CN105968382B - A kind of more amine cations of lignin split type asphalt emulsifier and preparation method thereof soon - Google Patents
A kind of more amine cations of lignin split type asphalt emulsifier and preparation method thereof soon Download PDFInfo
- Publication number
- CN105968382B CN105968382B CN201610459555.1A CN201610459555A CN105968382B CN 105968382 B CN105968382 B CN 105968382B CN 201610459555 A CN201610459555 A CN 201610459555A CN 105968382 B CN105968382 B CN 105968382B
- Authority
- CN
- China
- Prior art keywords
- lignin
- reaction
- soon
- preparation
- 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.)
- Expired - Fee Related
Links
- 0 C*c(cc1*)cc(*I)c1O Chemical compound C*c(cc1*)cc(*I)c1O 0.000 description 1
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
Abstract
The invention discloses a kind of more amine cations of lignin to split type asphalt emulsifier and preparation method and application soon, and its general formula of molecular structure is：Wherein, R is methyl (CH3), ethyl (C2H5) or ethoxy (C2H4OH)；LIGNIN represents lignin molecule chain.It is to be prepared by the raw material of following quality proportioning：Lignin：Water：Sodium hydroxide：Diethylenetriamine：Acrylic acid：Formaldehyde (37%)：Low carbon number tertiary amine：Technical hydrochloric acid (30%)：Epoxychloropropane=100：(159‑230)：(19‑27)：(32‑40)：(23‑29)：(30‑36)：(35‑82)：(42‑50)：(31‑37).The synthesis material that the more amine cations of lignin of the present invention split type asphalt emulsifier soon is easy to get, production cost is low, technique is simple, does not need pyroreaction.The pitch of emulsifiable a variety of different models, the emulsified asphalt of preparation is fine and smooth uniformly, and storage stability is good, can prepare and split type cationic emulsified asphalt soon.
Description
Technical field
The present invention relates to a kind of more amine cations of lignin to split type asphalt emulsifier and preparation method thereof soon, belongs to fine
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, it is strong with building stones adhesion, 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.The shortcomings that this method is to need pyroreaction when preparing.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 cations of lignin to split type pitch breast soon
Agent and preparation method thereof.Raw material sources needed for the preparation method are extensive, and production cost is low, and preparation technology is simple, without high temperature
Reaction.The asphalt emulsifier function admirable being prepared, the pitch of emulsifiable a variety of different models, the emulsified asphalt of preparation are fine and smooth
Uniformly, storage stability is good.
To achieve the above object, the present invention uses following technical proposals：
A kind of more 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.
A kind of more amine cations of lignin split the preparation method of type asphalt emulsifier soon, comprise the following steps：
1) by diethylenetriamine and acrylic acid hybrid reaction, reaction intermediate I is obtained, intermediate compound I is
NH2C2H4NHC2H4NHCH2CH2COOH；
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, reacts, that is, it is fast to obtain the more amine cations of lignin
Split type asphalt emulsifier；
As long as above step does not influence to prepare, interchangeable.
Preferably, the concentration of the formalin is 37%, and trimethylamine uses concentration as 33% trimethylamine aqueous solution, work
The concentration of industry hydrochloric acid be 30%, triethanolamine use concentration for 85% the triethanolamine aqueous solution.
Preferably, the raw material that uses and raw material proportioning for, lignin, water, sodium hydroxide, diethylenetriamine, acrylic acid,
37% formalin, 33% trimethylamine aqueous solution, the mass ratio of 30% technical hydrochloric acid and epoxychloropropane are 100：
(159-230)：(19-27)：(32-40)：(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, diethylenetriamine, acrylic acid,
37% formalin, triethylamine, the mass ratio of 30% technical hydrochloric acid and epoxychloropropane are 100：(159-230)：
(19-27)：(32-40)：(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, diethylenetriamine, acrylic acid,
37% formalin, the 85% triethanolamine aqueous solution, the mass ratio of 30% technical hydrochloric acid and epoxychloropropane are
100：(159-230)：(19-27)：(32-40)：(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.
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 above-mentioned more amine cations of lignin split the preparation method of type asphalt emulsifier soon, specifically comprise the following steps：
(1) diethylenetriamine 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 cations of element split type asphalt emulsifier soon；
As long as not influenceing to prepare, above step is interchangeable.
The above-mentioned more amine cations of lignin split type asphalt emulsifier in type cationic emulsified bitumen is split in preparation soon soon
Using.
A kind of preparation method for splitting type cationic emulsified bitumen soon, comprises the following steps：The dosage of asphalt emulsifier is system
The 1.0-3.0% of standby emulsified asphalt gross mass, the more amine cations of above-mentioned lignin are split into type asphalt emulsifier soon and add water to match somebody with somebody
The aqueous solution is made, with salt acid for adjusting pH value to 2-3, is heated to 60-70 DEG C, soap lye is made；By the pitch and emulsifying agent after heating
Soap lye is prepared by colloid mill emulsification splits type cationic emulsified bitumen soon.
What described preparation method was prepared splits type cationic emulsified bitumen soon.
A kind of more amine sun of lignin of brand new have been prepared by the reasonable selection to reaction raw materials in the present invention
Ion splits type asphalt emulsifier soon.Wherein, the present invention is using acrylic acid as the reaction raw materials of asphalt emulsifier, in asphalt emulsifier
Molecular structure in by adding acrylic acid introduce carboxylic acid group, add the hydrophily of asphalt emulsifier, and emulsifying agent with
The compatibility of pitch.In addition, consider HLB value (hydrophilic/lipophilic balance value) and CMC of the carbon chain lengths for asphalt emulsifier
The influence of (critical micelle concentration), select to be used as reaction using lignin, diethylenetriamine, epoxychloropropane and low carbon number tertiary amine
Raw material, the HLB value of asphalt emulsifier of preparation is set to improve the emulsifiability to pitch within optimum range.
Beneficial effects of the present invention：
(1) the more amine cations of lignin of the invention split the raw material wood element of type asphalt emulsifier relative to current soon
Raw material used in cationic asphalt emulsifier is cheap, wide material sources, and asphalt emulsifier production cost is low.
(2) the more amine cations of lignin of the invention split soon type asphalt emulsifier preparation method technique it is simple, be not required to
Want pyroreaction.
(3) the more amine cations of lignin prepared by the present invention split the emulsifiable a variety of different models of type asphalt emulsifier soon
Pitch, the emulsified asphalt of preparation is fine and smooth uniform, and storage stability is good, suitable for the spread of highway priming oil or sticking layer oil, and
For crushed stone sealing, screening seal coat, mist sealing and slight check crack in road surface etc. is repaired, there is the characteristic for splitting type asphalt emulsifier soon.
Obtained emulsified asphalt properties can meet the cationic emulsified bitumen standard (JTJ052- that Chinese transportation portion works out
2000)。
(4) made in raw material of the invention by adding acrylic acid, diethylenetriamine, low carbon number tertiary amine and epoxychloropropane
The asphalt emulsification agent molecule that must be prepared has more amine cation type chemical constitutions, and the electric charge for enhancing asphalt emulsification agent molecule is strong
Degree, improve the hydrophily of asphalt emulsification agent molecule.The emulsifiability of asphalt emulsifier is so not only increased, and is improved
The performance of emulsified asphalt.
It is stronger to split the ionization of type asphalt emulsifier soon due to the more amine cations of lignin of the present invention, is increasing
Asphalt emulsifier it is hydrophilic at the same time it can also make interfacial film carry corresponding more positive charge, there is a stratum boundary
Surface charge, thus there is interface charge layer.The formation of interface charge layer keeps them by making bitumen particle mutually exclusive
Certain distance, 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) the more amine cations of lignin split the preparation of type asphalt emulsifier soon：
1) 103.2g diethylenetriamines 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
Cationoid splits type asphalt emulsifier soon, gives over to emulsified asphalt experiment.
The more amine cations of the lignin of preparation are split into type asphalt emulsifier soon FTIR detections are carried out after separating-purifying, tied
Fruit is as follows：3320-3516cm-1Superposition peak, 2970cm are absorbed for O-H stretching vibrations and N-H stretching vibrations-1It is non-right for methylene
Claim stretching vibration absworption peak, 2835cm-1For methylene symmetrical stretching vibration absworption peak, 1635cm-1For N-H flexural vibrations and carboxylic
C=O stretching vibration absworption peaks in hydrochlorate, 1574cm-1And 1464cm-1For the skeletal vibration absworption peak of phenyl ring, 1410cm-1With
1323cm-1For O-H in-plane bending vibration absworption peaks, 1103cm-1For C-H in-plane bending vibration absworption peaks, 1037cm-1For Ar-O-
C stretching vibration absworption peaks, 960cm-1For the hydrogen out-of-plane bending vibration absworption peak isolated on phenyl ring, 611cm-1For O-H out-of-plane bendings
Vibration absorption peak.
Reaction equation is as follows：
NH2C2H4NHC2H4NH2+CH2=CHCOOH → NH2C2H4NHC2H4NHCH2CH2COOH (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, pH value is adjusted to 2-3 with technical hydrochloric acid, 65 DEG C is heated to, soap lye is made.Pitch and emulsifying agent soap lye are passed through into glue
Cationic emulsified asphalt is prepared in body 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 58%, and surplus is on sieve
0.03%, area is wrapped more than 2/3 with mineral aggregate, and storage stability (1d) is 0.6%；Mixed and stirred, can be mixed and stirred using material is mixed and stirred
Time is 4 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) the more amine cations of lignin split the preparation of type asphalt emulsifier soon：
1) 103.2g diethylenetriamines 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
Cationoid splits type asphalt emulsifier soon, gives over to emulsified asphalt experiment.
The more amine cations of the lignin of preparation are split into type asphalt emulsifier soon FTIR detections are carried out after separating-purifying, tied
Fruit is as follows：3245-3425cm-1Superposition peak, 2946cm are absorbed for O-H stretching vibrations and N-H stretching vibrations-1It is non-right for methylene
Claim stretching vibration absworption peak, 2833cm-1For methylene symmetrical stretching vibration absworption peak, 1639cm-1For N-H flexural vibrations and carboxylic
C=O stretching vibration absworption peaks in hydrochlorate, 1585cm-1And 1454cm-1For the skeletal vibration absworption peak of phenyl ring, 1407cm-1With
1306cm-1For O-H in-plane bending vibration absworption peaks, 1121cm-1For C-H in-plane bending vibration absworption peaks, 1096cm-1Stretched for C-O
Contracting vibration absorption peak, 1026cm-1For Ar-O-C stretching vibration absworption peaks, 789cm-1For C-H out-of-plane bending vibration absworption peaks,
623cm-1For O-H out-of-plane bending vibration absworption peaks.
Reaction equation is as follows：
NH2C2H4NHC2H4NH2+CH2=CHCOOH → NH2C2H4NHC2H4NHCH2CH2COOH (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, pH value is adjusted to 2-3 with technical hydrochloric acid, 65 DEG C is heated to, soap lye is made.Pitch and emulsifying agent soap lye are passed through into glue
Cationic emulsified asphalt is prepared in body mill emulsification.
(3) emulsified asphalt performance detection：
Detection method is with embodiment 1, testing result：Emulsified asphalt is uniform, fine and smooth, bitumen content 59%, is remained on sieve
Surplus is 0.04%, wraps area more than 2/3 with mineral aggregate, storage stability (1d) is 0.8%；Mixed and stirred using material is mixed and stirred,
Can it be 6 seconds the mixing time.Show that asphalt emulsion prepared by the emulsifying agent is to split type cationic emulsified bitumen, the equal energy of properties soon
Meet the requirement of JTJ052-2000 standards.
Embodiment 3
(1) the more amine cations of lignin split the preparation of type asphalt emulsifier soon：
1) 103.2g diethylenetriamines 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% (mass fraction) technical hydrochloric acid, then 97.1g epoxychloropropane is gradually added into, 45 DEG C of stirring reaction 2h, obtain anti-
Answer 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
Cationoid splits type asphalt emulsifier soon, gives over to emulsified asphalt experiment.
The more amine cations of the lignin of preparation are split into type asphalt emulsifier soon FTIR detections are carried out after separating-purifying, tied
Fruit is as follows：3242-3525cm-1Superposition peak, 2953cm are absorbed for O-H stretching vibrations and N-H stretching vibrations-1It is non-right for methylene
Claim stretching vibration absworption peak, 2833cm-1For methylene symmetrical stretching vibration absworption peak, 1649cm-1For N-H flexural vibrations and carboxylic
C=O stretching vibration absworption peaks in hydrochlorate, 1573cm-1And 1454cm-1For the skeletal vibration absworption peak of phenyl ring, 1398cm-1With
1309cm-1For O-H in-plane bending vibration absworption peaks, 1121cm-1For C-H in-plane bending vibration absworption peaks, 1065cm-1Stretched for C-O
Contracting vibration absorption peak, 1030cm-1For Ar-O-C stretching vibration absworption peaks, 925cm-1And 880cm-1For the hydrogen face isolated on phenyl ring
Outside sweep vibration absorption peak, 606cm-1For O-H out-of-plane bending vibration absworption peaks.
Reaction equation is as follows：
NH2C2H4NHC2H4NH2+CH2=CHCOOH → NH2C2H4NHC2H4NHCH2CH2COOH (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, pH value is adjusted to 2-3 with technical hydrochloric acid, 65 DEG C is heated to, soap lye is made.Pitch and emulsifying agent soap lye are passed through into glue
Cationic emulsified asphalt is prepared in body 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 0.01%, wraps area more than 2/3 with mineral aggregate, storage stability (1d) is 0.5%；Mixed and stirred using material is mixed and stirred,
Can it be 5 seconds the mixing time.Show that asphalt emulsion prepared by the emulsifying agent is to split type cationic emulsified bitumen, the equal energy of properties soon
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 more 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, ethyl or ethoxy；LIGNIN represents lignin molecule chain.
2. a kind of more amine cations of lignin split the preparation method of type asphalt emulsifier soon, it is characterised in that：Including following step
Suddenly：
1) by diethylenetriamine and acrylic acid hybrid reaction, reaction intermediate I, intermediate compound I NH are obtained2C2H4NHC2H4NHCH2CH2COOH；
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 cations of lignin and split type soon
Asphalt emulsifier；
As long as above step does not influence to prepare, interchangeable.
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, diethylenetriamine, acrylic acid, 37% formalin, 33% trimethylamine aqueous solution, 30% Nacl
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).
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, diethylenetriamine, acrylic acid, 37% formalin, triethylamine, 30% technical hydrochloric acid 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)。
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, diethylenetriamine, acrylic acid, 37% formalin, the 85% triethanolamine aqueous solution, 30% industry
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 any described preparation methods of claim 2-5, it is characterised in that：Described lignin is alkali lignin.
7. the more amine cations of lignin described in claim 2 split the preparation method of type asphalt emulsifier soon, it is characterised in that：Tool
Body comprises the following steps：
(1) diethylenetriamine 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 cation splits type asphalt emulsifier soon；
As long as not influenceing to prepare, above step is interchangeable.
8. the more amine cations of lignin described in claim 1 split type asphalt emulsifier and split the cation emulsified drip of type soon in preparation soon
Application in green grass or young crops.
A kind of 9. preparation method for splitting type cationic emulsified bitumen soon, it is characterised in that：Comprise the following steps：Claim 1 institute
The dosage for the asphalt emulsifier stated for prepare emulsified asphalt gross mass 1.0-3.0%, by the more amine sun of above-mentioned lignin from
Son splits type asphalt emulsifier and adds water to be configured to the aqueous solution soon, with salt acid for adjusting pH value to 2-3, is heated to 60-70 DEG C, and soap is made
Liquid；Pitch after heating and emulsifying agent soap lye are prepared by colloid mill emulsification and split type cationic emulsified bitumen soon.
What 10. the preparation method described in claim 9 was 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 CN105968382A (en) | 2016-09-28 |
| CN105968382B true 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) |
Families Citing this family (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 |
| 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 |
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 |
|---|
| "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";施来顺等;《石油沥青》;20140425;第28卷(第2期);第6-14页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105968382A (en) | 2016-09-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106008996B (en) | A kind of more amine cation type asphalt emulsifiers of lignin and preparation method and application | |
| 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 | |
| CN105399645B (en) | A kind of polycation acid amide 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 | |
| CN105384948B (en) | A kind of dication dual anion 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 | |
| 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 | |
| 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 | |
| CN106831478A (en) | Asphalt emulsifier of type or slow breaking and preparation method thereof is split in a kind of polycation teritary amide class | |
| 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 | |
| CN109456499B (en) | Amide bis-quaternary ammonium salt type sodium hydroxypropyl phosphate asphalt emulsifier and preparation method thereof | |
| CN109694481B (en) | Carboxylic acid bis-quaternary ammonium salt type sodium hydroxypropyl phosphate asphalt emulsifier and preparation method thereof | |
| CN106928470A (en) | A kind of teritary amide double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier and preparation method thereof | |
| CN108517040A (en) | A kind of cellulose family quaternary ammonium salt cation 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 | |
| CN106995393B (en) | A kind of double quaternary ammonium salt type hydroxypropyl azochlorosulfonate acid sodium asphalt emulsifier and preparation method thereof | |
| CN108586772A (en) | A kind of lignin polyether class quaternary ammonium salt cation asphalt emulsifier and preparation method thereof | |
| CN107880070B (en) | A kind of 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 |
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 |