CN106589407B - A kind of SBS modified pitch emulsifier and preparation method thereof and modified emulsifying asphalt product - Google Patents
A kind of SBS modified pitch emulsifier and preparation method thereof and modified emulsifying asphalt product Download PDFInfo
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- CN106589407B CN106589407B CN201611161197.2A CN201611161197A CN106589407B CN 106589407 B CN106589407 B CN 106589407B CN 201611161197 A CN201611161197 A CN 201611161197A CN 106589407 B CN106589407 B CN 106589407B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2395/00—Bituminous materials, e.g. asphalt, tar or pitch
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2453/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
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Abstract
The present invention provides a kind of SBS modified pitch emulsifiers, belong to modified pitch preparation field, it is prepared by the raw material for including following parts by weight: 20~30 parts of fatty acid, 20~30 parts of acrylic acid, 15~30 parts of aminated compounds, 5~10 parts of non-solvent alcohol compound, 5~15 parts of alkyl quaternary ammonium salts, 5~15 parts of alkyl amido betaine, by the way that a small amount of nonionic surface active agent: alkyl amido betaine, alkyl quaternary ammonium salts is added, the critical micelle concentration for adjusting emulsifier, enhances the storage stability of SBS modified emulsifying asphalt；By the mixing of fatty acid, alkyl amido betaine, alkyl quaternary ammonium salts different structure surfactant, the HLB value range of emulsifier is increased, improves emulsifier to the emulsifying capacity of various SBS modified pitch；The SBS modified emulsifying asphalt produced using this emulsifier all has great advantage to the compatibility of various building stones, mix flexibility and later period demulsification intensity, demulsification time.
Description
Technical field
The present invention relates to modified pitch preparation fields more particularly to a kind of modified pitch emulsifier and preparation method thereof.
Background technique
In recent years, domestic highway engineering cause rapidly develops, the micro-surface area preventive maintenance especially on high-grade highway
Means using more and more extensive, the technological merit and economic benefit of micro-surface area are gradually recognized and pay attention to.Micro-surface area makes
The modifying agent of modified emulsifying asphalt is mainly butadiene-styrene rubber modifying agent (SBR) and styrene-butadiene modifying agent (SBS).
With the fast development of China's expressway construction cause, the requirement of traffic and weather conditions to Expressway Pavement Performance
Also higher and higher.Currently, most of China's micro-surface area construction is the construction technology based on SBR modification, but since SBS is modified
The excellent application effect of pitch makes it be used widely in more and more emulsified asphalt construction technologies.
China's all parts of the country summer universal temperature is higher, harsher to the high-temperature stability requirement of micro-surface area, and SBS changes
Property micro-surfacing emulsified bitumen have good high-temperature stability, low-temperature cracking-resistance, higher cohesive force and adhesion strength, it is stronger
Rutting resistance is strong with the cohesive force of building stones；Anti-fatigue performance with higher simultaneously extends pavement life.And it limits at present
Can the matter of utmost importance of the modified micro-surface area application of SBS be exactly that produce qualified SBS modified emulsifying asphalt, and the cream produced
Can pitch be changed meet Emulsified Asphalt Mixture in " highway engineering pitch and Asphalt Mixture Experiment engineering " (JTJ052-2000)
Related request.The asphalt emulsifier produced in the prior art splits type in being mostly, as YJ-1 type asphalt emulsifier (" discusses YJ -1
In split succeeding in developing for type anionic asphalt emulsion ", Chen Qingyun etc., Guangxi transport science and techonologies, 1994 (2): 26-30), exist and stir
The demulsification time is short when mixing, and is not achieved and splits the poor problem of fast solidifying effect, emulsified asphalt storing stability slowly.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of SBS modified pitch emulsifier, for different modified drips
Blueness has good emulsifying effectiveness；In different construction seasons, gather materials for difference, splits fast coagulate slowly and work well.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of SBS modified pitch emulsifiers, are prepared by the raw material for including following parts by weight: fat
20~30 parts of acid, 20~30 parts of acrylic acid, 15~30 parts of aminated compounds, 5~10 parts of non-solvent alcohol compound, alkyl quaternary
5~15 parts of ammonium salt, 5~15 parts of alkyl amido betaine.
Preferably, the fatty acid includes the mixture of one or more of C12~C18 fatty acid.
Preferably, the aminated compounds includes triethylene tetramine, tetraethylenepentamine, polyethylene polyamine and aminoethyl piperazine
One or more of mixture.
Preferably, the alkyl quaternary ammonium salts includes the mixing of one or more of C12~C18 alkyl trimethyl ammonium chloride
Object.
Preferably, the alkyl amido betaine includes the mixed of one or more of C12~C18 alkyl amido betaine
Close object.
The present invention also provides the preparation methods of above-mentioned SBS modified pitch emulsifier, comprising the following steps:
(1) fatty acid, acrylic acid, aminated compounds and non-solvent alcohol compound are mixed, it is anti-that nucleophilic displacement of fluorine occurs
It answers, obtains nucleophilic displacement of fluorine product；
(2) the nucleophilic displacement of fluorine product that the step (1) obtains is mixed with alkyl quaternary ammonium salts, obtains complex；
(3) complex that the step (2) obtains is mixed with alkyl amido betaine, obtains the emulsification of SBS modified pitch
Agent.
Preferably, the mass ratio of the nucleophilic displacement of fluorine product, alkyl quaternary ammonium salts and alkyl amido betaine is 4~18:0.3
~3:1.
Preferably, the temperature of nucleophilic substitution is 100~220 DEG C in the step (1), the time of nucleophilic substitution
For 8~13h.
Preferably, the temperature mixed in the step (2) and step (3) is independently selected from 60~100 DEG C, the mixed time
Independently selected from 10~30min.
The present invention also provides a kind of modified emulsifying asphalt products, by above-mentioned SBS modified pitch emulsifier or above-mentioned preparation
The SBS modified pitch emulsifier that method obtains is modified to obtain to pitch.
The present invention provides a kind of SBS modified pitch emulsifiers, are prepared by the raw material for including following parts by weight: fat
20~30 parts of acid, 20~30 parts of acrylic acid, 15~30 parts of aminated compounds, 5~10 parts of non-solvent alcohol compound, alkyl quaternary
5~15 parts of ammonium salt, 5~15 parts of alkyl amido betaine.It is that a kind of slow solidifying type SBS fastly that splits of cation changes that the present invention, which provides emulsifier,
Property asphalt emulsifier, in the present invention, alkyl amido betaine and alkyl quaternary ammonium salts, can as nonionic surface active agent
The critical micelle concentration for adjusting emulsifier, enhances the storage stability of SBS modified emulsifying asphalt；The fatty acid and alkyl acyl
The mixing of amine glycine betaine, alkyl quaternary ammonium salts different structure surfactant increases the HLB value range of emulsifier, improves cream
Emulsifying capacity of the agent to various SBS modified pitch.
The SBS modified emulsifying asphalt produced using this emulsifier is to the compatibility of various building stones, mix is flexible and the later period
Demulsification intensity, demulsification time all have great advantage.
Specific embodiment
The present invention provides a kind of SBS modified pitch emulsifiers, are prepared by the raw material for including following parts by weight: fat
20~30 parts of acid, 20~30 parts of acrylic acid, 15~30 parts of aminated compounds, 5~10 parts of non-solvent alcohol compound, alkyl quaternary
5~15 parts of ammonium salt, 5~15 parts of alkyl amido betaine.
In the present invention, the SBS modified pitch emulsifier, preferably by including that the raw material of following parts by weight is prepared:
24~26 parts of fatty acid, 24~26 parts of acrylic acid, 20~25 parts of aminated compounds, 6~8 parts of non-solvent alcohol compound, alkane
8~12 parts of based quaternary ammonium salt, 8~12 parts of alkyl amido betaine.
In the present invention, the fatty acid preferably includes the mixture of one or more of C12~C18 fatty acid, more
The mixture of one or more of C14~C16 fatty acid is preferably comprised, more preferably ready denier oil acid and oleic acid is mixed
Close the mixture of object, ready denier oil acid and palmitinic acid.The present invention does not limit the mass ratio of each fatty acid in the mixture
System, those skilled in the art can select the mixture of the fatty acid of any mass ratio according to actual needs；In the embodiment of the present invention
The mass ratio of ready denier oil acid and oleic acid is preferably 20~70:30~80 in the mixture of middle ready denier oil acid and oleic acid,
More preferably 30~60:40~70, most preferably 40~50:50~60.
In the present invention, the aminated compounds preferably includes triethylene tetramine, tetraethylenepentamine, polyethylene polyamine and ammonia
The mixture of one or more of ethyl piperazidine, more preferably triethylene tetramine, tetraethylenepentamine, polyethylene polyamine and ammonia second
Two kinds of mixture in base piperazine, the most preferably mixture of triethylene tetramine and tetraethylenepentamine, triethylene tetramine and ammonia second
The mixture of base piperazine.There is no limit those skilled in the art for mass ratio of the present invention to each aminated compounds in the mixture
Member can select the mixture of the aminated compounds of any mass ratio according to actual needs；Triethylene tetramine in embodiments of the present invention
Independent with the mass ratio of tetraethylenepentamine, triethylene tetramine and aminoethyl piperazine is preferably 10~50:50~90, more preferably
20~40:60~80, most preferably 25~35:65~75.
In the present invention, the alkyl quaternary ammonium salts preferably includes one of C12~C18 alkyl trimethyl ammonium chloride or several
The mixture of kind, the more preferably mixture of one or more of C14~C16 alkyl trimethyl ammonium chloride, most preferably ten
The mixture of tetraalkyl trimethyl ammonium chloride and hexadecyltrimethylammonium chloride.The present invention is to each alkyl quaternary in the mixture
There is no limit those skilled in the art can select the alkyl quaternary ammonium salts of any mass ratio to the mass ratio of ammonium salt according to actual needs
Mixture；The mass ratio of tetradecyl trimethyl ammonium chloride and hexadecyltrimethylammonium chloride is preferred in embodiments of the present invention
For 20~70:30~80, more preferably 30~60:40~70, most preferably 40~50:50~60.
In the present invention, the alkyl amido betaine includes one or more of C12~C18 alkyl amido betaine
Mixture, the more preferably mixture of one or more of C14~C16 alkyl amido betaine, most preferably cocounut oil acyl
The mixture of amine glycine betaine and hexadecyl amide glycine betaine.Matter of the present invention to each alkyl amido betaine in the mixture
Amount is than there is no limit those skilled in the art can select the mixing of the alkyl amido betaine of any mass ratio according to actual needs
Object；The mass ratio of cocoamido betaine and hexadecyl amide glycine betaine is preferably 20~70:30 in embodiments of the present invention
~80, more preferably 30~60:40~70, most preferably 40~45:55~60.
In the present invention, the non-solvent alcohol compound preferably includes at least one of ethylene glycol and diethylene glycol,
The more preferably mixture of ethylene glycol and diethylene glycol.Matter of the present invention to non-solvent alcohol compound each in the mixture
Amount is than there is no limit those skilled in the art can select the non-solvent alcohol compound of any mass ratio according to actual needs
Mixture；The mass ratio of ethylene glycol and diethylene glycol is preferably 30~70:70~30 in embodiments of the present invention, and more preferably 40
~60:60~40, most preferably 40~50:50~60.
The present invention does not have any special restriction to the source of each raw material, using city well known to those skilled in the art
Sell commodity.
The present invention also provides the preparation methods of SBS modified pitch emulsifier described in above-mentioned technical proposal, including following step
It is rapid:
(1) fatty acid, acrylic acid, aminated compounds and non-solvent alcohol compound are mixed, it is anti-that nucleophilic displacement of fluorine occurs
It answers, obtains nucleophilic displacement of fluorine product；
(2) the nucleophilic displacement of fluorine product that the step (1) obtains is mixed with alkyl quaternary ammonium salts, obtains complex；
(3) complex that the step (2) obtains is mixed with alkyl amido betaine, obtains the emulsification of SBS modified pitch
Agent.
The present invention mixes fatty acid, acrylic acid, aminated compounds and non-solvent alcohol compound, and nucleophilic displacement of fluorine occurs
Reaction, obtains nucleophilic displacement of fluorine product.In the present invention, the temperature of the nucleophilic substitution is 100~220 DEG C, more preferably
140~200 DEG C, most preferably 160~180 DEG C, the time of the nucleophilic substitution is preferably 8~13h, more preferably 9~
12h, most preferably 10~11h.
In the present invention, suitable to the charging of the fatty acid, acrylic acid, aminated compounds and non-solvent alcohol compound
Sequence does not have any special restriction, using charging sequence well known to those skilled in the art.In embodiments of the present invention, excellent
Choosing uses following sequential feeds: being mixed to get mixed acid with acrylic acid after fatty acid is heated；The mixed acid is successively heated,
It is mixed after cooling treatment with aminated compounds, amidation process occurs and obtains amide product；After the amide product is cooling with it is non-
Solvent type alcohol compound is mixed to get nucleophilic displacement of fluorine product.
In the present invention, the heating temperature of the fatty acid is preferably 100~130 DEG C, and more preferably 105~120 DEG C, most
Preferably 110~115 DEG C；The heating time of the fatty acid is preferably 0.5~2h, more preferably 1~1.5h；
The heating temperature of the mixed acid is preferably 180~210 DEG C, and more preferably 190~205 DEG C, most preferably 195~
200℃；The heating time of the mixed acid is preferably 0.5~2h, more preferably 1~1.5h；
The cooling temperature of the mixed acid is preferably 100~120 DEG C, and more preferably 105~115 DEG C, most preferably 110~
112 DEG C, the present invention does not have any special restriction to the rate of the cooling, using cooling side well known to those skilled in the art
Formula, in embodiments of the present invention preferably by the way of natural cooling；
The temperature of the amidation process is preferably 160~200 DEG C, and more preferably 170~190 DEG C, most preferably 180~
185℃；The time of the amidation process is preferably 1~5h, more preferably 2~4h, most preferably 2.5~3h；
The amide product cooling temperature is preferably 80~110 DEG C, more preferably 85~100 DEG C, most preferably 90~95
℃；The present invention does not have any special restriction to the rate of the cooling, using the type of cooling well known to those skilled in the art
, in embodiments of the present invention preferably by the way of natural cooling.
After obtaining nucleophilic displacement of fluorine product, the present invention mixes nucleophilic displacement of fluorine product with alkyl quaternary ammonium salts, obtains complex.?
In the present invention, the mixed temperature is preferably 60~100 DEG C, more preferably 70~90 DEG C, most preferably 80~85 DEG C；It is described
The mixed time is preferably 10~30min.More preferably 15~25min, most preferably 20~22min；In the present invention, to institute
The mode for stating mixing does not have any special restriction, using hybrid mode well known to those skilled in the art, in the present invention
It is preferably mixed by the way of stirring in embodiment, the stirring is more preferably magnetic agitation；The stirring rate is preferably 200
~800rpm, more preferably 400~600rpm, most preferably 500~550rpm.
After obtaining complex, the present invention mixes complex with alkyl amido betaine, obtains the emulsification of SBS modified pitch
Agent.In the present invention, the mixed temperature is preferably 60~100 DEG C, more preferably 70~90 DEG C, most preferably 80~85
℃；The mixed time is preferably 10~30min.More preferably 15~25min, most preferably 20~22min；In the present invention
In, there is no any special restriction to the mixed mode, using hybrid mode well known to those skilled in the art,
It is preferably mixed by the way of stirring in the embodiment of the present invention, the stirring is more preferably magnetic agitation；The stirring rate is excellent
It is selected as 1000~1500rpm, more preferably 1200~1400rpm, most preferably 1300~1350rpm.
In the present invention, the mass ratio of the nucleophilic displacement of fluorine product, alkyl quaternary ammonium salts and alkyl amido betaine is preferably 4
~18:0.3~3:1, more preferably 5~15:0.5~2.5:1, most preferably 8~12:1~2:1.
The present invention also provides a kind of modified emulsifying asphalt products, by above-mentioned SBS modified pitch emulsifier or above-mentioned preparation
The SBS modified pitch emulsifier that method obtains is modified to obtain to pitch, and the modified bitumen product includes SBS modified pitch
The mass ratio of emulsifier and SBS modified pitch, the SBS modified pitch emulsifier and SBS modified pitch is preferably 1~10:
100, more preferably 1.5~6:100, most preferably 2~5:100.
In the present invention, the preparation method of the modified emulsifying asphalt product preferably includes following steps:
SBS modified pitch emulsion is mixed with water, obtains SBS modified pitch emulsion aqueous solution；
The pH value for adjusting the SBS modified pitch emulsion aqueous solution with hydrochloric acid solution obtains soap lye to 2~3；
The soap lye is mixed with SBS modified pitch, obtains modified emulsifying asphalt product.
In the present invention, the mass fraction of the SBS modified pitch emulsion aqueous solution is preferably 1~10%, and more preferably 2
~8%, most preferably 3~7%.
In the present invention, the mass concentration of the hydrochloric acid solution is preferably 30%.
In the present invention, the mass ratio of the SBS modified pitch emulsion and SBS modified pitch be preferably 37~40:60~
63；When the soap lye is mixed with SBS modified pitch, the temperature of the SBS modified pitch is preferably 140~160 DEG C, more preferably
150~155 DEG C, the temperature of the soap lye is preferably 60~70 DEG C；The mixing is preferably colloid mill shear-mixed, the colloid
Preferred the pre-heat treatment is ground, the temperature that is preheated to of the colloid mill is preferably 60~80 DEG C, and more preferably 65~75 DEG C.
In the present invention, there is no any special restriction to the source of the SBS modified pitch, using those skilled in the art
SBS modified bitumen product known to member.
The present invention provides a kind of SBS modified pitch emulsifiers, are prepared by the raw material for including following parts by weight: fat
20~30 parts of acid, 20~30 parts of acrylic acid, 15~30 parts of aminated compounds, 5~10 parts of non-solvent alcohol compound, alkyl quaternary
5~15 parts of ammonium salt, 5~15 parts of alkyl amido betaine.Emulsifier provided by the invention, which is that a kind of cation is slow, splits solidifying type SBS fastly
Modified pitch emulsifier, in the present invention, alkyl amido betaine and alkyl quaternary ammonium salts are as nonionic surface active agent, energy
The critical micelle concentration for enough adjusting emulsifier, enhances the storage stability of SBS modified emulsifying asphalt；The fatty acid and alkyl
The mixing of amide betaine, alkyl quaternary ammonium salts different structure surfactant increases the HLB value range of emulsifier, improves
Emulsifying capacity of the emulsifier to various SBS modified pitch.
The SBS modified emulsifying asphalt produced using this emulsifier is to the compatibility of various building stones, mix is flexible and the later period
Demulsification intensity, demulsification time all have great advantage.
A kind of SBS modified pitch emulsifier provided by the invention and preparation method thereof is carried out below with reference to embodiment detailed
Explanation, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
300g ready denier oil acid is added in polymeric kettle, stirs and is warming up to 120 DEG C, 300g propylene is added into kettle
Acid stirs and is warming up to 210 DEG C, and heat preservation 3.5 hours is cooled to 120 DEG C later, and 300g aminoethyl piperazine is added at 200 DEG C
Reaction 3 hours is heated to 220 DEG C until reaction is without distillate, is cooled to 100 DEG C, and 50g ethylene glycol is added, and reaction 0.5 is small
When, obtain nucleophilic displacement of fluorine product.
50g dodecyl trimethyl ammonium chloride is added in nucleophilic displacement of fluorine product, is stirred 0.5 hour under 200rpm,
Obtain complex.
150g cocoamido betaine is added into complex, stirs 10min under 1000rpm, obtains SBS modified pitch
Emulsifier.
It takes SBS modified pitch emulsifier 60g, the water 6000g of above-mentioned preparation to mix, with 30% salt acid for adjusting pH value to 2, adds
Heat obtains soap lye to 60 DEG C, and 400g soap lye and 600g are heated to 160 DEG C of SBS modified pitch in preheating as in 60 DEG C of colloid mills
It is uniformly mixed, obtains modified emulsifying asphalt product.
The performance of obtained modified emulsifying asphalt product is tested, is shown in Table 1.
The performance measurement result of 1 modified emulsifying asphalt product of table
According to the grading limit suggested in China " micro-surface area and Slurry Seal Technology guide ", test uses MS-3 type gradation
Standard tests modified bitumen product, as a result such as table 2.
Table 2 uses the performance measurement result of modified emulsifying asphalt product after MS-3 type gradation standard
| Detection project | Unit | Standard | Testing result | Test method |
| It can duration of mixing (30 DEG C) | s | ≥120 | >120 | ISSA TB 113 |
| It is demulsified the time | min | -- | 5 | T 0753-1993 |
Embodiment 2
200g oleic acid is added in polymeric kettle, stirs and is warming up to 100 DEG C, 200g acrylic acid is added into kettle, stirring is simultaneously
180 DEG C are warming up to, keeps the temperature 3.5 hours, is cooled to 100 DEG C later, 150g polyethylene polyamine is added and is reacted 3 hours at 160 DEG C,
220 DEG C are heated to until reaction is without distillate, is cooled to 100 DEG C, 100g diethylene glycol is added, reacts 0.5 hour, obtains
Nucleophilic displacement of fluorine product.
150g octadecyltrimethylammonium chloride is added in nucleophilic displacement of fluorine product, 10min is stirred under 800rpm, obtains
To complex.
50g octadecyl amide glycine betaine is added into complex, is stirred 0.5 hour under 1500rpm, obtains SBS and change
Property asphalt emulsifier.
It takes SBS modified pitch emulsifier 40g, the water 400g of above-mentioned preparation to mix, with 30% salt acid for adjusting pH value to 3, adds
Heat obtains soap lye to 70 DEG C, and 400g soap lye and 600g are heated to 140 DEG C of SBS modified pitch in preheating as in 80 DEG C of colloid mills
It is uniformly mixed, obtains modified emulsifying asphalt product.
The performance of obtained modified emulsifying asphalt product is tested, is shown in Table 3.
The performance measurement result of 3 modified emulsifying asphalt product of table
According to the grading limit suggested in China " micro-surface area and Slurry Seal Technology guide ", test uses MS-3 type gradation
Standard tests modified bitumen product, as a result such as table 4.
Table 4 uses the performance measurement result of modified emulsifying asphalt product after MS-3 type gradation standard
| Detection project | Unit | Standard | Testing result | Test method |
| It can duration of mixing (30 DEG C) | s | ≥120 | >120 | ISSA TB 113 |
| It is demulsified the time | min | -- | 4 | T 0753-1993 |
Embodiment 3
140g ready denier oil acid, 100g oleic acid are added in polymeric kettle, stirs and is warming up to 120 DEG C, be added into kettle
260g acrylic acid stirs and is warming up to 205 DEG C, keeps the temperature 3 hours, is cooled to 115 DEG C later, be added 100g aminoethyl piperazine,
150g triethylene tetramine reacts 2 hours at 190 DEG C, is heated to 230 DEG C until reaction is without distillate, is cooled to 90 DEG C,
40g ethylene glycol, 40g diethylene glycol is added, reacts 0.5 hour, obtains nucleophilic displacement of fluorine product.
80g tetradecyl trimethyl ammonium chloride is added in nucleophilic displacement of fluorine product, 15min is stirred under 600rpm, obtains
To complex.
120g laurylamide glycine betaine is added into complex, stirs 25min under 1400rpm, it is modified to obtain SBS
Asphalt emulsifier.
It takes SBS modified pitch emulsifier 36g, the water 375g of above-mentioned preparation to mix, with 30% salt acid for adjusting pH value to 2, adds
Heat obtains soap lye to 70 DEG C, and 370g soap lye and 630g are heated to 150 DEG C of SBS modified pitch in preheating as in 65 DEG C of colloid mills
It is uniformly mixed, obtains modified emulsifying asphalt product.
The performance of obtained modified emulsifying asphalt product is tested, is shown in Table 5.
The performance measurement result of 5 modified emulsifying asphalt product of table
According to the grading limit suggested in China " micro-surface area and Slurry Seal Technology guide ", test uses MS-3 type gradation
Standard tests modified bitumen product, as a result such as table 6.
Table 6 uses the performance measurement result of modified emulsifying asphalt product after MS-3 type gradation standard
| Detection project | Unit | Standard | Testing result | Test method |
| It can duration of mixing (30 DEG C) | s | ≥120 | >120 | ISSA TB 113 |
| It is demulsified the time | min | -- | 8 | T 0753-1993 |
Embodiment 4
80g ready denier oil acid, 180g oleic acid are added in polymeric kettle, stirs and is warming up to 110 DEG C, be added into kettle
240g acrylic acid stirs and is warming up to 195 DEG C, keeps the temperature 2.5 hours, is cooled to 110 DEG C later, be added 100g tetraethylenepentamine,
100g triethylene tetramine reacts 3 hours at 185 DEG C, is heated to 210 DEG C until reaction is without distillate, is cooled to 95 DEG C,
20g ethylene glycol, 50g diethylene glycol is added, reacts 1.5 hours, obtains nucleophilic displacement of fluorine product.
30g tetradecyl trimethyl ammonium chloride, 70g hexadecyltrimethylammonium chloride are added to nucleophilic displacement of fluorine product
In, 15min is stirred, complex is obtained.
40g cocoamido betaine, 80g hexadecyl amide glycine betaine are added into complex, stirs 25min, obtains
SBS modified pitch emulsifier.
It takes SBS modified pitch emulsifier 32g, the water 375g of above-mentioned preparation to mix, with 30% salt acid for adjusting pH value to 3, adds
Heat obtains soap lye to 60 DEG C, and 370g soap lye and 630g are heated to 155 DEG C of SBS modified pitch in preheating as in 75 DEG C of colloid mills
It is uniformly mixed, obtains modified emulsifying asphalt product.
The performance of obtained modified emulsifying asphalt product is tested, is shown in Table 7.
The performance measurement result of 7 modified bitumen product of table
According to the grading limit suggested in China " micro-surface area and Slurry Seal Technology guide ", test uses MS-3 type gradation
Standard tests modified bitumen product, as a result such as table 8.
Table 8 uses the performance measurement result of modified emulsifying asphalt product after MS-3 type gradation standard
| Detection project | Unit | Standard | Testing result | Test method |
| It can duration of mixing (30 DEG C) | s | ≥120 | >120 | ISSA TB 113 |
| It is demulsified the time | min | -- | 7 | T 0753-1993 |
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (6)
1. a kind of SBS modified pitch emulsifier, which is characterized in that be prepared for the raw material of following parts by weight: fatty acid 20~
30 parts, 20~30 parts of acrylic acid, 15~30 parts of aminated compounds, 5~10 parts of non-solvent alcohol compound, alkyl quaternary ammonium salts 5
~15 parts, 5~15 parts of alkyl amido betaine, the fatty acid includes the mixed of one or more of C12~C18 fatty acid
It closes；The aminated compounds includes one of triethylene tetramine, tetraethylenepentamine, polyethylene polyamine and aminoethyl piperazine or several
The mixture of kind；The alkyl quaternary ammonium salts includes the mixture of one or more of C12~C18 alkyl trimethyl ammonium chloride；
The alkyl amido betaine includes the mixture of one or more of C12~C18 alkyl amido betaine.
2. the preparation method of SBS modified pitch emulsifier described in claim 1, comprising the following steps:
(1) fatty acid, acrylic acid, aminated compounds and non-solvent alcohol compound are mixed, nucleophilic substitution occurs, obtains
To nucleophilic displacement of fluorine product；
(2) the nucleophilic displacement of fluorine product that the step (1) obtains is mixed with alkyl quaternary ammonium salts, obtains complex；
(3) complex that the step (2) obtains is mixed with alkyl amido betaine, obtains SBS modified pitch emulsifier.
3. preparation method according to claim 2, which is characterized in that the nucleophilic displacement of fluorine product, alkyl quaternary ammonium salts and alkane
The mass ratio of base amide betaine is 4~18:0.3~3:1.
4. preparation method according to claim 2, which is characterized in that the temperature of nucleophilic substitution in the step (1)
It is 100~220 DEG C, the time of nucleophilic substitution is 8~13h.
5. preparation method according to claim 2, which is characterized in that the temperature mixed in the step (2) and step (3)
Independently selected from 60~100 DEG C, the mixed time is independently selected from 10~30min.
6. a kind of modified emulsifying asphalt product, by SBS modified pitch emulsifier described in claim 1 or claim 2~5 times
The SBS modified pitch emulsifier that a preparation method obtains of anticipating is modified to obtain to SBS modified pitch.
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| CN106589407B (en) * | 2016-12-15 | 2019-05-10 | 天津康泽威科技有限公司 | A kind of SBS modified pitch emulsifier and preparation method thereof and modified emulsifying asphalt product |
| 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 |
| CN111320595B (en) * | 2019-01-15 | 2021-04-27 | 山东大学 | Secondary amide cyclic amine quaternary ammonium salt amphoteric asphalt emulsifier and preparation method thereof |
| CN110591399A (en) * | 2019-09-23 | 2019-12-20 | 黄河三角洲京博化工研究院有限公司 | Modified emulsified asphalt with high viscosity and high softening point and preparation method thereof |
| CN113698596B (en) * | 2021-09-03 | 2023-07-21 | 天津康泽威科技有限公司 | Cationic asphalt emulsifier, preparation method thereof and asphalt emulsion preparation method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101927139A (en) * | 2010-07-12 | 2010-12-29 | 孙安顺 | Self-emulsifier and use thereof in tertiary oil recovery |
| CN103666260A (en) * | 2013-09-12 | 2014-03-26 | 宁波镭纳涂层技术有限公司 | Color polymer modified emulsion asphalt-base waterproof paint and preparation method thereof |
| CN105330873A (en) * | 2015-12-14 | 2016-02-17 | 广东鑫大公路材料有限公司 | Novel slow-breaking and quick-setting asphalt emulsifier and preparation method thereof |
| CN106589407A (en) * | 2016-12-15 | 2017-04-26 | 天津康泽威科技有限公司 | SBS (Styrene Butadiene Styrene) modified asphalt emulsifier, preparation method thereof, and modified emulsified asphalt product |
-
2016
- 2016-12-15 CN CN201611161197.2A patent/CN106589407B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101927139A (en) * | 2010-07-12 | 2010-12-29 | 孙安顺 | Self-emulsifier and use thereof in tertiary oil recovery |
| CN103666260A (en) * | 2013-09-12 | 2014-03-26 | 宁波镭纳涂层技术有限公司 | Color polymer modified emulsion asphalt-base waterproof paint and preparation method thereof |
| CN105330873A (en) * | 2015-12-14 | 2016-02-17 | 广东鑫大公路材料有限公司 | Novel slow-breaking and quick-setting asphalt emulsifier and preparation method thereof |
| CN106589407A (en) * | 2016-12-15 | 2017-04-26 | 天津康泽威科技有限公司 | SBS (Styrene Butadiene Styrene) modified asphalt emulsifier, preparation method thereof, and modified emulsified asphalt product |
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