CN105885060B - A kind of more amine quaternary ammonium salt cationic type asphalt emulsifiers of lignin and preparation method thereof - Google Patents

A kind of more amine quaternary ammonium salt cationic type asphalt emulsifiers of lignin and preparation method thereof Download PDF

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CN105885060B
CN105885060B CN201610457735.6A CN201610457735A CN105885060B CN 105885060 B CN105885060 B CN 105885060B CN 201610457735 A CN201610457735 A CN 201610457735A CN 105885060 B CN105885060 B CN 105885060B
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lignin
reaction
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asphalt
reaction intermediate
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CN105885060A (en
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施来顺
李德梅
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Shandong University
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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
    • 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
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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    • C08L2201/54—Aqueous solutions or dispersions

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Abstract

The invention discloses more amine quaternary ammonium salt cationic type asphalt emulsifiers of a kind of lignin and preparation method and application, its general formula of molecular structure is：Wherein, R is methyl (CH3), ethyl (C2H5) or ethoxy (C2H4OH)；LIGNIN represents lignin molecule chain.By adding acrylic acid, TEPA, low carbon number tertiary amine and epoxychloropropane in the raw material of the present invention, so that the asphalt emulsification agent molecule prepared has more amine quaternary ammonium salt cationic type chemical constitutions, the charge density of asphalt emulsification agent molecule is enhanced, improves the hydrophily of asphalt emulsification agent molecule.The emulsifiability of asphalt emulsifier is so not only increased, and improves the performance of emulsified asphalt.

Description

A kind of more amine quaternary ammonium salt cationic type asphalt emulsifiers of lignin and preparation method thereof
Technical field
The present invention relates to more amine quaternary ammonium salt cationic type asphalt emulsifiers of a kind of lignin and preparation method thereof, belong to essence Thin chemical technology field.
Background technology
Emulsified asphalt be pitch and water in the presence 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 With energy-conserving and environment-protective, execution conditions can be improved and building stones adhesion is strong, and it is many excellent effectively to reduce pitch overaging etc. Good application characteristic, and be widely used in road construction and pavement preservation.
The most critical factor for influenceing emulsified asphalt pavement performance is exactly asphalt emulsifier, at present domestic and international cationic pitch Emulsifying agent principal item has organic amine, quaternary ammonium salt, imidazolines, amide-type etc., with the application of cationic emulsified bitumen, The kind of asphalt emulsifier is also gradually enriched.
United States Patent (USP) USP4338136 is with C12-18Long carbon chain aliphatic acid reacts preparation under certain condition with diethylenetriamine Asphalt emulsifier.The shortcomings that this method is that the asphalt emulsifier prepared is expensive, when being constructed for slurry seal, is demulsified the time Long, molding time is slow, open to traffic time length.Chinese patent CN1096714 utilizes oil plant by-product aphthenic acids and alkenyl polyamine Reaction, prepares asphalt emulsifier.The shortcomings that this method be the raw material supply of emulsifying agent by severely restricts, being unfavorable for promoting should With.Chinese patent CN1861721A is related to a kind of rosin cation asphalt emulgent.The emulsifying agent is by rosin and alkenyl polyamine Reaction, obtain rosin intermediate, then, with different types of quaternary ammonium salt intermediate be condensed, be made function admirable rosin sun from Sub- asphalt emulsifier.The shortcomings that this method is that reactions steps are cumbersome, it is necessary to pyroreaction.Chinese patent CN101712625A is related to And a kind of method for synthesizing amphoteric slow-breaking quick-setting asphalt emulsifier, using oleic acid and polyamines reaction generation polyamide-polyamino, then add Halogenating reaction occurs for monoxone, and asphalt emulsifier is made, and is to need pyroreaction when preparing the shortcomings that this method.Chinese patent CN101745340A is related to a kind of cation asphalt emulgent preparation method, and host is reacted to obtain by mixed organic acid and organic amine Intermediate, then carry out quaterisation and be made, assistant agent is nonionic surfactant and modified additive.The shortcomings that this method is system Standby complex steps, cost are higher, it is necessary to pyroreaction.
The deficiency of above-mentioned cationic asphalt emulsifier and preparation method thereof generally existing is：Prepare the raw material of emulsifying agent into This is higher, and source is restricted, and needs pyroreaction during preparation, higher to productive experiment equipment requirement.Lignin is nature Middle storage is only second to the natural biological organic compound for being located at second of cellulose.Research lignin asphalt emulsifier can reduce The environmental pollution that black liquor is brought in papermaking.Being produced into for asphalt emulsifier can be reduced using lignin as the raw material of asphalt emulsifier This, and synthesis technique is simple, and raw material sources are extensive.Therefore, develop cheap for function admirable, the cost of raw material based on lignin Novel asphalt emulsifying agent there is highly important actual application value.
The content of the invention
For above-mentioned prior art, it is an object of the invention to provide a kind of more amine quaternary ammonium salt cationic type pitches of lignin Emulsifying agent and preparation method and application.Raw material sources needed for the preparation method are extensive, and production cost is low, and preparation technology is simple, Without pyroreaction.The asphalt emulsifier function admirable being prepared, the pitch of emulsifiable a variety of different models, the emulsification of preparation Pitch is fine and smooth uniformly, and storage stability is good.
To achieve the above object, the present invention uses following technical proposals：
A kind of more amine quaternary ammonium salt cationic type asphalt emulsifiers of lignin, its general formula of molecular structure are：
Wherein, R is methyl (- CH3), ethyl (- C2H5) or ethoxy (- C2H4OH)；LIGNIN represents lignin molecule chain.
A kind of preparation method of the more amine quaternary ammonium salt cationic type asphalt emulsifiers of lignin, comprises the following steps：
1) by TEPA and acrylic acid hybrid reaction, reaction intermediate I is obtained, intermediate compound I is NH2C2H4NHC2H4NHC2H4NHC2H4NHCH2CH2COOH；
2) low carbon number tertiary amine, technical hydrochloric acid and epoxychloropropane are mixed, reaction, obtains 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 added in reaction intermediate III, then formalin is added dropwise, reacted, obtained among reaction Body IV, intermediate compound IV are
5) reaction intermediate II is added drop-wise in reaction intermediate IV, reacted, that is, obtain the more amine quaternary ammonium salt sun of lignin Ionic asphalt emulsifier；
As long as above step does not influence to prepare, interchangeable.
Preferably, the concentration of the formalin is 37%, and the concentration of technical hydrochloric acid is 30%, trimethylamine aqueous solution Concentration is 33%.
Preferably, the raw material that uses and raw material proportioning for：Lignin, water, sodium hydroxide, TEPA, acrylic acid, 37% formalin, 33% trimethylamine aqueous solution, the mass ratio of 30% technical hydrochloric acid and epoxychloropropane are 100： (159-230)：(19-27)：(61-73)：(23-29)：(30-36)：(63-74)：(42-50)：(31-37).
Preferably, the raw material that uses and raw material proportioning for：Lignin, water, sodium hydroxide, TEPA, acrylic acid, 37% formaldehyde, triethylamine, the mass ratio of 30% technical hydrochloric acid and epoxychloropropane are 100：(159-230)：(19- 27)：(61-73)：(23-29)：(30-36)：(35-43)：(42-50)：(31-37).
Preferably, the raw material that uses and raw material proportioning for：Lignin, water, sodium hydroxide, TEPA, acrylic acid, 37% formaldehyde, 85% triethanolamine, the mass ratio of 30% technical hydrochloric acid and epoxychloropropane are 100：(159- 230)：(19-27)：(61-73)：(23-29)：(30-36)：(53-82)：(42-50)：(31-37).
Wherein, the water and sodium hydroxide mixing, the sodium hydroxide sodium hydroxide soluble in water obtained in step 3) The aqueous solution；85% triethanolamine refers to the triethanolamine aqueous solution that mass fraction is 85%.
Preferably, described lignin is alkali lignin.
Preferably, in step 1), the temperature of reaction is 30-60 DEG C, and the time of reaction is 0.5-2h.
Preferably, in step 2), the temperature of reaction is 30-70 DEG C.
Preferably, in step 4), the temperature of reaction is 60-80 DEG C, and preferably 65-75 DEG C, the time of reaction is 2-4h.
Preferably, in step 5), the temperature of reaction is 60-80 DEG C, and preferably 65-75 DEG C, the time of reaction is 2-4h.
The preparation method of the above-mentioned more amine quaternary ammonium salt cationic type asphalt emulsifiers of lignin, specifically comprises the following steps：
(1) TEPA is added in reaction vessel, then acrylic acid is added portionwise, after acrylic acid adds, 30-60 DEG C of stirring reaction 0.5-2h, obtains reaction intermediate I；
(2) low carbon number tertiary amine is added in second reactor, technical hydrochloric acid is added portionwise, after technical hydrochloric acid adds, Epoxychloropropane is added portionwise again, after epoxychloropropane adds, in 30-70 DEG C of stirring reaction 2-3h, obtains among 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 among Body III；
(4) reaction intermediate I is added in reaction intermediate III, then 37% formalin, 60-80 is added portionwise DEG C reaction 2-4h, obtain reaction intermediate IV；
(5) reaction intermediate II is added portionwise in reaction intermediate IV, 60-80 DEG C of reaction 2-4h, that is, obtained wooden The more amine quaternary ammonium salt cationic type asphalt emulsifiers of element；
As long as not influenceing to prepare, above step is interchangeable.
The above-mentioned more amine quaternary ammonium salt cationic type asphalt emulsifiers of lignin split type and slow breaking cationic galactomannan soon in preparation Change the application in pitch.
A kind of preparation method of cationic emulsified bitumen, comprises the following steps：The dosage of asphalt emulsifier is the breast prepared Change the 1.0-3.0% of pitch gross mass, add water to be configured to the more amine quaternary ammonium salt cationic type asphalt emulsifiers of above-mentioned lignin The aqueous solution, with salt acid for adjusting pH value to 2-3,60-70 DEG C is heated to, soap lye is made；By the pitch after heating and emulsifying agent soap lye Cationic emulsified bitumen is prepared by colloid mill emulsification.
The cationic emulsified bitumen that above-mentioned preparation method is prepared.
The present invention is using acrylic acid as the reaction raw materials of asphalt emulsifier, by adding in the molecular structure of asphalt emulsifier Enter acrylic acid and introduce carboxylic acid group, add the hydrophily of asphalt emulsifier, and the compatibility of emulsifying agent and pitch.In addition, Carbon chain lengths are considered for the HLB value (hydrophilic/lipophilic balance value) of asphalt emulsifier and CMC (critical micelle concentration) shadow Ring, select the raw material using lignin, TEPA, epoxychloropropane and low carbon number tertiary amine as reaction, make the pitch of preparation The HLB value of emulsifying agent improves the emulsifiability to pitch within optimum range.
Beneficial effects of the present invention are：
(1) the raw material wood element of the more amine quaternary ammonium salt cationic type asphalt emulsifiers of lignin of the invention is relative to current Cationic asphalt emulsifier used in raw material is cheap, wide material sources, asphalt emulsifier production cost is low.
(2) the preparation method technique of the more amine quaternary ammonium salt cationic type asphalt emulsifiers of lignin of the invention is simple, no Need pyroreaction.
(3) the more emulsifiable a variety of different models of amine quaternary ammonium salt cationic type asphalt emulsifier of lignin prepared by the present invention Pitch, the emulsified asphalt of preparation is fine and smooth uniformly, and storage stability is good, dilute suitable for the spread of highway priming oil or sticking layer oil Sealing construction is starched, and for crushed stone sealing, screening seal coat, mist sealing and repairs slight check crack in road surface etc., has and splits soon and slowly Split the characteristic of type asphalt emulsifier.Obtained emulsified asphalt properties can meet that Chinese transportation portion works out cation emulsified Design asphalt (JTJ052-2000).
(4) made in raw material of the invention by adding acrylic acid, TEPA, low carbon number tertiary amine and epoxychloropropane The asphalt emulsification agent molecule that must be prepared has more amine quaternary ammonium salt cationic type chemical constitutions, enhances asphalt emulsification agent molecule Charge density, improve the hydrophily of asphalt emulsification agent molecule.The emulsifiability of asphalt emulsifier is so not only increased, and Improve the performance of emulsified asphalt.
Because the ionization of the more amine quaternary ammonium salt cationic type asphalt emulsifiers of lignin of the present invention is stronger, increasing Add the hydrophilic at the same time it can also make interfacial film carry corresponding more positive charge of asphalt emulsifier, occur one layer Interface charge, thus there is interface charge layer.The formation of interface charge layer protects them by making bitumen particle mutually exclusive Certain distance is held, so as to allow pitch particle to maintain dispersity, peptizaiton is served to asphalt emulsion.Interface charge layer goes out Existing, the homogeneous stability system that is scattered, keeping asphalt emulsion of emulsification, pitch in aqueous phase for pitch has vital Effect.Due to the present invention emulsifying agent in water it is ionizable compared with polycation, so the effect of interface charge layer is stronger so that Its system is more stable after the emulsifier pitch of the present invention.
Embodiment
Below by instantiation, the present invention will be further elaborated, it should explanation, the description below be only for The present invention is explained, its content is not defined.
Used raw material, reagent are conventional chemical products in the embodiment of the present invention, can be purchased by commercial channel It can buy.
Embodiment 1
(1) preparation of the more amine quaternary ammonium salt cationic type asphalt emulsifiers of lignin：
1) 189.3g TEPAs are added in the reactor, then dropwise addition 72.1g acrylic acid, 45 DEG C of stirring reaction 1h, Obtain reaction intermediate I.
2) 193.1g 33% (mass fraction) trimethylamine aqueous solution is added in another reactor, is gradually added into 131.2g 30% (mass fraction) technical hydrochloric acid, then 97.1g epoxychloropropane is gradually added into, 45 DEG C of stirring reaction 2h, obtain among reaction Body II.
3) in another reactor by 283.0g lignin dissolutions in 649.6g 10.7% (mass fraction) sodium hydroxide water In solution, reaction is mixed, obtains reaction intermediate III.
4) reaction intermediate I is added in reaction intermediate III, then is gradually added into 92.5g 37% (mass fraction) first Aldehyde, 70 DEG C of reaction 3h, obtains reaction intermediate IV；
5) reaction intermediate II is added gradually in reaction intermediate IV, 70 DEG C of reaction 3h.Obtain lignin polyamines Class quaternary ammonium salt cationic type asphalt emulsifier, give over to emulsified asphalt experiment.
The more amine quaternary ammonium salt cationic type asphalt emulsifiers of the lignin of preparation are subjected to FTIR detections after separating-purifying, As a result it is as follows：3275-3540cm-1Superposition peak, 2943cm are absorbed for O-H stretching vibrations and N-H stretching vibrations-1It is non-for methylene Symmetrical stretching vibration absworption peak, 2841cm-1For methylene symmetrical stretching vibration absworption peak, 1647cm-1For N-H flexural vibrations and C=O stretching vibration absworption peaks in carboxylate, 1580cm-1And 1473cm-1For the skeletal vibration absworption peak of phenyl ring, 1418cm-1With 1312cm-1For O-H in-plane bending vibration absworption peaks, 1132cm-1For C-H in-plane bending vibrations, 1039cm-1Stretched for Ar-O-C Vibration absorption peak, 623cm-1For O-H out-of-plane bending vibration absworption peaks.
Reaction equation is as follows：
NH2C2H4NHC2H4NHC2H4NHC2H4NH2+CH2=CHCOOH →
NH2C2H4NHC2H4NHC2H4NHC2H4NHCH2CH2COOH (1)
(2) preparation of emulsified asphalt：
AH-90# pitch 300g are taken, are heated to 125 DEG C, 12.5g asphalt emulsifiers manufactured in the present embodiment are added to In 200g water, with 30% Nacl acid for adjusting pH value to 2-3,65 DEG C are heated to, soap lye is made.By pitch and emulsifying agent soap lye Cationic emulsified asphalt is prepared by colloid mill emulsification.
(3) emulsified asphalt performance detection：
The cationic emulsified bitumen standard (JTJ052-2000) that obtained emulsified asphalt is worked out by Chinese transportation portion is examined Survey, it is as a result as follows：Emulsified asphalt manufactured in the present embodiment is uniform, fine and smooth, bitumen content 57%, and surplus is on sieve 0.03%, area is wrapped more than 2/3 with mineral aggregate, and storage stability (1d) is 0.5%；Mixed and stirred, can be mixed and stirred using material is mixed and stirred Time is 8 seconds.Show that asphalt emulsion prepared by the emulsifying agent is to split type cationic emulsified bitumen soon, properties can meet The requirement of JTJ052-2000 standards.
Embodiment 2
(1) preparation of the more amine quaternary ammonium salt cationic type asphalt emulsifiers of lignin：
1) 189.3g TEPAs are added in the reactor, then dropwise addition 72.1g acrylic acid, 45 DEG C of stirring reaction 1h, Obtain reaction intermediate I.
2) 109.1g triethylamines are added in another reactor, are gradually added into 131.2g 30% (mass fraction) Nacl Acid, then 97.1g epoxychloropropane is gradually added into, 45 DEG C of stirring reaction 2h, obtain reaction intermediate II.
3) in another reactor by 283.0g lignin dissolutions in 649.6g 10.7% (mass fraction) sodium hydroxide water In solution, reaction is mixed, obtains reaction intermediate III.
4) reaction intermediate I is added in reaction intermediate III, then is gradually added into 92.5g 37% (mass fraction) first Aldehyde, 60 DEG C of reaction 4h, obtains reaction intermediate IV；
5) reaction intermediate II is added gradually in reaction intermediate IV, 80 DEG C of reaction 2h.Obtain lignin polyamines Class quaternary ammonium salt cationic type asphalt emulsifier, give over to emulsified asphalt experiment.
The more amine quaternary ammonium salt cationic type asphalt emulsifiers of the lignin of preparation are subjected to FTIR detections after separating-purifying, As a result it is as follows：3260-3500cm-1Superposition peak, 2941cm are absorbed for O-H stretching vibrations and N-H stretching vibrations-1It is non-for methylene Symmetrical stretching vibration absworption peak, 2839cm-1For methylene symmetrical stretching vibration absworption peak, 1639cm-1For N-H flexural vibrations and C=O stretching vibration absworption peaks in carboxylate, 1574cm-1And 1464cm-1For the skeletal vibration absworption peak of phenyl ring, 1406cm-1With 1306cm-1For O-H in-plane bending vibration absworption peaks, 1124cm-1For C-H in-plane bending vibration absworption peaks, 1096cm-1Stretched for C-O Contracting vibration absorption peak, 1038cm-1For Ar-O-C stretching vibration absworption peaks, 770cm-1Hydrogen out-of-plane bending to be isolated on phenyl ring shakes Dynamic absworption peak, 627cm-1For O-H out-of-plane bending vibration absworption peaks.
Reaction equation is as follows：
NH2C2H4NHC2H4NHC2H4NHC2H4NH2+CH2=CHCOOH →
NH2C2H4NHC2H4NHC2H4NHC2H4NHCH2CH2COOH (1)
(2) preparation of emulsified asphalt：
AH-70# pitch 300g are taken, are heated to 125 DEG C, 12.5g asphalt emulsifiers manufactured in the present embodiment are added to In 200g water, with 30% Nacl acid for adjusting pH value to 2-3,65 DEG C are heated to, soap lye is made.By pitch and emulsifying agent soap lye Cationic emulsified asphalt is prepared by colloid mill emulsification.
(3) emulsified asphalt performance detection：
Detection method is with embodiment 1, testing result：Emulsified asphalt is uniform, fine and smooth, bitumen content 58%, is remained on sieve Surplus is 0.03%, wraps area more than 2/3 with mineral aggregate, storage stability (1d) is 0.4%；Mixed and stirred using material is mixed and stirred, It can be more than 2 minutes the mixing time.Show that asphalt emulsion prepared by the emulsifying agent coagulates type cationic emulsified bitumen soon for slow split, it is every Performance can meet the requirement of JTJ052-2000 standards.
Embodiment 3
(1) preparation of the more amine quaternary ammonium salt cationic type asphalt emulsifiers of lignin：
1) 189.3g TEPAs are added in the reactor, then dropwise addition 72.1g acrylic acid, 45 DEG C of stirring reaction 1h, Obtain reaction intermediate I.
2) 189.6g 85% (mass fraction) triethanolamine aqueous solution is added in another reactor, is gradually added into 131.2g 30% technical hydrochloric acid, then 97.1g epoxychloropropane is gradually added into, 45 DEG C of stirring reaction 2h, obtain reaction intermediate II。
3) in another reactor by 283.0g lignin dissolutions in 649.6g 10.7% (mass fraction) sodium hydroxide water In solution, reaction is mixed, obtains reaction intermediate III.
4) reaction intermediate I is added in reaction intermediate III, then is gradually added into 92.5g 37% (mass fraction) first Aldehyde, 80 DEG C of reaction 2h, obtains reaction intermediate IV；
5) reaction intermediate II is added gradually in reaction intermediate IV, 60 DEG C of reaction 4h.Obtain lignin polyamines Class quaternary ammonium salt cationic type asphalt emulsifier, give over to emulsified asphalt experiment.
The more amine quaternary ammonium salt cationic type asphalt emulsifiers of the lignin of preparation are subjected to FTIR detections after separating-purifying, As a result it is as follows：3270-3545cm-1Superposition peak, 2945cm are absorbed for O-H stretching vibrations and N-H stretching vibrations-1It is non-for methylene Symmetrical stretching vibration absworption peak, 2833cm-1For methylene symmetrical stretching vibration absworption peak, 1649cm-1For N-H flexural vibrations and C=O stretching vibration absworption peaks in carboxylate, 1577cm-1And 1465cm-1For the skeletal vibration absworption peak of phenyl ring, 1394cm-1With 1317cm-1For O-H in-plane bending vibration absworption peaks, 1117cm-1For C-H in-plane bending vibration absworption peaks, 1070cm-1Stretched for C-O Contracting vibration absorption peak, 1030cm-1For Ar-O-C stretching vibration absworption peaks, 880cm-1Hydrogen out-of-plane bending to be isolated on phenyl ring shakes Dynamic absworption peak, 632cm-1For O-H out-of-plane bending vibration absworption peaks.
Reaction equation is as follows：
NH2C2H4NHC2H4NHC2H4NHC2H4NH2+CH2=CHCOOH →
NH2C2H4NHC2H4NHC2H4NHC2H4NHCH2CH2COOH (1)
(2) preparation of emulsified asphalt：
A-100# pitch 300g are taken, are heated to 125 DEG C, 12.5g asphalt emulsifiers manufactured in the present embodiment are added to In 200g water, with 30% Nacl acid for adjusting pH value to 2-3,65 DEG C are heated to, soap lye is made.By pitch and emulsifying agent soap lye Cationic emulsified asphalt is prepared by colloid mill emulsification.
(3) emulsified asphalt performance detection：
Detection method is with embodiment 1, testing result：Emulsified asphalt is uniform, fine and smooth, bitumen content 57%, is remained on sieve Surplus is 0.01%, wraps area more than 2/3 with mineral aggregate, storage stability (1d) is 0.6%；Mixed and stirred using material is mixed and stirred, It can be more than 2 minutes the mixing time.Show that asphalt emulsion prepared by the emulsifying agent coagulates type cationic emulsified bitumen soon for slow split, it is every Performance can meet the requirement of JTJ052-2000 standards.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment Limitation, one of ordinary skill in the art should be understood that on the basis of technical scheme those skilled in the art need not Various modifications or deformation that creative work can make are paid still within protection scope of the present invention.

Claims (10)

  1. A kind of 1. more amine quaternary ammonium salt cationic type asphalt emulsifiers of lignin, it is characterised in that：Its general formula of molecular structure is：
    Wherein, R is methyl, ethyl or ethoxy；LIGNIN represents lignin molecule chain.
  2. A kind of 2. preparation method of the more amine quaternary ammonium salt cationic type asphalt emulsifiers of lignin, it is characterised in that：Including as follows Step：
    1) by TEPA and acrylic acid hybrid reaction, reaction intermediate I is obtained, intermediate compound I is
    NH2C2H4NHC2H4NHC2H4NHC2H4NHCH2CH2COOH；
    2) low carbon number tertiary amine, technical hydrochloric acid and epoxychloropropane are mixed, reaction, obtains reaction intermediate II, low carbon number tertiary amine For trimethylamine, triethylamine or triethanolamine, intermediate II isR is methyl, ethyl or hydroxyl Ethyl；
    3) by lignin and sodium hydrate aqueous solution hybrid reaction, reaction intermediate III is obtained；
    4) reaction intermediate I is added in reaction intermediate III, then formalin is added dropwise, reacted, obtain reaction intermediate IV, intermediate compound IV are
    5) reaction intermediate II is added drop-wise in reaction intermediate IV, reacts, that is, obtain the more amine quaternary ammonium salt cationics of lignin Type asphalt emulsifier；
    As long as above step does not influence to prepare, interchangeable.
  3. 3. preparation method according to claim 2, it is characterised in that：The raw material that uses and raw material proportioning for：Lignin, Water, sodium hydroxide, TEPA, acrylic acid, 37% formalin, 33% trimethylamine aqueous solution, 30% Nacl The mass ratio of acid and epoxychloropropane is 100：(159-230)：(19-27)：(61-73)：(23-29)：(30-36)：(63- 74)：(42-50)：(31-37).
  4. 4. preparation method according to claim 2, it is characterised in that：The raw material that uses and raw material proportioning for：Lignin, Water, sodium hydroxide, TEPA, acrylic acid, 37% formalin, triethylamine, 30% technical hydrochloric acid and epoxy chlorine The mass ratio of propane is 100：(159-230)：(19-27)：(61-73)：(23-29)：(30-36)：(35-43)：(42-50)： (31-37)。
  5. 5. preparation method according to claim 2, it is characterised in that：The raw material that uses and raw material proportioning for：Lignin, Water, sodium hydroxide, TEPA, acrylic acid, 37% formalin, 85% triethanolamine, 30% technical hydrochloric acid with And the mass ratio of epoxychloropropane is 100：(159-230)：(19-27)：(61-73)：(23-29)：(30-36)：(53-82)： (42-50)：(31-37).
  6. 6. preparation method according to claim 2, it is characterised in that：Described lignin is alkali lignin.
  7. 7. the preparation method of the more amine quaternary ammonium salt cationic type asphalt emulsifiers of lignin described in claim 2, it is characterised in that： Specifically comprise the following steps：
    (1) TEPA is added in reaction vessel, then acrylic acid is added portionwise, after acrylic acid adds, in 30-60 DEG C stirring reaction 0.5-2h, obtains reaction intermediate I；
    (2) low carbon number tertiary amine is added in second reactor, technical hydrochloric acid is added portionwise, after technical hydrochloric acid adds, then divides 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 added in reaction intermediate III, then 37% formalin is added portionwise, 60-80 DEG C anti- 2-4h is answered, obtains reaction intermediate IV；
    (5) reaction intermediate II is added portionwise in reaction intermediate IV, 60-80 DEG C of reaction 2-4h, that is, it is more obtains lignin Amine quaternary ammonium salt cationic type asphalt emulsifier；
    As long as not influenceing to prepare, above step is interchangeable.
  8. 8. the more amine quaternary ammonium salt cationic type asphalt emulsifiers of lignin described in claim 1 split type and slow breaking sun soon in preparation Application in ion emulsified asphalt.
  9. A kind of 9. preparation method of cationic emulsified bitumen, it is characterised in that：Comprise the following steps：Drip described in claim 1 The dosage of blue or green emulsifying agent is the 1.0-3.0% of the emulsified asphalt gross mass prepared, adds water to be configured to water above-mentioned asphalt emulsifier Solution, with salt acid for adjusting pH value to 2-3,60-70 DEG C is heated to, soap lye is made；Pitch after heating and emulsifying agent soap lye are led to Cross colloid mill emulsification and prepare cationic emulsified bitumen.
  10. 10. the cationic emulsified bitumen that the preparation method described in claim 9 is prepared.
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CN108467495A (en) * 2018-05-15 2018-08-31 苏州太星新材料科技有限公司 A kind of lignin quaternary ammonium salt cation asphalt emulsifier and preparation method thereof
CN108485293A (en) * 2018-05-15 2018-09-04 苏州太星新材料科技有限公司 A kind of fibrination ethers quaternary ammonium salt cation asphalt emulsifier and preparation method thereof
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
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CN117430827B (en) * 2023-12-20 2024-02-23 德州坤鸿化工有限公司 High-performance cold-recycling asphalt emulsifier and preparation method thereof

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