CN105968382A - Lignin polyamine cation rapid-cracking type asphalt emulsifier and preparation method thereof - Google Patents
Lignin polyamine cation rapid-cracking type asphalt emulsifier and preparation method thereof Download PDFInfo
- Publication number
- CN105968382A CN105968382A CN201610459555.1A CN201610459555A CN105968382A CN 105968382 A CN105968382 A CN 105968382A CN 201610459555 A CN201610459555 A CN 201610459555A CN 105968382 A CN105968382 A CN 105968382A
- Authority
- CN
- China
- Prior art keywords
- lignin
- reaction
- preparation
- soon
- reaction intermediate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Civil Engineering (AREA)
- Dispersion Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Road Paving Structures (AREA)
Abstract
The invention discloses a lignin polyamine cation rapid-cracking type asphalt emulsifier and a preparation method thereof. The molecular structure of the emulsifier is as shown in the specification. In the formula, R is methyl (-CH3), ethyl (-C2H5) or ethoxyl (-C2H4OH); LIGNIN represents a lignin molecular chain. The lignin polyamine cation rapid-cracking type asphalt emulsifier is prepared from the following raw materials in parts by weight: lignin, water, sodium hydroxide, diethylenetriamine, crylic acid, formaldehyde (37%), low-carbon-number tertiary amine and industrial hydrochloric acid in a ratio of 100:(159-230):(19-27):(32-40):(23-29):(30-36):(35-82):(42-50):(31-37). The lignin polyamine cation rapid-cracking type asphalt emulsifier disclosed by the invention is high in synthesis raw material availability, low in production cost, simple in process and free of high-temperature reaction. Multiple types of asphalt of different models can be emulsified, the prepared emulsified asphalt is fine and uniform, the storage stability is good, and the rapid-cracking type cation emulsified asphalt can be prepared.
Description
Technical field
The present invention relates to a kind of many amine cations of lignin and split type asphalt emulsifier and preparation method thereof soon, belong to fine
Chemical technology field.
Background technology
Emulsified asphalt be Colophonium and water under the effect of emulsifying agent, form oil-in-water liquid bitumen emulsion.Emulsified asphalt
It is broadly divided into cationic emulsified bitumen, 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 it is excellent effectively to reduce the many such as Colophonium overaging
Good 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 Colophonium
Emulsifying 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 C12-18Long carbon chain fatty acid and diethylenetriamine react preparation under certain condition
Asphalt emulsifier.The shortcoming of the method is that the asphalt emulsifier prepared is expensive, when slurry seal is constructed, and the breakdown of emulsion time
Long, molding time is slow, and the open to traffic time is long.Chinese patent CN1096714 utilizes oil plant by-product aphthenic acids and alkenyl polyamine
Reaction, prepares asphalt emulsifier.The shortcoming of the method be the raw material supply of emulsifying agent by severely restricts, be unfavorable for promote should
With.Chinese patent CN1861721A relates to a kind of rosin cation asphalt emulgent.This emulsifying agent is by Colophonium and alkenyl polyamine
Reaction, obtain Colophonium intermediate, then, be condensed with different types of quaternary ammonium salt intermediate, prepare function admirable Colophonium sun from
Sub-asphalt emulsifier.The shortcoming of this method is that reactions steps is loaded down with trivial details, needs pyroreaction.Chinese patent CN101712625A relates to
And one method for synthesizing amphoteric slow-breaking quick-setting asphalt emulsifier, use oleic acid and polyamines to react generation polyamide-polyamino, be subsequently adding
Monoxone generation halogenating reaction, prepares asphalt emulsifier.The shortcoming of the method needs pyroreaction when being to prepare.Chinese patent
CN101745340A relates to a kind of cation asphalt emulgent preparation method, and host is reacted by mixed organic acid and organic amine and obtained
Intermediate, then carry out quaterisation prepare, adjuvant is nonionic surfactant and modified additive.The shortcoming of the method is system
Standby complex steps, relatively costly, need pyroreaction.
The deficiency that above-mentioned cationic asphalt emulsifier and preparation method thereof generally exists is: the raw material preparing emulsifying agent becomes
This is higher, and source is restricted, and needs pyroreaction during preparation, higher to productive experiment equipment requirements.Lignin is nature
Middle storage be only second to cellulose be positioned at second natural biological organic compound.Research lignin asphalt emulsifier can reduce
The environmental pollution that in papermaking, black liquor brings.The production of asphalt emulsifier can be reduced using lignin as the raw material of asphalt emulsifier to become
This, and synthesis technique is simple, and raw material sources are extensive.Therefore, exploitation is based on the function admirable that lignin is raw material, with low cost
Novel asphalt emulsifying agent there is 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 many amine cations of lignin and split type Colophonium breast soon
Agent and preparation method thereof.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 fine and smooth
Uniformly, storage stability is good.
For achieving the above object, the present invention uses following technical proposals:
A kind of many amine cations of lignin split type asphalt emulsifier soon, and its general formula of molecular structure is:
Wherein, R is methyl (-CH3), ethyl (-C2H5) or ethoxy (-C2H4OH)；LIGNIN represents lignin molecule chain.
The many amine cations of a kind of lignin split the preparation method of type asphalt emulsifier soon, comprise the steps:
1) by diethylenetriamine and acrylic acid hybrid reaction, obtaining reaction intermediate I, intermediate compound I is
NH2C2H4NHC2H4NHCH2CH2COOH；
2) low carbon number tertiary amine, technical hydrochloric acid and epoxychloropropane are mixed, reaction, obtain reaction intermediate II, low carbon number
Tertiary amine is trimethylamine, triethylamine or triethanolamine, and intermediate II isR be 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 in the middle of reaction
Body IV, intermediate compound IV is
5) reaction intermediate II is added drop-wise in reaction intermediate IV, reaction, i.e. obtains the many amine cations of lignin fast
Split type asphalt emulsifier；
As long as above step does not affect preparation, interchangeable.
Preferably, the concentration of described formalin is 37%, and trimethylamine uses concentration to be the trimethylamine aqueous solution of 33%, work
The concentration of industry hydrochloric acid is 30%, the triethanolamine aqueous solution that triethanolamine uses concentration to be 85%.
Preferably, the raw material of employing and proportioning raw materials be, lignin, water, sodium hydroxide, diethylenetriamine, 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): (32-40): (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, diethylenetriamine, acrylic acid,
The mass ratio of formalin, triethylamine, the technical hydrochloric acid of 30% and the epoxychloropropane of 37% is 100:(159-230):
(19-27): (32-40): (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, diethylenetriamine, acrylic acid,
The mass ratio of the formalin of 37%, the triethanolamine aqueous solution of 85%, the technical hydrochloric acid of 30% and epoxychloropropane is
100:(159-230): (19-27): (32-40): (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
Aqueous solution.
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 many amine cations of above-mentioned lignin split the preparation method of type asphalt emulsifier soon, specifically include following steps:
(1) diethylenetriamine 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,
It is dividedly in some parts epoxychloropropane again, after epoxychloropropane adds, at 30-70 DEG C of stirring reaction 2-3h, obtains in the middle of reaction
Body 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 in the middle of
Body 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, obtain 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 wooden
The many amine cations of element split type asphalt emulsifier soon；
As long as not affecting preparation, above step is interchangeable.
The many amine cations of above-mentioned lignin split type asphalt emulsifier soon and split soon in type cationic emulsified bitumen in preparation
Application.
A kind of preparation method splitting type cationic emulsified bitumen soon, comprises the steps: that the consumption of asphalt emulsifier is system
Many for above-mentioned lignin amine cations are split type asphalt emulsifier and add water and join by the 1.0-3.0% of standby emulsified asphalt gross mass soon
Make aqueous solution, with salt acid for adjusting pH value to 2-3, be heated to 60-70 DEG C, prepare soap lye；By the Colophonium after heating and emulsifying agent
Soap lye is prepared by colloid mill emulsifying and is split type cationic emulsified bitumen soon.
What described preparation method prepared splits type cationic emulsified bitumen soon.
The present invention, by the reasonable selection to reaction raw materials, has prepared lignin many amines sun of a kind of brand new
Ion splits type asphalt emulsifier soon.Wherein, the present invention is using acrylic acid as the reaction raw materials of asphalt emulsifier, at asphalt emulsifier
Molecular structure in introduce carboxylic acid group by adding acrylic acid, add the hydrophilic of asphalt emulsifier, and emulsifying agent with
The compatibility of Colophonium.It addition, consider carbon chain lengths for the HLB value (hydrophilic/lipophilic balance value) of asphalt emulsifier and CMC
The impact of (critical micelle concentration), selects using lignin, diethylenetriamine, epoxychloropropane and low carbon number tertiary amine as reaction
Raw material, makes the HLB value of asphalt emulsifier of preparation within optimum range, improves the emulsifiability to Colophonium.
Beneficial effects of the present invention:
(1) the many amine cations of the lignin of the present invention split the raw material wood element of type asphalt emulsifier soon relative to current
Raw material used by cationic asphalt emulsifier is cheap, wide material sources, and asphalt emulsifier production cost is low.
(2) the many amine cations of the lignin of the present invention split that the preparation method technique of type asphalt emulsifier is simple soon, are not required to
Want pyroreaction.
(3) the many amine cations of lignin that prepared by the present invention split the emulsifiable multiple different model of type asphalt emulsifier soon
Colophonium, the emulsified asphalt of preparation is fine and smooth, and uniformly storage stability is good, it is adaptable to highway priming oil or the spread of sticking layer oil, and
For crushed stone sealing, screening seal coat, the slight check crack of mist sealing and reparation road surface etc., there is the characteristic splitting type asphalt emulsifier soon.
The emulsified asphalt properties prepared all can meet the cationic emulsified bitumen standard (JTJ052-that Chinese transportation portion works out
2000)。
(4) by adding acrylic acid, diethylenetriamine, low carbon number tertiary amine and epoxychloropropane in the raw material of the present invention, make
The asphalt emulsification agent molecule that must prepare has many amine cations type chemical constitution, and the electric charge enhancing asphalt emulsification agent molecule is strong
Degree, improves the hydrophilic of asphalt emulsification agent molecule.So not only increase the emulsifiability of asphalt emulsifier, and improve
The serviceability of emulsified asphalt.
Due to the many amine cations of the lignin of the present invention, to split the ionization of type asphalt emulsifier soon stronger, is increasing
Asphalt emulsifier hydrophilic at the same time it can also be make interfacial film carry the most more positive charge, occurs in that a stratum boundary
Surface charge, thus occurs in that interface charge layer.The formation of interface charge layer, by making bitumen particle mutually exclusive, makes them keep
Certain distance, thus allow pitch particle maintain dispersity, asphalt emulsion is served peptizaiton.Going out of interface charge layer
Existing, for the dispersion in aqueous phase of the emulsifying of Colophonium, Colophonium, keep the homogeneous stability system of asphalt emulsion to have vital
Effect.Due to emulsifying agent ionizable relatively polycation in water of the present invention, so interface charge layer effect is relatively strong, so that
After the emulsifier Colophonium of the present invention, its system is more stable.
Detailed description of the invention
Below by instantiation, the present invention will be further elaborated, it should explanation, the description below be only for
The explanation present invention, is not defined its content.
Raw material, reagent used in the embodiment of the present invention are conventional chemical products, all can be purchased by commercial channel
Can buy.
Embodiment 1:
(1) the many amine cations of lignin split the preparation of type asphalt emulsifier soon:
1) 103.2g diethylenetriamine, then dropping 72.1g acrylic acid are added in the reactor, 45 DEG C of stirring reaction 1h,
Obtain reaction intermediate I.
2) in another reactor, add 193.1g 33% (mass fraction) trimethylamine aqueous solution, be gradually added into 131.2g
30% (mass fraction) technical hydrochloric acid, then it is gradually added into 97.1g epoxychloropropane, 45 DEG C of stirring reaction 2h, obtain in the middle of reaction
Body II.
3) in another reactor by 283.0g lignin dissolution at 649.6g 10.7% (mass fraction) sodium hydroxide water
In solution, mix and blend reacts, and obtains reaction intermediate III.
4) reaction intermediate I is joined in reaction intermediate III, then be gradually added into 92.5g 37% (mass fraction) first
Aldehyde, 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 lignin polyamines
Cationoid splits type asphalt emulsifier soon, gives over to emulsified asphalt test.
FTIR detection is carried out, knot after many for the lignin of preparation amine cations are split the separated purification of type asphalt emulsifier soon
Fruit is as follows: 3320-3516cm-1Superposition peak, 2970cm is absorbed for O-H stretching vibration and N-H stretching vibration-1Non-right for methylene
Claim stretching vibration absworption peak, 2835cm-1For methylene symmetrical stretching vibration absworption peak, 1635cm-1For N-H bending vibration and carboxylic
C=O stretching vibration absworption peak, 1574cm in hydrochlorate-1And 1464cm-1For the skeletal vibration absworption peak of phenyl ring, 1410cm-1With
1323cm-1For O-H in-plane bending vibration absworption peak, 1103cm-1For C-H in-plane bending vibration absworption peak, 1037cm-1For Ar-O-
C stretching vibration absworption peak, 960cm-1For hydrogen out-of-plane bending vibration absworption peak isolated on phenyl ring, 611cm-1For O-H out-of-plane bending
Vibration absorption peak.
Reaction equation is as follows:
NH2C2H4NHC2H4NH2+CH2=CHCOOH → NH2C2H4NHC2H4NHCH2CH2COOH (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
In 200g water, with technical hydrochloric acid regulation pH value to 2-3, it is heated to 65 DEG C, prepares soap lye.Colophonium and emulsifying agent soap lye are passed through glue
Cationic emulsified asphalt is prepared in body 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 is examined
Surveying, result 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
0.03%, wrap area with mineral aggregate and be more than 2/3, storage stability (1d) is 0.6%；Employing is mixed and stirred material and is mixed and stirred, and can mix and stir
Time is 4 seconds.Show asphalt emulsion prepared by this emulsifying agent for split type cationic emulsified bitumen soon, properties all can meet
The requirement of JTJ052-2000 standard.
Embodiment 2:
(1) the many amine cations of lignin split the preparation of type asphalt emulsifier soon:
1) 103.2g diethylenetriamine, then dropping 72.1g acrylic acid are added in the reactor, 45 DEG C of stirring reaction 1h,
Obtain reaction intermediate I.
2) in another reactor, add 109.1g triethylamine, be gradually added into 131.2g 30% (mass fraction) Nacl
Acid, then it is 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 hydroxide water
In solution, mix and blend reacts, and obtains reaction intermediate III.
4) reaction intermediate I is joined in reaction intermediate III, then be gradually added into 92.5g 37% (mass fraction) first
Aldehyde, 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 lignin polyamines
Cationoid splits type asphalt emulsifier soon, gives over to emulsified asphalt test.
FTIR detection is carried out, knot after many for the lignin of preparation amine cations are split the separated purification of type asphalt emulsifier soon
Fruit is as follows: 3245-3425cm-1Superposition peak, 2946cm is absorbed for O-H stretching vibration and N-H stretching vibration-1Non-right for methylene
Claim stretching vibration absworption peak, 2833cm-1For methylene symmetrical stretching vibration absworption peak, 1639cm-1For N-H bending vibration and carboxylic
C=O stretching vibration absworption peak, 1585cm in hydrochlorate-1And 1454cm-1For the skeletal vibration absworption peak of phenyl ring, 1407cm-1With
1306cm-1For O-H in-plane bending vibration absworption peak, 1121cm-1For C-H in-plane bending vibration absworption peak, 1096cm-1Stretch for C-O
Contracting vibration absorption peak, 1026cm-1For Ar-O-C stretching vibration absworption peak, 789cm-1For C-H out-of-plane bending vibration absworption peak,
623cm-1For O-H out-of-plane bending vibration absworption peak.
Reaction equation is as follows:
NH2C2H4NHC2H4NH2+CH2=CHCOOH → NH2C2H4NHC2H4NHCH2CH2COOH (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
In 200g water, with technical hydrochloric acid regulation pH value to 2-3, it is heated to 65 DEG C, prepares soap lye.Colophonium and emulsifying agent soap lye are passed through glue
Cationic emulsified asphalt is prepared in body 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%, surplus on sieve
Surplus is 0.04%, wraps area with mineral aggregate and is more than 2/3, and storage stability (1d) is 0.8%；Employing is mixed and stirred material and is mixed and stirred,
Can it be 6 seconds the mixing time.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) the many amine cations of lignin split the preparation of type asphalt emulsifier soon:
1) 103.2g diethylenetriamine, then dropping 72.1g acrylic acid are added in the reactor, 45 DEG C of stirring reaction 1h,
Obtain reaction intermediate I.
2) in another reactor, add 189.6g 85% (mass fraction) triethanolamine aqueous solution, be gradually added into
131.2g 30% (mass fraction) technical hydrochloric acid, then it is gradually added into 97.1g epoxychloropropane, 45 DEG C of stirring reaction 2h, obtain anti-
Answer intermediate II.
3) in another reactor by 283.0g lignin dissolution at 649.6g 10.7% (mass fraction) sodium hydroxide water
In solution, mix and blend reacts, and obtains reaction intermediate III.
4) reaction intermediate I is joined in reaction intermediate III, then be gradually added into 92.5g 37% (mass fraction) first
Aldehyde, 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 lignin polyamines
Cationoid splits type asphalt emulsifier soon, gives over to emulsified asphalt test.
FTIR detection is carried out, knot after many for the lignin of preparation amine cations are split the separated purification of type asphalt emulsifier soon
Fruit is as follows: 3242-3525cm-1Superposition peak, 2953cm is absorbed for O-H stretching vibration and N-H stretching vibration-1Non-right for methylene
Claim stretching vibration absworption peak, 2833cm-1For methylene symmetrical stretching vibration absworption peak, 1649cm-1For N-H bending vibration and carboxylic
C=O stretching vibration absworption peak, 1573cm in hydrochlorate-1And 1454cm-1For the skeletal vibration absworption peak of phenyl ring, 1398cm-1With
1309cm-1For O-H in-plane bending vibration absworption peak, 1121cm-1For C-H in-plane bending vibration absworption peak, 1065cm-1Stretch for C-O
Contracting vibration absorption peak, 1030cm-1For Ar-O-C stretching vibration absworption peak, 925cm-1And 880cm-1For hydrogen face isolated on phenyl ring
Outside sweep vibration absorption peak, 606cm-1For O-H out-of-plane bending vibration absworption peak.
Reaction equation is as follows:
NH2C2H4NHC2H4NH2+CH2=CHCOOH → NH2C2H4NHC2H4NHCH2CH2COOH (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
In 200g water, with technical hydrochloric acid regulation pH value to 2-3, it is heated to 65 DEG C, prepares soap lye.Colophonium and emulsifying agent soap lye are passed through glue
Cationic emulsified asphalt is prepared in body 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%, surplus on sieve
Surplus is 0.01%, wraps area with mineral aggregate and is more than 2/3, and storage stability (1d) is 0.5%；Employing is mixed and stirred material and is mixed and stirred,
Can it be 5 seconds the mixing time.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 are not by above-described embodiment
Limiting, one of ordinary skill in the art should be understood that, on the basis of technical scheme, those skilled in the art need not
Pay various amendments or deformation that creative work can make still within protection scope of the present invention.
Claims (10)
1. the many amine cations of lignin split type asphalt emulsifier soon, 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. many amine cations of lignin split the preparation method of type asphalt emulsifier soon, it is characterised in that: include walking as follows
Rapid:
1) by diethylenetriamine and acrylic acid hybrid reaction, obtaining reaction intermediate I, intermediate compound I is
NH2C2H4NHC2H4NHCH2CH2COOH；
2) low carbon number tertiary amine, technical hydrochloric acid and epoxychloropropane are mixed, reaction, obtain reaction intermediate II, low carbon number tertiary amine
For trimethylamine, triethylamine or triethanolamine, intermediate II isR is methyl (-CH3), second
Base (-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 many amine cations of lignin and split type soon
Asphalt emulsifier；
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, diethylenetriamine, acrylic acid, the formalin of 37%, the trimethylamine aqueous solution of 33%, the Nacl of 30%
The mass ratio of acid and epoxychloropropane is 100:(159-230): (19-27): (32-40): (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, diethylenetriamine, acrylic acid, the formalin of 37%, triethylamine, the technical hydrochloric acid of 30% and epoxy chlorine
The mass ratio of propane is 100:(159-230): (19-27): (32-40): (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, diethylenetriamine, acrylic acid, the formalin of 37%, the triethanolamine aqueous solution of 85%, the industry of 30%
The mass ratio of hydrochloric acid and epoxychloropropane is 100:(159-230): (19-27): (32-40): (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 many amine cations of the arbitrary described lignin of claim 2-6 split the preparation method of type asphalt emulsifier, its feature soon
It is: specifically include following steps:
(1) diethylenetriamine is joined in reaction vessel, then be dividedly in some parts acrylic acid, after acrylic acid adds, at 30-60
DEG C stirring reaction 0.5-2h, obtain 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 divide
Criticize and add epoxychloropropane, after epoxychloropropane adds, 30-70 DEG C of stirring reaction 2-3h, obtain reaction intermediate II, its
In, 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 is anti-
Answer 2-4h, obtain 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 cation splits type asphalt emulsifier soon；
As long as not affecting preparation, above step is interchangeable.
8. the many amine cations of lignin described in claim 1 split type asphalt emulsifier soon and split the cation emulsified drip of type soon in preparation
Application in green grass or young crops.
9. the preparation method splitting type cationic emulsified bitumen soon, it is characterised in that: comprise the steps: claim 1 institute
The consumption of the asphalt emulsifier stated is the 1.0-3.0% of emulsified asphalt gross mass of preparation, by many for above-mentioned lignin amines sun from
Son splits type asphalt emulsifier soon and adds water and be configured to aqueous solution, with salt acid for adjusting pH value to 2-3, is heated to 60-70 DEG C, prepares soap
Liquid；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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610459555.1A CN105968382B (en) | 2016-06-22 | 2016-06-22 | A kind of more amine cations of lignin split type asphalt emulsifier and preparation method thereof soon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610459555.1A CN105968382B (en) | 2016-06-22 | 2016-06-22 | A kind of more amine cations of lignin split type asphalt emulsifier and preparation method thereof soon |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105968382A true CN105968382A (en) | 2016-09-28 |
| CN105968382B CN105968382B (en) | 2018-03-20 |
Family
ID=57022177
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610459555.1A Expired - Fee Related CN105968382B (en) | 2016-06-22 | 2016-06-22 | A kind of more amine cations of lignin split type asphalt emulsifier and preparation method thereof soon |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105968382B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108559104A (en) * | 2018-05-15 | 2018-09-21 | 苏州太星新材料科技有限公司 | A kind of lignin imines quaternary ammonium salt cation asphalt emulsifier and preparation method thereof |
| CN108912347A (en) * | 2018-08-17 | 2018-11-30 | 佛山市森昂生物科技有限公司 | A kind of preparation method of high stable type lignin asphalt emulsifier |
| CN111320764A (en) * | 2019-01-15 | 2020-06-23 | 山东大学 | Secondary amide polyamine quaternary ammonium salt amphoteric asphalt emulsifier and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105384948A (en) * | 2015-12-21 | 2016-03-09 | 山东大学 | Dication and dianion type asphalt emulsifier and preparation method thereof |
| CN105399645A (en) * | 2015-12-21 | 2016-03-16 | 山东大学 | Multi-positive-ion amide-type asphalt emulsifier and preparation method thereof |
-
2016
- 2016-06-22 CN CN201610459555.1A patent/CN105968382B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105384948A (en) * | 2015-12-21 | 2016-03-09 | 山东大学 | Dication and dianion type asphalt emulsifier and preparation method thereof |
| CN105399645A (en) * | 2015-12-21 | 2016-03-16 | 山东大学 | Multi-positive-ion amide-type asphalt emulsifier and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 施来顺等: ""四乙烯五胺/甲醛改性木质素胺沥青乳化剂的合成及在线红外研究"", 《石油沥青》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108559104A (en) * | 2018-05-15 | 2018-09-21 | 苏州太星新材料科技有限公司 | A kind of lignin imines quaternary ammonium salt cation asphalt emulsifier and preparation method thereof |
| CN108912347A (en) * | 2018-08-17 | 2018-11-30 | 佛山市森昂生物科技有限公司 | A kind of preparation method of high stable type lignin asphalt emulsifier |
| CN111320764A (en) * | 2019-01-15 | 2020-06-23 | 山东大学 | Secondary amide polyamine quaternary ammonium salt amphoteric asphalt emulsifier and preparation method thereof |
| CN111320764B (en) * | 2019-01-15 | 2021-04-27 | 山东大学 | Secondary amide polyamine quaternary ammonium salt amphoteric asphalt emulsifier and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105968382B (en) | 2018-03-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106008996B (en) | A kind of more amine cation type asphalt emulsifiers of lignin and preparation method and application | |
| CN105399645B (en) | A kind of polycation acid amide type asphalt emulsifier and preparation method thereof | |
| CN105860092B (en) | A kind of lignin diamine cationoid type asphalt emulsifier and preparation method thereof | |
| CN106084250B (en) | A kind of lignin cyclammonium cationoid type asphalt emulsifier and preparation method thereof | |
| CN105418942B (en) | A kind of dication acid amide type asphalt emulsifier and preparation method thereof | |
| CN106946747B (en) | A kind of carboxylic acid double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier and preparation method thereof | |
| CN105384948B (en) | A kind of dication dual anion type asphalt emulsifier and preparation method thereof | |
| CN105885060B (en) | A kind of more amine quaternary ammonium salt cationic type asphalt emulsifiers of lignin and preparation method thereof | |
| CN106977431B (en) | A kind of primary amide quaternary hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier and preparation method thereof | |
| CN104151179B (en) | A kind of dication type asphalt emulsifier and preparation method thereof | |
| CN106977432B (en) | A kind of teritary amide quaternary hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier and preparation method thereof | |
| CN105968382B (en) | A kind of more amine cations of lignin split type asphalt emulsifier and preparation method thereof soon | |
| CN107903194A (en) | A kind of amidoquat salt form hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier and preparation method thereof | |
| CN107056637A (en) | A kind of dication teritary amide type asphalt emulsifier and preparation method thereof | |
| CN106947093B (en) | A kind of primary amide double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier and preparation method thereof | |
| CN108467495A (en) | A kind of lignin quaternary ammonium salt cation asphalt emulsifier and preparation method thereof | |
| CN108517040A (en) | A kind of cellulose family quaternary ammonium salt cation asphalt emulsifier and preparation method thereof | |
| CN109694481B (en) | Carboxylic acid bis-quaternary ammonium salt type sodium hydroxypropyl phosphate asphalt emulsifier and preparation method thereof | |
| CN109456499B (en) | Amide bis-quaternary ammonium salt type sodium hydroxypropyl phosphate asphalt emulsifier and preparation method thereof | |
| CN106995393B (en) | A kind of double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier and preparation method thereof | |
| CN110305336A (en) | A kind of polyamide-polyamino type asphalt emulsifier, emulsified asphalt and the preparation method and application thereof | |
| CN107892753B (en) | A kind of secondary amide quaternary Hydroxypropyl phosphate ester sodium asphalt emulsifier and preparation method thereof | |
| CN108794762A (en) | A kind of cellulose imines quaternary ammonium salt cation asphalt emulsifier and preparation method thereof | |
| CN108559104A (en) | A kind of lignin imines quaternary ammonium salt cation asphalt emulsifier and preparation method thereof | |
| CN108586772A (en) | A kind of lignin polyether class quaternary ammonium salt cation asphalt emulsifier and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180320 Termination date: 20190622 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |