CN105837750A - Styrene-butadiene latex for road emulsified asphalt modification and preparation method thereof - Google Patents
Styrene-butadiene latex for road emulsified asphalt modification and preparation method thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/06—Butadiene
Abstract
The invention relates to styrene-butadiene latex for road emulsified asphalt modification and a preparation method thereof .The styrene-butadiene latex for road emulsified asphalt modification is specifically compound styrene-butadiene latex .The compound styrene-butadiene latex is composed of modified styrene-butadiene latex and a cross-linking agent .The modified styrene-butadiene latex is large-particle-size high-solid-content cation styrene-butadiene latex .The cross-linking agent is 40% KH-560 silane coupling agent water emulsion .The modified styrene-butadiene latex is prepared through the production process of emulsion polymerization, residue removal and agglomeration, ion type conversion and centrifugal concentration .The modified styrene-butadiene latex keeps original characteristics of styrene-butadiene latex for road emulsified asphalt modification, is matched with the cross-linking agent added in the modified emulsified asphalt preparation process, can achieve room-temperature cross-linking, prevents amine and polyamine cationic asphalt emulsification agent migration, obviously reduces rainwater soluble substances of a modified emulsified asphalt road surface, reduces environment water pollution, and prolongs the service life of the road surface.
Description
Technical field
The present invention relates to a kind of road emulsified asphalt modification styrene-butadiene latex and preparation method.
Background technology
Ended for the end of the year 2014, the total mileage of highway of China oneself through more than 435.6 ten thousand kilometers, wherein highway
Total kilometrage has reached 10.8 ten thousand kilometers, and the Jin Ci U.S. occupies the whole world second.Bituminous paving has well due to it
Making, the suitability, driving and maintenance so that bituminous paving is in the highway construction of each department
Being widely applied, in completed express highway pavement, asphaltic road-mix surface course accounts for more than 90%.
Along with the popularization and application of asphaltic road-mix surface course, and arriving along with the major part expressway surface maintenance time limit
Coming, the maintenance work of bituminous paving becomes big difficult point and a focus of China's transportation industry.
China successively introduced several effective road maintenance maintenance new technique in recent years, such as mist sealing, dilute
Slurry sealing, micro-surface area, cold renewal, crushed stone sealing etc., be the most no longer using single heated bitumen as aggregate
Binding agent, and be all to need the support that develops into emulsified asphalt technology, modified emulsifying asphalt can improve road surface
Flatness, the performance such as wear-resisting, waterproof, have that construction is fast, pavement quality is good, fuel consumption is few, engineering is made
The features such as valency is low, environmental pollution is little, labor intensity is low, construction seasons length.
As emulsified bitumen modifying agent, polymer modifiers be most widely used general, be also to study the most deep one
Class.At present, that commonly uses both at home and abroad is divided three classes: type thermoplastic resin, thermoplastic elastomer (TPE) class and rubber
Class.Styrene-butadiene latex belongs to rubber-like, can significantly improve the low-temperature cracking-resistance of basic asphalt.Because it is of a great variety,
Yield is big, cheap, has the preferable compatibility with Colophonium.By the concept of macromolecular design, synthesis tool
There is the styrene-butadiene latex of thermoplastic elastomer (TPE), again because being that liquid can be directly dispersing in Colophonium matrix, therefore becoming
Research direction for the outer asphalt modifier of Present Domestic.
Having studied discovery, at the emulsified asphalt breakdown of emulsion initial stage, precipitation is formed gel by the rubber particle of dispersion phase,
Asphalt system is changed into rubber continuous phase from Colophonium continuous phase, forms rubber network structure.Styrene-butadiene latex (SBR)
In rubber particles, play the effect of physical crosslinking point, latex particle size is the biggest, physical crosslinking point more close and firm,
Therefore by increasing styrene-butadiene latex particle diameter, the rubber increased in Colophonium can reach more preferable modified effect mutually.But
Latex particle size is excessive, and solubility to dispersion is deteriorated, also by steady for the storage that directly affects latex and modified emulsifying asphalt
It is qualitative, so by size controlling in certain distribution, product serviceability and product stability can be obtained
Balance.
SBR used by modified emulsifying asphalt is divided into cation, anion and nonionic, its cationic
There is breakdown of emulsion in the moment contacted with building stones in modified emulsifying asphalt, makes Colophonium be attached on stone surface securely,
Even if running into moistening building stones, also can quickly breakdown of emulsion, reach the strong bonded with building stones.No matter winter or
Rainy season construction, does not all interfere with construction quality, and can quickly open to traffic, be highly suitable for the maintenance on road surface
With repairing.
JTG F40-2004 specifies: should not be less than as the solid contents in the SBR latex of modifying agent
45%.The different preparation methoies of modified emulsifying asphalt, different to the requirement of active constituent content in latex, >=60%
Latex will be applicable to all of method of modifying, and large arch dam is more easy to obtain the more preferably Colophonium assurance to aggregate simultaneously
Power and adhesion strength.
So, as Emulsified Asphalt modifying agent, large arch dam (>=60%), big particle diameter (300～400nm),
Cationic styrene-butadiene latex is total development trend.
It addition, along with the increase of Emulsified Asphalt Mixture pavement life and the enhancing of people's environmental consciousness,
The environmental impact issues that emulsified asphalt road surface exists the most gradually manifests.
Emulsified asphalt is that Colophonium is added heat fusing, under mechanical agitation power, divides with tiny particulate form
Dissipate the emulsion oil-in-water formed in the aqueous solution containing emulsifying agent and auxiliary agent thereof.It is solidified on the Colophonium on road surface
Other all the components than water is present in wherein, expose bituminous paving in the environment by rainwater and
The long period of soaking of other current and washing away, residuing in the emulsifying agent within Colophonium can be flooded out, and by breast
Change insoluble polluter, such as " fragrance point " etc. of emulsifying the easiest in Colophonium, together enter environment, dirty
Dye soil and water body environment, make water quality deterioration, affect organism in water, make water body self-purification ability be obstructed；Additionally,
Due to the effect of emulsifying agent remaining in Colophonium, make part asphalt component with the loss of runoff water, Colophonium group
Proportion by subtraction changes, and is allowed to progressively lose caking property, causes bituminous paving to damage.So to emulsified asphalt road
The research that road extractum pollutes also will become the task of top priority with administering.
The emulsifying agent of emulsified asphalt has anion, cation, nonionic, amphion emulsifying agent.For road
Bitumen for road use emulsifying agent, compared with anionic emulsified bitumen, cationic emulsified bitumen and aggregate mix have well
Adhesiveness, and synthesis technique is relatively easy, and cost is relatively low, and raw material is easy to get, so application is more and more wider
General.
Cationic asphalt emulsifier mainly has quaternary ammonium salt, lignin amine, amide groups amine, alkyl many
Amine, imidazolines etc..China commonly uses and mainly has first three class at present, and wherein quaternary ammonium salt emulsifying agent belongs to
In splitting type emulsified asphalt soon, it is only applicable at adhesion coating spread and table construct.Lignin amine class belongs to slow breaking,
Amide groups many amines emulsifying agent, through structurally-modified prepare fast, in, split the emulsifying agents such as fast solidifying type slowly, can
It is suitable for different purposes.(NHR, R are H or alkane all to contain amido in all of amine and many amines emulsifying agent
Base) functional group, acidified rear formation cation base.If emulsified asphalt is after pavement construction, will remain in
Emulsifying agent in Colophonium, utilizes the amido in its molecular structure, be allowed to each other or between high polymer
Produce chemical crosslinking under room temperature, form polymer, it will reduce emulsifying agent amount of precipitation in rainwater, subtract
The light pollution to environment；Alleviate Colophonium Moisture Damage, improve the service life on road surface.
Currently without finding by styrene butadiene latex modified, control the asphalt emulsifier relevant report in road surface amount of precipitation
Road.
Summary of the invention
One the invention solves the problems that technical problem is that: based on the problems referred to above, and the present invention provides the one can room temperature
Cross-link, prevent amine and the big particle diameter of many amine cations emulsifying agent migration, large arch dam, cation styrene-butadiene latex
And preparation method, prepare road modified emulsifying asphalt being used for, this product maintains road emulsified asphalt and changes
The primary characteristic of property styrene-butadiene latex, significantly reduces the rainwater leachable on modified emulsifying asphalt road surface simultaneously,
Reduce and environment water is polluted, improve service life of road surface.
The technical solution adopted for the present invention to solve the technical problems is: provide a kind of road emulsified asphalt modified
With styrene-butadiene latex, being specially the compound styrene-butadiene latex of one, this compound styrene-butadiene latex is by modified butadiene-styrene latex and friendship
Connection agent double-component composition, described modified butadiene-styrene latex is mean diameter 320nm～420nm, solid content >=60%
Cation styrene-butadiene latex, its main component includes: with the butadienestyrene copolymer of high gel content
For core, with low-gel content and side chain with the butadiene styrene methyl of epoxy radicals and alkoxysilyl group
The high-molecular copolymer of Glycidyl Acrylate KH-570 is the emulsion particle that shell is constituted, and anionic/nonionic is multiple
Co-emulsifier, tertiary amines cationic emulsifier and water；Described cross-linking agent is the KH-560 silane coupler of 40%
Aqueous emulsion；The weight ratio of modified butadiene-styrene latex and cross-linking agent is: 1:0.06～1:0.07.
The present invention solves another technical scheme that its technical problem used: road emulsified asphalt modification is used
The preparation method of styrene-butadiene latex, including following technical process:
A, emulsion are polymerized:
Raw material is grouped into by the one-tenth of following weight portion:
Butadiene: 72～80 parts；Styrene: 20～28 parts；Glytidyl methacrylate: 2～4 parts；
Silane coupling reagent KH-570 or silane coupler KH-151:1～2 parts；Lauryl mercaptan: 0.3～0.7
Part；Including at least a kind of compound emulsifying agent rolled into a ball containing carboxylic acid potassium or sodio: 1.5～4.0 parts；Ammonium Persulfate 98.5:
0.2～0.3 part；Sodium sulfite: 0.1～0.15 part；The aqueous phase densities regulator of alkali metal inorganic salt: 0.3～
0.6 part；Deionized water: 100～130 parts；Compound terminator: 0.02～0.04 part；
Polymerization technique: use polymeric kettle, add above-mentioned raw materials under vacuum conditions in polymeric kettle, prepare base
Plinth emulsion；
B, remove residual single agglomeration: step (a) product is squeezed into degassing still, use live (open) steam air-extraction
Removing residual monomer；Add 0.1～0.5 part of agglomerant aqueous solution, continue degassing >=30 minutes, obtain big grain
Footpath anionic latex；
C, ion-type are changed: by step (b) product, squeeze into ion-type conversion still, with sprinkling side under stirring
Formula is slowly added to be diluted to the aqueous solution of the tertiary amines cationic emulsifier of 20%～30%, then delays with spray pattern
Slow dilute hydrochloric acid adjustment system pH that adds, to 4～5, completes ion-type conversion, prepares big particle diameter cation butadiene-styrene rubber
Breast；
Wherein, tertiary amines cationic emulsifier is Rosin Amine Polyoxyethylene Ether ether 1～2 parts and aliphatic amine polyoxyethylene
Ether 1～the mixture of 2 parts；
D, centrifugal concentrating；By step (c) product, it is continually introduced into dish-style latex seperator, by concentrated
Styrene-butadiene latex adds containing age resistor 0.8～the aqueous emulsion of 1.0 parts, obtains modified butadiene-styrene latex: mean diameter
Position 320nm～420nm, the cation styrene-butadiene latex of solid content >=60%.
Further, the polymerization technique of described step (a) is particularly as follows: employing with anion surfactant is
The mixed emulsifier of master, semi-continuous emulsion polymerizing, reaction temperature 50～55 DEG C, total reaction time 15～18
Hour；Use polymeric kettle, in polymeric kettle, add the deionized water of 85%～88% under vacuum conditions, add
The compound emulsifying agent rolled into a ball containing carboxylic acid potassium or sodio including at least a kind of of total addition 70%, alkali metal inorganic salt
Aqueous phase densities regulator, the styrene of 50%, the lauryl mercaptan of 20%；3 are replaced with nitrogen in polymeric kettle
After secondary, add the butadiene of 50%, stirring and emulsifying 15 minutes；Reaction system is heated to 50 DEG C～55 DEG C,
Add the initiator ammonium persulfate of total addition 30%, accelerator aqueous solution of sodium bisulfite, work as reaction conversion ratio
When reaching to add monomer total amount about 70%, start to be continuously added to the oil phase of remaining mixing and aqueous phase material；First
Base Glycidyl Acrylate, Silane coupling reagent KH-570 (or silane coupler KH-151) all add remaining
In oil mixture material, remaining mixture material adds for about 6 hours, adds lauryl mercaptan 0.05～0.1
Part, continue insulated and stirred more than 5 hours, control this condition, until monomer total conversion >=98.5%, add
Compound terminator aqueous solution, obtains the basis of dry matter content 50 ± 0.5%, mean diameter 180nm～230nm
Emulsion.
Further, described compound terminator is N-isopropylhydroxyla and monomethyl nabam
Mixture, weight ratio is 2:1～3:1.
The reaction temperature of above-mentioned emulsion polymerization process sets, and styrene-butadiene latex emulsion polymerization technique can be divided into by temperature
Low temperature (5 DEG C) and high temperature (70 DEG C) two kinds, theoretically, polymerization temperature is low, beneficially butadiene Isosorbide-5-Nitrae
The formation of addition structure, branched little with the degree of cross linking, the mooney viscosity of latex is little, and structural gel content is low, rubber
Glue low temperature extensibility is preferable, but resilience and pliability are poor.During polymerization temperature height, beneficially 1,2 addition knots
The formation of structure, product adds branched and crosslinking, and the mooney viscosity of latex is big, and structural gel content is high, tool
There is good toughness, but low temperature extensibility is impacted.
Low temperature prepares styrene-butadiene latex, and equipment is more complicated, and production cost is higher；The fourth of high temperature emulsion polymerization preparation
Benzene latex is conducive to improving the high temperature toughness of Colophonium, and equipment is relatively easy, and cost is relatively low, is conducive to extensive
Commercial production, but other performance is also by impacted.Consider, select 50～55 DEG C of higher polymerization temperatures,
And use change chain-transferring agent feed postition to control physical property.
Gel content and the molecular size range of gel mass fraction in styrene-butadiene latex, particularly emulsion particle top layer are direct
Affect the latex particle in modified pitch and interpenetrating between bitumen base phase, affect micelle circle after breakdown of emulsion
Fusion degree between face, and then affect rubber network formation effect and Stress Transfer ability, affect modified pitch
High and low temperature performance.
Gel content is high, and Colophonium is poor with interpenetrating property of latex particle, and the compatibility is the best, and then reduces modification
Asphalt performance.If but gel content is on the low side, modified pitch poor toughness, resilience and high-temperature behavior are the best.
In the emulsion of SBR is polymerized, the amount of polymerization monomer Chain transfer agent directly affects structural gel in latex
Amount.The Adding Way of above-mentioned emulsion polymerization process Chain transfer agent lauryl mercaptan, the polymerization initial stage is at head
In the main monomer styrene of secondary addition total amount 50% and butadiene, add the chain-transferring agent of total amount 20%；Even
Another 50% main monomer of continuous dropping adds the chain-transferring agent of 80% total amount.Add monomer conversion at head and be about 70%
Time start to drip continuously, and after monomer all adds, add chain-transferring agent again.In whole polymerization process,
Polymerization monomer in chain tra nsfer concentration by 35% emulsion particle kernel to outermost layer, define concentration from less to more
Gradient.Chain transfer agent content determines the gel content in polymer molecular weight size, and formed rubber.?
Under above-mentioned polymerizing condition, the core of high gel content, the core/shell structure emulsion particle of low-gel content shell will be formed.
Low-gel content shell will have low mooney viscosity, add and the intermiscibility of bitumen base phase, add breakdown of emulsion
Syncretizing effect between rear latex particle, the rubber network being easily formed in Colophonium, it is ensured that low temperature extensibility.High
The core of gel content has high temperature toughness, is distributed in emulsion particle shell silanol base, between attainable particle in addition
Silanol base condensation, add the intensity of rubber network, viscous toughness and the toughness of modified pitch can be remarkably reinforced.
Function monomer glytidyl methacrylate is increased, at formed butadiene-styrene rubber high score in emulsion is polymerized
Epoxy radicals is introduced on sub-side chain, can be with amido (NHR, the R in asphalt emulsifier molecular structure at room temperature
For H or alkyl) reaction, play fixing emulsifying agent, prevent it from meeting the effect that water migrates.Addition is polymerization
The 2～3% of total monomer weight, such as ＜ 2% antimigration poor effect；In the polymerization of ＞ 4% then emulsion, solid residue amount increases
Add, and affect the emulsifying effectiveness of Colophonium.
Function monomer Silane coupling reagent KH-570 methacryloxypropyl front three is increased in emulsion is polymerized
TMOS (or KH-151 vinyl three ethoxy silane), its effect has 2 points, plays action of coupling agents and strengthens
Colophonium and stone material (aggregate) surface adhesion；Play cross-linking agent effect, the cross-linking agent emulsifying supporting with the present invention
KH-560 (adding in prepared by emulsified asphalt) is condensed between silanol under few water or anhydrous state, plays crosslinking solid
Fixed many amines asphalt emulsifier effect；Inclusive NAND ionic surface active agent hydrophilic group terminal hydroxyl is condensed, and plays
Fixing nonionic emulsifier effect.
Glytidyl methacrylate in emulsion is polymerized, KH-570 (or KH-151) feed way: complete
Portion adds in remaining oil mixture material.Its objective is to make glycidyl and alkoxysilyl group distribution as far as possible
At latex particle shell, at utmost increase and amine and the reaction probabilities of many amines asphalt emulsifier, or fused
Latex particle between chemical crosslinking.
The emulsifying agent rolled into a ball containing carboxylic acid potassium or sodio added in emulsion is polymerized, including C12～C18Saturated fat acid,
Oleic acid and disproportionated rosin acid potassium or soda soap.
The compound terminator added after emulsion is polymerized is N-isopropylhydroxyla and monomethyl dithiocarbamates first
Acid sodium mixture, weight ratio is 2:1～3:1.This compound terminator is the acid bar forming gel at latex
Under part, it is formed without the environment-friend auxiliaries of nitrosamine, and all can produce good at the liquid and gas of system
Chain termination and polymerization inhibition effect.
The agglomerant of the little molecule organic polycarboxylic acid ammonium added in step (b), including oxalic acid, O-phthalic
The ammonium salt of the polybasic carboxylic acid of acid and maleic acid.
Further, the Rosin Amine Polyoxyethylene Ether ether in described step (c), oxygen vinyl polymerization degree is 10～15,
Aliphatic amine polyoxyethylene ether is 16～18 fatty amines, and oxygen vinyl polymerization degree is 10～15.
Rosin Amine Polyoxyethylene Ether ether in step (c), oxygen vinyl polymerization degree is 10～15；Aliphatic amine polyoxyethylene
Ether is 16～18 fatty amines, and oxygen vinyl polymerization degree is 10～15.Rosin Amine Polyoxyethylene Ether ether and fatty amine
Polyoxyethylene ether has good emulsibility to styrene-butadiene latex, and under the conditions of neutrality and meta-alkalescence, with nonionic
Characteristic is main, has a good compatibility with the anion emulsifier in substance system, in acid condition in sun from
Sub-property.
Further, the age resistor EPPD in described step (d), specially N (1,3 one dimethylbutyl)
N ' diphenyl-para-phenylene diamine and N (Isosorbide-5-Nitrae dimethyl amyl group) N ' diphenyl-para-phenylene diamine mixture,
Weight ratio is that 4:6 is compounding to be formed.
Age resistor EPPD is not produce phenol wastewater after gel, do not produce nitrosamine and waste water that gel separates out
Environment-friendly type age resistor relatively low for middle COD.
Another component cross-link agent that double-component of the present invention is combined in styrene-butadiene latex: the KH-560 silane of 40% is even
Connection agent aqueous emulsion.Silane coupler KH-560 is γ-glycidyl ether oxygen propyl trimethoxy silicane, its point
Epoxy radicals in son can divide greatly the epoxy radicals function on side chain identical with the aforementioned butylbenzene high polymer that is in, permissible
React with the amido (NHR, R are H or alkyl) of amine and many amine cations asphalt emulsifier；Point
Three the methoxyl group silicon keys contained in son, hydrolyze to form three silanol bases in water, at the few water or anhydrous of room temperature
Under the conditions of can be the silanol base each other and on butadiene-styrene rubber macromolecular chain and the silicone hydroxyl of stone surface,
And it is condensed between the terminal hydroxy group in nonionic surfactant, makes the cation in emulsified asphalt and containing end hydroxyl
The emulsifying agents such as the nonionic of base are cross-linked into polymer, reduce the amount of precipitation in water.Simultaneously by with stone material
The coupled action on (aggregate) surface improves adhesion.
The determination of the addition of KH-560:
Total solid content about 60% of general polymerization thing modified emulsifying heavy traffic paving asphalt, water 40%, wherein effective ingredient:
Heavy traffic paving asphalt 54～56%, emulsifying agent 0.6～1.6%, styrene-butadiene latex 3～4% (butt), stabilizer 0.1～
0.3%, pH=3～4.
The organic stabilizer that emulsified asphalt is conventional includes polyvinyl alcohol, sodium carboxymethyl cellulose, starch and poly-third
The macromolecule stabilizers such as acrylamide, such stabilizer is the most nontoxic, owing to being that in polymer water, amount of precipitation is few,
Effect on environment is the least.
In, split fast solidifying type heavy traffic paving asphalt slowly and commonly use emulsifying agent, mainly lignin amine and the many amines of amide groups,
General molecular weight ratio is bigger.Styrene-butadiene latex addition is 3～time 4% (butt), by the aforementioned proportioning of the present invention,
Pure KH-560 addition is 0.18%～0.22%, in conjunction with the epoxy radicals introduced by function monomer during latex polymerization and
Alkoxysilyl group, can be controlled effectively to the amount of precipitation of emulsifying agent, makes amount of precipitation reduce 70%～80%,
And the stability of modified emulsifying asphalt will not be constituted a threat to.
The feed postition of cross-linking agent 40%KH-560 aqueous emulsion: add in modified emulsifying asphalt preparation process.
Preparing modified emulsifying asphalt for inner blending method, after asphalt emulsification completes, below 50 DEG C, stirring is lower to add
40% silane coupler KH-560 aqueous emulsion, stirs evenly；Prepared by modified emulsifying asphalt for extravasation method, with butylbenzene
Latex is simultaneously introduced.
The invention has the beneficial effects as follows:
1. use the emulsion polymerization way of higher temperature, chain-transferring agent three sections charging, polymerization introducing latter half to contain
The function monomer of epoxy radicals and alkoxysilyl group, be prepared for having high gel content core and low-gel content shell and
The core/shell type emulsion of epoxy radicals and alkoxysilyl group (or silanol base) is distributed at shell；Due to high gel core
And the crosslinked action between latex particle, modified emulsifying asphalt can be significantly improved and glue toughness and toughness, and have relatively
Low manufacturing cost；
2. and introducing in modified emulsifying asphalt preparation process in the shell monomer of emulsion polymerization can be in amine and many amine
The monomer containing epoxy radicals of cation asphalt emulgent reaction, introducing can produce crosslinking and prevent asphalt emulsifier from moving
The two kinds of silane couplers moved, can make the water precipitate reduction by more than 75% of road surface modified emulsifying asphalt, favorably
In reducing environmental pollution, alleviating Water Damage on Asphalt Pavement, improve service life.
Detailed description of the invention
Presently in connection with specific embodiment, the invention will be further described, and following example are intended to the present invention is described
Rather than limitation of the invention further.
Embodiment: prepare road emulsified asphalt modification styrene-butadiene latex:
A, emulsion are polymerized:
Raw material is grouped into by the one-tenth of following weight portion:
Butadiene 76 parts, styrene 24 parts, glytidyl methacrylate 3 parts, KH-151 1.5 parts,
Lauryl mercaptan 0.45 part, 1.2 parts of disproportionated rosin acid potassium, enuatrol 0.3 part, Nonyl pheno
(12) 0.9 part of ether, sodium hexameta phosphate 0.5 part, ammonium persulfate aqueous solution 0.24, sodium sulfite 0.12,
Deionized water (electrical conductivity≤5 μ S/cm) 103 parts, N-isopropylhydroxyla 0.02 part, monomethyl dithio
0.01 part of carbamic acid sodium；
Polymerization technique:
Deionized water 91 parts, 0.9 part of disproportionated rosin acid potassium, enuatrol 0.23 is added in polymerization reaction kettle
Part, NPE (12) 0.63 parts, sodium hexameta phosphate 0.35 part, after stirring and dissolving, add
Styrene 12 parts, lauryl mercaptan 0.08 part, be evacuated to-0.05MPa, inflated with nitrogen to 0.3MPa,
3 times repeatedly, pressure-fired in denitrogen gas to still, then in reactor, add butadiene 38 parts, stirring and emulsifying 15
Minute, heat to 50 DEG C, in reaction system, add 15% ammonium persulfate aqueous solution 0.48 part, sulfurous
Acid sodium aqueous solution 0.27 part, controls reaction temperature 50 DEG C～55 DEG C.Record system dry matter content >=34%
Time, start to drip leftover materials continuously.Oil phase: styrene 12 parts, butadiene 38 parts, methacrylic acid
Polyglycidyl 3 parts, KH-151 1.5 parts, lauryl mercaptan 0.32 part；Aqueous phase 1: 8 parts of water, disproportionation
Potassium rosinate 0.3 part, enuatrol 0.07 part, NPE (12) 0.27 parts, hexa metaphosphoric acid
0.15 part of sodium, sodium sulfite 0.08 part；Aqueous phase 2: 4 parts of water, Ammonium persulfate. 0.168 part；Within 6 hours, add
Complete aqueous phase 1 and oil phase；Within 6.5 hours, add aqueous phase 2, add lauryl mercaptan 0.05 part, continue insulation
Stirring more than 5 hours, during until conversion ratio reaches the 98.5% of monomer total amount, total reaction time 15～18 is little
Time, add 10% terminator N-isopropylhydroxyla aqueous solution 0.2 part, 10% monomethyl nabam
Aqueous solution 0.1 part, obtains the basic emulsion of dry matter content 50 ± 0.5%, mean diameter 180nm～230nm；
B, remove residual single agglomeration:
The basic emulsion whole suction degassing still that will obtain in step (a) by vacuum, continues to evacuation
-0.085Mpa about 20 minutes, after liquid level is substantially steady, opens steam valve (steam pressure >=0.3Mpa),
Heat temperature raising, controls degassing still temperature about 70 DEG C, maintains 3～4 hours, when volatility unsaturates in material
When≤0.02%, addition ammonia adjusts agglomerant (the ammonium oxalate 0.2 part) aqueous solution that pH is 7～8, continues
Continuous steam deaerates 30 minutes, closes vacuum, and adjustment still pressure is normal pressure, and fall still temperature, to less than 50 DEG C, obtains average
Grain 300nm～400nm, the large grain size latex of dry matter content 50 ± 0.5%；
C, ion-type are changed:
The product of step (b) is squeezed into ion-type conversion still, under stirring, by the Rosin Amine Polyoxyethylene Ether of 20%
(15) 10 parts of ether, the mixed aqueous solution of 5 parts of 18-amine. polyoxyethylene (10) ether, delays with spray pattern
In slow addition still, within about 1 hour, adding, after stirring 10 minutes, the dilute hydrochloric acid by 5% about 2～2.5 parts is with spray
The mode of spilling is slowly added in still, adjusts still liquid pH to 4～5, continues stirring 20 minutes, completes ion-type conversion,
Obtain the big particle diameter cation styrene-butadiene latex of solid content about 47.5%, mean diameter 300nm～400nm；
D, centrifugal concentrating:
Product in step (c) is continually introduced into dish-style latex seperator, is continuously separated out that to account for being centrifuged thing total
The 79% of amount, dry matter content 62 ± 1% High Solid Content SBR Latex, adds the water of age resistor EPPD0.8 part
Solution, i.e. this technique purpose product；Account for being centrifuged thing total amount 21%, dry matter content about it addition, isolate
The small grain size latex of 5%, is back to use emulsion polymerization technique as seed emulsion,
The quality index of products therefrom:
Outward appearance: milky white liquid；Solid content: 62.0 ± 1%；
Viscosity: 800～1600mPa.s；PH value: 4～5；
Ionic: cation；Density (g/m3): 0.95；
Total unsaturated volatile content :≤200ppm.
The styrene-butadiene latex obtained such as above-described embodiment prepares modified emulsifying asphalt (outer doping):
Cationic emulsifier is added in a certain amount of distilled water, stirring and dissolving, adjust pH=3～4, obtain emulsifying
Liquid, is heated to 75 DEG C, adds in colloid mill, then will warm up the 90 of 140 DEG C#Heavy traffic paving asphalt is slowly added to
Rotating speed is in the colloid mill of 12000r/min, stirs 3min, adds quantitative cation styrene-butadiene latex,
40%KH-560 aqueous emulsion, stirs 2min, obtains cation-modified emulsified asphalt.
Modified emulsifying asphalt quality index: solid content 62%, pH=3～4.
Constituent: 90#Heavy traffic paving asphalt 56%, emulsifier is 1.5% (this quality amine: amide groups polyamines
=8:4), stabilizer is 0.2%, and embodiment styrene-butadiene latex is 4% (butt), 40%KH-560 aqueous emulsion 0.45%,
Water: 48%.
Comparative example:
Commercially available cation styrene-butadiene latex technical specification:
Outward appearance: milky white liquid；Ionic: cation；
Solid content: 60%；PH value: 3～5；
Density (g/m3): 0.95；Mechanical stability :≤1.0；
Modified emulsifying asphalt is prepared (outer doping):
Preparation method: by styrene-butadiene latex in embodiment and 40%KH-560 aqueous emulsion, change the commercially available fourth of comparative example into
Benzene latex, other same embodiment.
The modified emulsifying asphalt prepared with two kinds of styrene-butadiene latexes, the physical property after solidification is shown in Table 1；
Table 1: modified emulsifying asphalt evaporated residue character:
| Sequence number | Project name | Standard index[1] | Embodiment | Comparative example |
| 1 | Evaporated residue content/% | ≥62 | 62 | 62 |
| 2 | Needle penetration/10-1mm | ≤100 | 78 | 79 |
| 3 | Ductility (5 DEG C)/cm | ＞ 20 | ≥150 | ≥150 |
| 4 | Softening point/DEG C | ＞ 50 | 53 | 52 |
| 5 | Viscous toughness (25 DEG C)/N m | ＞ 3.0 | 7.2 | 6.4 |
| 6 | Toughness (25 DEG C)/N m | ＞ 2.5 | 4.9 | 4.3 |
[1] note: this achievement data is from JTG F40-2004 standard specification for construction and acceptance of highway asphalt pavement.
Modified emulsifying asphalt water leachability:
The water leachability detection of modified emulsifying asphalt evaporated residue, the test side used in reference literature [1]
Method, prepared by detection dry film: use 500 μm coating devices to scratch on sheet glass by modified emulsifying asphalt, in 40 DEG C
Constant temperature oven stands 12 hours, obtains modified emulsifying asphalt dry film；With 500ml water (pH=5～6) in 60 DEG C
Soak 4 hours, detection leaching water liquid: cation emulsified agent content, filtrate chemical oxygen consumption (COC) (COD), solid
Particle amount (SS).SS refers to soak water liquid by the solid under remaining after filter membrane that aperture is O.45 μm
Material amount content in water.
Table 2: extractum testing result in modified emulsifying asphalt water
| Cation emulsified agent content (mg/L) | COD(mg/L) | SS(mg/L) | |
| Embodiment Colophonium | 1.8 | 13 | 11 |
| Comparative example Colophonium | 8.6 | 52 | 58 |
| Decreasing value | 79% | 75% | 81% |
[1] note: Wang Zhenjun, Wei Yongfeng, etc., cationic emulsified bitumen leaching characteristic [J] in an acidic solution,
Journal of Building Materials, 2015,18 (1): 65-68.
As seen from Table 1, using styrene-butadiene latex of the present invention is modified emulsifying asphalt prepared by modifying agent, its evaporation
Residue physical index and existing market styrene-butadiene latex compared with, altogether in five indices, three basic phases
With, viscous toughness improves more than 10% with toughness index.
From the modified emulsifying asphalt water of table 2 in extractum testing result, cation emulsified agent content,
Filtrate chemical oxygen consumption (COC) (COD), solid suspended particle amount (SS), three index drop-out values are all >=75%.
With the above-mentioned desirable embodiment according to the present invention for enlightenment, by above-mentioned description, related work
Personnel can carry out various change and amendment completely in the range of without departing from this invention technological thought.
The content that the technical scope of this invention is not limited in description, it is necessary to according to right
Determine its technical scope.
Claims (6)
1. a road emulsified asphalt modification styrene-butadiene latex, is specially the compound styrene-butadiene latex of one, its feature
It is: this compound styrene-butadiene latex is made up of modified butadiene-styrene latex and cross-linking agent double-component, described modified butadiene-styrene rubber
Breast is mean diameter 320nm～420nm, the cation styrene-butadiene latex of solid content >=60%, and its main component includes:
With the butadienestyrene copolymer of high gel content as core, with low-gel content and side chain with epoxy radicals
Polymer copolymerization with butadiene styrene glytidyl methacrylate KH-570 of alkoxysilyl group
Thing is the emulsion particle that shell is constituted, anionic/nonionic compound emulsifying agent, tertiary amines cationic emulsifier and water；
Described cross-linking agent is the KH-560 silane coupler aqueous emulsion of 40%；Modified butadiene-styrene latex and the weight of cross-linking agent
Ratio is: 1:0.06～1:0.07.
2. the preparation method of road emulsified asphalt modification styrene-butadiene latex as claimed in claim 1, its feature
It is: include following technical process:
A, emulsion are polymerized:
Raw material is grouped into by the one-tenth of following weight portion:
Butadiene: 72～80 parts；Styrene: 20～28 parts；Glytidyl methacrylate: 2～4 parts；
Silane coupling reagent KH-570 or silane coupler KH-151:1～2 parts；Lauryl mercaptan: 0.3～0.7
Part；Including at least a kind of compound emulsifying agent rolled into a ball containing carboxylic acid potassium or sodio: 1.5～4.0 parts；Ammonium Persulfate 98.5:
0.2～0.3 part；Sodium sulfite: 0.1～0.15 part；The aqueous phase densities regulator of alkali metal inorganic salt: 0.3～
0.6 part；Deionized water: 100～130 parts；Compound terminator: 0.02～0.04 part；
Polymerization technique: use polymeric kettle, add above-mentioned raw materials under vacuum conditions in polymeric kettle, prepare base
Plinth emulsion；
B, remove residual single agglomeration: step (a) product is squeezed into degassing still, use live (open) steam air-extraction
Removing residual monomer；Add 0.1～0.5 part of agglomerant aqueous solution, continue degassing >=30 minutes, obtain big grain
Footpath anionic latex；
C, ion-type are changed: by step (b) product, squeeze into ion-type conversion still, with sprinkling side under stirring
Formula is slowly added to be diluted to the aqueous solution of the tertiary amines cationic emulsifier of 20%～30%, then delays with spray pattern
Slow dilute hydrochloric acid adjustment system pH that adds, to 4～5, completes ion-type conversion, prepares big particle diameter cation butadiene-styrene rubber
Breast；
Wherein, tertiary amines cationic emulsifier is Rosin Amine Polyoxyethylene Ether ether 1～2 parts and aliphatic amine polyoxyethylene
Ether 1～the mixture of 2 parts；
D, centrifugal concentrating；By step (c) product, it is continually introduced into dish-style latex seperator, by concentrated
Styrene-butadiene latex adds containing age resistor 0.8～the aqueous emulsion of 1.0 parts, obtains modified butadiene-styrene latex: mean diameter
Position 320nm～420nm, the cation styrene-butadiene latex of solid content >=60%.
The preparation method of road emulsified asphalt modification styrene-butadiene latex the most according to claim 2, it is special
Levy and be: the polymerization technique of described step (a) is particularly as follows: use answering based on anion surfactant
Mould assembly emulsifying agent, semi-continuous emulsion polymerizing, reaction temperature 50～55 DEG C, total reaction time 15～18 hours；
Use polymeric kettle, in polymeric kettle, add the deionized water of 85%～88% under vacuum conditions, add total addition
The compound emulsifying agent rolled into a ball containing carboxylic acid potassium or sodio including at least a kind of of amount 70%, alkali metal inorganic salt aqueous phase close
Degree regulator, the styrene of 50%, the lauryl mercaptan of 20%；After replacing 3 times with nitrogen in polymeric kettle,
Add the butadiene of 50%, stirring and emulsifying 15 minutes；Reaction system is heated to 50 DEG C～55 DEG C, adds total
The initiator ammonium persulfate of addition 30%, accelerator aqueous solution of sodium bisulfite, when reaction conversion ratio reaches
When adding monomer total amount about 70%, start to be continuously added to the oil phase of remaining mixing and aqueous phase material；Metering system
Acid polyglycidyl, Silane coupling reagent KH-570 (or silane coupler KH-151) all add remaining oil phase to be mixed
In compound material, remaining mixture material adds for about 6 hours, adds lauryl mercaptan 0.05～0.1 part,
Continue insulated and stirred more than 5 hours, control this condition, until monomer total conversion >=98.5%, add compound
Terminator aqueous solution, obtains the basic emulsion of dry matter content 50 ± 0.5%, mean diameter 180nm～230nm.
The preparation method of road emulsified asphalt modification styrene-butadiene latex the most according to claim 3, it is special
Levy and be: described compound terminator is the mixing of N-isopropylhydroxyla and monomethyl nabam
Thing, weight ratio is 2:1～3:1.
The preparation method of a kind of modifying road asphalt styrene-butadiene latex the most according to claim 2, it is special
Levying and be: the Rosin Amine Polyoxyethylene Ether ether in described step (c), oxygen vinyl polymerization degree is 10～15, fat
Amine polyoxyethylene ether is 16～18 fatty amines, and oxygen vinyl polymerization degree is 10～15.
The preparation method of a kind of modifying road asphalt styrene-butadiene latex the most according to claim 2, it is special
Levy and be: the age resistor EPPD in described step (d), specially N (1,3 one dimethylbutyl) N '
Diphenyl-para-phenylene diamine and N (Isosorbide-5-Nitrae dimethyl amyl group) N ' diphenyl-para-phenylene diamine mixture, weight
Form than for 4:6 is compounding.
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