereof Download PDFInfo
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- CN106008996A CN106008996A CN201610462551.9A CN201610462551A CN106008996A CN 106008996 A CN106008996 A CN 106008996A CN 201610462551 A CN201610462551 A CN 201610462551A CN 106008996 A CN106008996 A CN 106008996A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
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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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
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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 invention discloses a lignin polyamine cation type asphalt emulsifier as well as a preparation method and an application thereof. The asphalt emulsifier has the molecular structural general formula shown in the specification, wherein R refers to methyl (-CH3), ethyl (-C2H5) or an ethoxy group (-C2H4OH); LIGNIN refers to a lignin molecular chain. Acrylic acid, triethylene tetramine, low-carbon-number tertiary amine and epoxy chloropropane are added to raw materials, so that a prepared asphalt emulsifier molecule adopts the polyamine cation type chemical structure, the charge strength of the asphalt emulsifier molecule is enhanced, and the hydrophilia of the asphalt emulsifier molecule is improved.
Description
Technical field
Present invention relates particularly to a kind of lignin many amine cations type asphalt emulsifier and preparation method and application, belong to essence
Thin chemical technology field.
Background technology
Emulsified asphalt refers to that Colophonium and water, under the effect of emulsifying agent, form oil-in-water liquid bitumen emulsion.Emulsified asphalt master
Cationic emulsified bitumen to be divided into, anionic emulsified bitumen and non ionic emulsified bitumen.Wherein, cationic emulsified bitumen due to
There are energy-conserving and environment-protective, execution conditions can be improved, strong with building stones adhesion, and can effectively reduce the many such as Colophonium overaging
Excellent application characteristic, and be widely used in road construction and pavement preservation.
The most critical factor affecting emulsified asphalt pavement performance is exactly asphalt emulsifier, the most both at home and abroad cationic asphalt emulsification
Agent principal item has organic amine, quaternary ammonium salt, imidazolines, amide-type etc., along with the application of cationic emulsified bitumen,
The kind of asphalt emulsifier is the most gradually enriched.
United States Patent (USP) USP4338136 is with C12-18Colophonium breast is prepared in Long carbon chain fatty acid and diethylenetriamine reaction under certain condition
Agent.The shortcoming of the method is that the asphalt emulsifier prepared is expensive, and when slurry seal is constructed, the breakdown of emulsion time is long, becomes
The type time is slow, and the open to traffic time is long.Chinese patent CN1096714 utilizes oil plant by-product aphthenic acids to react with alkenyl polyamine,
Prepare asphalt emulsifier.The shortcoming of the method be the raw material supply of emulsifying agent by severely restricts, be unfavorable for popularization and application.China
Patent CN1861721A relates to a kind of rosin cation asphalt emulgent.This emulsifying agent is to be reacted by Colophonium and alkenyl polyamine, obtains
Colophonium intermediate, then, is condensed with different types of quaternary ammonium salt intermediate, prepares the rosin cation asphalt emulsifying of function admirable
Agent.The shortcoming of this method is that reactions steps is loaded down with trivial details, needs pyroreaction.Chinese patent CN101712625A relates to a kind of both sexes
Slowly split quick-setting asphalt emulsifying agent synthetic method, use oleic acid and polyamines to react generation polyamide-polyamino, be subsequently adding monoxone generation halogen
Generation reaction, prepares asphalt emulsifier.The shortcoming of the method needs pyroreaction when being to prepare.Chinese patent CN101745340A
Relating to a kind of cation asphalt emulgent preparation method, host is reacted by mixed organic acid and organic amine and is obtained intermediate, then carries out
Quaterisation prepares, and adjuvant is nonionic surfactant and modified additive.The shortcoming of the method is that preparation process is loaded down with trivial details, becomes
This is higher, needs pyroreaction.
The deficiency that above-mentioned cationic asphalt emulsifier and preparation method thereof generally exists is: the cost of material preparing emulsifying agent is higher,
Source is restricted, and needs pyroreaction during preparation, higher to productive experiment equipment requirements.Lignin is that in nature storage is only
Inferior to cellulose be positioned at second natural biological organic compound.Research lignin asphalt emulsifier can reduce black liquor in papermaking
The environmental pollution brought.The production cost of asphalt emulsifier can be reduced using lignin as the raw material of asphalt emulsifier, and synthesize
Technique is simple, and raw material sources are extensive.Therefore, exploitation is based on the function admirable that lignin is raw material, novel asphalt with low cost
Emulsifying agent has highly important actual application value.
Summary of the invention
For above-mentioned prior art, it is an object of the invention to provide a kind of lignin many amine cations type asphalt emulsifier and
Preparation method and application.These preparation method needed raw material wide material sources, production cost is low, and preparation technology is simple, it is not necessary to high temperature
Reaction.The asphalt emulsifier function admirable prepared, the Colophonium of emulsifiable multiple different model, the emulsified asphalt of preparation is thin
Greasy uniformly, storage stability is good.
For achieving the above object, the present invention is by the following technical solutions:
A kind of lignin many amine cations type asphalt emulsifier, its general formula of molecular structure is:
Wherein, R is methyl (-CH3), ethyl (-C2H5) or ethoxy (-C2H4OH)；LIGNIN represents lignin molecule chain.
The preparation method of a kind of lignin many amine cations type asphalt emulsifier, comprises the steps:
1) by triethylene tetramine and acrylic acid hybrid reaction, obtaining reaction intermediate I, intermediate compound I is
NH2C2H4NHC2H4NHC2H4NHCH2CH2COOH；
2) low carbon number tertiary amine, technical hydrochloric acid and epoxychloropropane are mixed, reaction, obtain reaction intermediate II, low carbon number uncle
Amine is trimethylamine, triethylamine or triethanolamine, and intermediate II isR is methyl (-CH3)、
Ethyl (-C2H5) or ethoxy (-C2H4OH)；
3) by lignin and sodium hydrate aqueous solution hybrid reaction, reaction intermediate III is obtained；
4) reaction intermediate I is joined in reaction intermediate III, then drip formalin, reaction, obtain reaction intermediate
IV, intermediate compound IV is
5) reaction intermediate II is added drop-wise in reaction intermediate IV, reaction, i.e. obtains the drip of lignin many amine cations type
Blue or green emulsifying agent；
As long as above step does not affect preparation, interchangeable.
Preferably, the concentration of described formalin is 37%, and the concentration of trimethylamine aqueous solution is 33%, the concentration of technical hydrochloric acid
It is 30%.
Preferably, raw material and the proportioning raw materials of employing is: lignin, water, sodium hydroxide, triethylene tetramine, acrylic acid,
The mass ratio of the formalin of 37%, the trimethylamine aqueous solution of 33%, the technical hydrochloric acid of 30% and epoxychloropropane is 100:
(159-230): (19-27): (47-55): (23-29): (30-36): (63-74): (42-50): (31-37).
Preferably, the raw material of employing and proportioning raw materials be lignin, water, sodium hydroxide, triethylene tetramine, acrylic acid, 37%
The mass ratio of formalin, triethylamine, the technical hydrochloric acid of 30% and epoxychloropropane be 100:(159-230): (19-27):
(47-55): (23-29): (30-36): (35-43): (42-50): (31-37).
Preferably, the raw material of employing and proportioning raw materials be lignin, water, sodium hydroxide, triethylene tetramine, acrylic acid, 37%
The mass ratio of formalin, the triethanolamine aqueous solution of 85%, the technical hydrochloric acid of 30% and epoxychloropropane be 100:
(159-230): (19-27): (47-55): (23-29): (30-36): (53-82): (42-50): (31-37).
Wherein, described water and described sodium hydroxide mixing, sodium hydroxide is soluble in water obtains step 3) in sodium hydroxide water-soluble
Liquid.
Preferably, described lignin is alkali lignin.
Preferably, step 1) in, the temperature of reaction is 30-60 DEG C, and the time of reaction is 0.5-2h.
Preferably, step 2) in, the temperature of reaction is 30-70 DEG C.
Preferably, step 4) in, the temperature of reaction is 60-80 DEG C, preferably 65-75 DEG C, and the time of reaction is 2-4h.
Preferably, step 5) in, the temperature of reaction is 60-80 DEG C, preferably 65-75 DEG C, and the time of reaction is 2-4h.
The preparation method of above-mentioned lignin many amine cations type asphalt emulsifier, specifically includes following steps:
(1) triethylene tetramine is joined in reaction vessel, then be dividedly in some parts acrylic acid, after acrylic acid adds,
30-60 DEG C of stirring reaction 0.5-2h, obtains reaction intermediate I；
(2) in the second reactor, add low carbon number tertiary amine, be dividedly in some parts technical hydrochloric acid, after technical hydrochloric acid adds, then
It is dividedly in some parts epoxychloropropane, after epoxychloropropane adds, at 30-70 DEG C of stirring reaction 2-3h, obtains reaction intermediate
II, wherein, low carbon number tertiary amine is trimethylamine, triethylamine or triethanolamine；
(3) in the 3rd reactor by lignin dissolution in sodium hydrate aqueous solution, stirring reaction, obtain reaction intermediate
III；
(4) reaction intermediate I is joined in reaction intermediate III, then be dividedly in some parts 37% formalin, 60-80 DEG C
Reaction 2-4h, obtains reaction intermediate IV；
(5) reaction intermediate II is dividedly in some parts in reaction intermediate IV, 60-80 DEG C of reaction 2-4h, i.e. obtains lignin
Many amine cations type asphalt emulsifier；
As long as not affecting preparation, above step is interchangeable.
Above-mentioned lignin many amine cations type asphalt emulsifier splits the application in type cationic emulsified bitumen soon in preparation.
A kind of preparation method splitting type cationic emulsified bitumen soon, comprises the steps: that the consumption of asphalt emulsifier is preparation
The 1.0-3.0% of emulsified asphalt gross mass, adds water above-mentioned lignin many amine cations type asphalt emulsifier and is configured to aqueous solution,
With salt acid for adjusting pH value to 2-3, it is heated to 60-70 DEG C, prepares soap lye；Colophonium after heating and emulsifying agent soap lye are passed through
Colloid mill emulsifying is prepared and is split type cationic emulsified bitumen soon.
What described preparation method prepared splits type cationic emulsified bitumen soon.
The present invention is using acrylic acid as the reaction raw materials of asphalt emulsifier, by adding third in the molecular structure of asphalt emulsifier
Olefin(e) acid introduces carboxylic acid group, adds the hydrophilic of asphalt emulsifier, and the compatibility of emulsifying agent and Colophonium.It addition, combine
Close and consider that carbon chain lengths is for the HLB value (hydrophilic/lipophilic balance value) of asphalt emulsifier and CMC (critical micelle concentration)
Impact, select using lignin, triethylene tetramine, epoxychloropropane and low carbon number tertiary amine as reaction raw material, make preparation
The HLB value of asphalt emulsifier within optimum range, improve the emulsifiability to Colophonium.
The invention have the benefit that
(1) the raw material wood element of lignin many amine cations type asphalt emulsifier of the present invention is relative to current cationic drip
Blue or green raw material used by emulsifying agent is cheap, wide material sources, and asphalt emulsifier production cost is low.
(2) the preparation method technique of lignin many amine cations type asphalt emulsifier of the present invention is simple, it is not necessary to pyroreaction.
(3) Colophonium of the lignin emulsifiable multiple different model of many amine cations type asphalt emulsifier that prepared by the present invention, preparation
Emulsified asphalt fine and smooth uniformly storage stability is good, it is adaptable to highway priming oil or the spread of sticking layer oil, and seal for rubble
Layer, screening seal coat, the slight check crack of mist sealing and reparation road surface etc., have the characteristic splitting asphalt emulsifier soon.The emulsifying drip prepared
Blue or green properties all can meet the cationic emulsified bitumen standard (JTJ052-2000) that Chinese transportation portion works out.
(4) by adding acrylic acid, triethylene tetramine, low carbon number tertiary amine and epoxychloropropane in the raw material of the present invention so that system
Standby asphalt emulsification agent molecule has many amine cations type chemical constitution, enhances the charge density of asphalt emulsification agent molecule, carries
The high hydrophilic of asphalt emulsification agent molecule.So not only increase the emulsifiability of asphalt emulsifier, and improve emulsifying drip
Blue or green serviceability.
Owing to the ionization of lignin many amine cations type asphalt emulsifier of the present invention is stronger, adding asphalt emulsification
Agent hydrophilic at the same time it can also be make interfacial film carry the most more positive charge, occurs in that a bed boundary electric charge, thus
Occur in that interface charge layer.The formation of interface charge layer, by making bitumen particle mutually exclusive, makes them keep certain distance, from
And allow pitch particle maintain dispersity, asphalt emulsion is served peptizaiton.The appearance of interface charge layer, for Colophonium
The dispersion in aqueous phase of emulsifying, Colophonium, the homogeneous stability system of asphalt emulsion is kept to have vital effect.Due to this
Bright emulsifying agent is ionizable more cation in water, so interface charge layer effect is relatively strong, so that the emulsifying of the present invention
After agent emulsified asphalt, its system is more stable.
Detailed description of the invention
Below by instantiation, the present invention will be further elaborated, it should explanation, and the description below is merely to solve
Release the present invention, its content is not defined.
Raw material, reagent used in the embodiment of the present invention are conventional chemical products, all can be commercially available by commercial channel.
Embodiment 1
(1) preparation of lignin many amine cations type asphalt emulsifier:
1) 146.2g triethylene tetramine, then dropping 72.1g acrylic acid are added in the reactor, 45 DEG C of stirring reaction 1h,
To reaction intermediate I.
2) in another reactor, add 193.1g 33% (mass fraction) trimethylamine aqueous solution, be gradually added into 131.2g 30%
Technical hydrochloric acid, then be gradually added into 97.1g epoxychloropropane, 45 DEG C of stirring reaction 2h, obtain reaction intermediate II.
3) in another reactor by 283.0g lignin dissolution at 649.6g 10.7% (mass fraction) sodium hydrate aqueous solution
In, mix and blend reacts, and obtains reaction intermediate III.
4) reaction intermediate I is joined in reaction intermediate III, then is gradually added into 92.5g 37% (mass fraction) formaldehyde,
70 DEG C of reaction 3h, obtain reaction intermediate IV；
5) reaction intermediate II is added gradually in reaction intermediate IV, 70 DEG C of reaction 3h.I.e. obtain the many amines of lignin
Cationic asphalt emulsifier, gives over to emulsified asphalt test.
Carrying out FTIR detection after lignin many amine cations separated purification of type asphalt emulsifier of preparation, result is as follows:
3250-3500cm-1Superposition peak, 2947cm is absorbed for O-H stretching vibration and N-H stretching vibration-1Asymmetric flexible for methylene
Vibration absorption peak, 2841cm-1For methylene symmetrical stretching vibration absworption peak, 1634cm-1For N-H bending vibration and carboxylate
Middle C=O stretching vibration absworption peak, 1568cm-1And 1466cm-1For the skeletal vibration absworption peak of phenyl ring, 1396cm-1With
1325cm-1For O-H in-plane bending vibration absworption peak, 1130cm-1For C-H in-plane bending vibration absworption peak, 1042cm-1For
Ar-O-C stretching vibration absworption peak, 615cm-1For O-H out-of-plane bending vibration absworption peak.
Reaction equation is as follows:
NH2C2H4NHC2H4NHC2H4NH2+CH2=CHCOOH → NH2C2H4NHC2H4NHC2H4NHCH2CH2COOH (1)
(2) preparation of emulsified asphalt:
Take AH-90# Colophonium 300g, be heated to 125 DEG C, asphalt emulsifier prepared by 12.5g the present embodiment is joined 200g
In water, the Nacl acid for adjusting pH value with 30%, to 2-3, is heated to 65 DEG C, prepares soap lye.By Colophonium and emulsifying agent soap lye
Cationic emulsified asphalt is prepared by colloid mill emulsifying.
(3) emulsified asphalt performance detection:
The cationic emulsified bitumen standard (JTJ052-2000) that the emulsified asphalt prepared is worked out by Chinese transportation portion detects, knot
Fruit is as follows: emulsified asphalt prepared by the present embodiment is uniform, fine and smooth, and bitumen content is 58%, and on sieve, surplus is 0.02%,
Wrapping area with mineral aggregate and be more than 2/3, storage stability (1d) is 0.4%；Employing is mixed and stirred material and is mixed and stirred, and can be 13 the mixing time
Second.Show asphalt emulsion prepared by this emulsifying agent for split type cationic emulsified bitumen soon, properties all can meet JTJ052-2000
The requirement of standard.
Embodiment 2
(1) preparation of lignin many amine cations type asphalt emulsifier:
1) 146.2g triethylene tetramine, then dropping 72.1g acrylic acid are added in the reactor, 45 DEG C of stirring reaction 1h,
To reaction intermediate I.
2) in another reactor, add 109.1g triethylamine, be gradually added into the technical hydrochloric acid of 131.2g 30%, then be gradually added into
97.1g epoxychloropropane, 45 DEG C of stirring reaction 2h, obtain reaction intermediate II.
3) in another reactor by 283.0g lignin dissolution at 649.6g 10.7% (mass fraction) sodium hydrate aqueous solution
In, mix and blend reacts, and obtains reaction intermediate III.
4) reaction intermediate I is joined in reaction intermediate III, then is gradually added into 92.5g 37% (mass fraction) formaldehyde,
60 DEG C of reaction 4h, obtain reaction intermediate IV；
5) reaction intermediate II is added gradually in reaction intermediate IV, 80 DEG C of reaction 2h.I.e. obtain the many amines of lignin
Cationic asphalt emulsifier, gives over to emulsified asphalt test.
Carrying out FTIR detection after lignin many amine cations separated purification of type asphalt emulsifier of preparation, result is as follows:
3255-3508cm-1Superposition peak, 2963cm is absorbed for O-H stretching vibration and N-H stretching vibration-1Asymmetric flexible for methylene
Vibration absorption peak, 2833cm-1For methylene symmetrical stretching vibration absworption peak, 1634cm-1For N-H bending vibration and carboxylate
Middle C=O stretching vibration absworption peak, 1560cm-1And 1460cm-1For the skeletal vibration absworption peak of phenyl ring, 1394cm-1With
1304cm-1For O-H in-plane bending vibration absworption peak, 1138cm-1For C-H in-plane bending vibration absworption peak, 1092cm-1For
C-O stretching vibration absworption peak, 1040cm-1For Ar-O-C stretching vibration absworption peak, 798cm-1For C-H out-of-plane bending vibration
Absworption peak, 606cm-1For O-H out-of-plane bending vibration absworption peak.
Reaction equation is as follows:
NH2C2H4NHC2H4NHC2H4NH2+CH2=CHCOOH → NH2C2H4NHC2H4NHC2H4NHCH2CH2COOH (1)
(2) preparation of emulsified asphalt:
Take AH-70# Colophonium 300g, be heated to 125 DEG C, asphalt emulsifier prepared by 12.5g the present embodiment is joined 200g
In water, the Nacl acid for adjusting pH value with 30%, to 2-3, is heated to 65 DEG C, prepares soap lye.By Colophonium and emulsifying agent soap lye
Cationic emulsified asphalt is prepared by colloid mill emulsifying.
(3) emulsified asphalt performance detection:
Detection method with embodiment 1, testing result is: emulsified asphalt is uniform, fine and smooth, and bitumen content is 58%, and sieve remains
Amount is 0.01%, wraps area with mineral aggregate and is more than 2/3, and storage stability (1d) is 0.6%；Employing is mixed and stirred material and is mixed and stirred, can
Mixing time is 5 seconds.Show that asphalt emulsion prepared by this emulsifying agent is to split type cationic emulsified bitumen, the equal energy of properties soon
Meet the requirement of JTJ052-2000 standard.
Embodiment 3
(1) preparation of lignin many amine cations type asphalt emulsifier:
1) 146.2g triethylene tetramine, then dropping 72.1g acrylic acid are added in the reactor, 45 DEG C of stirring reaction 1h,
To reaction intermediate I；
2) in another reactor, add 189.6g 85% (mass fraction) triethanolamine aqueous solution, be gradually added into 131.2g 30%
Technical hydrochloric acid, then be gradually added into 97.1g epoxychloropropane, 45 DEG C of stirring reaction 2h, obtain reaction intermediate II；
3) in another reactor by 283.0g lignin dissolution at 649.6g 10.7% (mass fraction) sodium hydrate aqueous solution
In, mix and blend reacts, and obtains reaction intermediate III；
4) reaction intermediate I is joined in reaction intermediate III, then is gradually added into 92.5g 37% (mass fraction) formaldehyde,
80 DEG C of reaction 2h, obtain reaction intermediate IV；
5) reaction intermediate II is added gradually in reaction intermediate IV, 60 DEG C of reaction 4h.I.e. obtain the many amines of lignin
Cationic asphalt emulsifier, gives over to emulsified asphalt test.
Carrying out FTIR detection after lignin many amine cations separated purification of type asphalt emulsifier of preparation, result is as follows:
3270-3500cm-1Superposition peak, 2959cm is absorbed for O-H stretching vibration and N-H stretching vibration-1Asymmetric flexible for methylene
Vibration absorption peak, 2833cm-1For methylene symmetrical stretching vibration absworption peak, 1649cm-1For N-H bending vibration and carboxylate
Middle C=O stretching vibration absworption peak, 1561cm-1And 1458cm-1For the skeletal vibration absworption peak of phenyl ring, 1400cm-1For O-H
In-plane bending vibration absworption peak, 1076cm-1For C-O stretching vibration absworption peak, 1034cm-1Absorb for Ar-O-C stretching vibration
Peak, 880cm-1For hydrogen out-of-plane bending vibration absworption peak isolated on phenyl ring, 669cm-1For O-H out-of-plane bending vibration absworption peak.
Reaction equation is as follows:
NH2C2H4NHC2H4NHC2H4NH2+CH2=CHCOOH → NH2C2H4NHC2H4NHC2H4NHCH2CH2COOH (1)
(2) preparation of emulsified asphalt
Take A-100# Colophonium 300g, be heated to 125 DEG C, asphalt emulsifier prepared by 12.5g the present embodiment is joined 200g
In water, the Nacl acid for adjusting pH value with 30%, to 2-3, is heated to 65 DEG C, prepares soap lye.By Colophonium and emulsifying agent soap lye
Cationic emulsified asphalt is prepared by colloid mill emulsifying.
(3) emulsified asphalt performance detection:
Detection method with embodiment 1, testing result is: emulsified asphalt is uniform, fine and smooth, and bitumen content is 59%, and sieve remains
Amount is 0.02%, wraps area with mineral aggregate and is more than 2/3, and storage stability (1d) is 0.3%；Employing is mixed and stirred material and is mixed and stirred, can
Mixing time is 5 seconds.Show that asphalt emulsion prepared by this emulsifying agent is to split type cationic emulsified bitumen, the equal energy of properties soon
Meet the requirement of JTJ052-2000 standard.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention being not restricted to the described embodiments,
One of ordinary skill in the art should be understood that on the basis of technical scheme, and those skilled in the art need not pay
Various amendments that creative work can be made or deformation are still within protection scope of the present invention.
Claims (10)
1. lignin many amine cations type asphalt emulsifier, it is characterised in that: its general formula of molecular structure is:
Wherein, R is methyl (-CH3), ethyl (-C2H5) or ethoxy (-C2H4OH)；LIGNIN represents lignin molecule chain.
2. the preparation method of lignin many amine cations type asphalt emulsifier, it is characterised in that: comprise the steps:
1) by triethylene tetramine and acrylic acid hybrid reaction, obtaining reaction intermediate I, intermediate compound I is
NH2C2H4NHC2H4NHC2H4NHCH2CH2COOH；
2) low carbon number tertiary amine, technical hydrochloric acid and epoxychloropropane are mixed, reaction, obtain reaction intermediate II, low carbon number uncle
Amine is trimethylamine, triethylamine or triethanolamine, and intermediate II isR is methyl (-CH3),
Ethyl (-C2H5) or ethoxy (-C2H4OH)；
3) by lignin and sodium hydrate aqueous solution hybrid reaction, reaction intermediate III is obtained；
4) reaction intermediate I is joined in reaction intermediate III, then drip formalin, reaction, obtain reaction intermediate
IV, intermediate compound IV is
5) reaction intermediate II is added drop-wise in reaction intermediate IV, reaction, i.e. obtains the drip of lignin many amine cations type
Blue or green emulsifying agent；
As long as above step does not affect preparation, interchangeable.
Preparation method the most according to claim 2, it is characterised in that: the raw material of employing and proportioning raw materials be lignin,
Water, sodium hydroxide, triethylene tetramine, acrylic acid, the formalin of 37%, the trimethylamine aqueous solution of 33%, the industry of 30%
The mass ratio of hydrochloric acid and epoxychloropropane is 100:(159-230): (19-27): (47-55): (23-29): (30-36):
(63-74): (42-50): (31-37).
Preparation method the most according to claim 2, it is characterised in that: the raw material of employing and proportioning raw materials be lignin,
Water, sodium hydroxide, triethylene tetramine, acrylic acid, the formalin of 37%, triethylamine, the technical hydrochloric acid of 30% and epoxy
The mass ratio of chloropropane is 100:(159-230): (19-27): (47-55): (23-29): (30-36): (35-43): (42-50):
(31-37)。
Preparation method the most according to claim 2, it is characterised in that: the raw material of employing and proportioning raw materials be lignin,
Water, sodium hydroxide, triethylene tetramine, acrylic acid, the formalin of 37%, the triethanolamine aqueous solution of 85%, the work of 30%
The mass ratio of industry hydrochloric acid and epoxychloropropane is 100:(159-230): (19-27): (47-55): (23-29): (30-36):
(53-82): (42-50): (31-37).
6. according to the preparation method described in claim 2-5, it is characterised in that: described lignin is alkali lignin.
7. the preparation method of the arbitrary described lignin many amine cations type asphalt emulsifier of claim 2-6, it is characterised in that:
Specifically include following steps:
(1) triethylene tetramine is joined in reaction vessel, then be dividedly in some parts acrylic acid, after acrylic acid adds,
30-60 DEG C of stirring reaction 0.5-2h, obtains reaction intermediate I；
(2) in the second reactor, add low carbon number tertiary amine, be dividedly in some parts technical hydrochloric acid, after technical hydrochloric acid adds, then
It is dividedly in some parts epoxychloropropane, after epoxychloropropane adds, 30-70 DEG C of stirring reaction 2-3h, obtain reaction intermediate II,
Wherein, low carbon number tertiary amine is trimethylamine, triethylamine or triethanolamine；
(3) in the 3rd reactor by lignin dissolution in sodium hydrate aqueous solution, stirring reaction, obtain reaction intermediate
III；
(4) reaction intermediate I is joined in reaction intermediate III, then be dividedly in some parts 37% formalin, 60-80 DEG C
Reaction 2-4h, obtains reaction intermediate IV；
(5) reaction intermediate II is dividedly in some parts in reaction intermediate IV, 60-80 DEG C of reaction 2-4h, i.e. obtains lignin
Many amine cations type asphalt emulsifier；
As long as not affecting preparation, above step is interchangeable.
8. lignin many amine cations type asphalt emulsifier described in claim 1 splits in type cationic emulsified bitumen soon in preparation
Application.
9. the preparation method splitting type cationic emulsified bitumen soon, it is characterised in that: comprise the steps: claim 1
The consumption of described asphalt emulsifier is the 1.0-3.0% of emulsified asphalt gross mass of preparation, by many for above-mentioned lignin amines sun from
Subtype asphalt emulsifier adds water and is configured to aqueous solution, with salt acid for adjusting pH value to 2-3, is heated to 60-70 DEG C, prepares soap lye；
Colophonium and emulsifying agent soap lye after heating are prepared by colloid mill emulsifying and are split type cationic emulsified bitumen soon.
10. what the preparation method described in claim 9 prepared splits type cationic emulsified bitumen soon.
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| CN106750374A (en) * | 2016-12-15 | 2017-05-31 | 天津康泽威科技有限公司 | A kind of asphalt emulsifier and preparation method thereof and emulsified asphalt product |
| CN106831478A (en) * | 2017-01-23 | 2017-06-13 | 山东大学 | Asphalt emulsifier of type or slow breaking and preparation method thereof is split in a kind of polycation teritary amide class |
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| CN106832328A (en) * | 2016-12-31 | 2017-06-13 | 山西省交通科学研究院 | A kind of retarder for being applied to emulsified asphalt cold in-plant recycling compound and preparation method thereof |
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