CN110358315A - A kind of preparation method of core-shell structure epoxy resin modified asphalt lotion - Google Patents
A kind of preparation method of core-shell structure epoxy resin modified asphalt lotion Download PDFInfo
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- CN110358315A CN110358315A CN201910679134.3A CN201910679134A CN110358315A CN 110358315 A CN110358315 A CN 110358315A CN 201910679134 A CN201910679134 A CN 201910679134A CN 110358315 A CN110358315 A CN 110358315A
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- epoxy resin
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- shell structure
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- modified asphalt
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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
- 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
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses the preparation methods of core-shell structure epoxy resin modified asphalt lotion, the following steps are included: being emulsified again after self-emulsifying epoxy resin or in which addition oiliness epoxy resin are mixed with heated bitumen, asphalt emulsion is made, the asphalt emulsion is that emulsion particle kernel is pitch, the core-shell structure of outer layer covers epoxy resin；Heated bitumen viscosity be can reduce convenient for emulsification, reduce the partial size of modified emulsifying asphalt latex simultaneously, epoxy resin can achieve the dispersion effect of micron-nanometer degree in pitch, the loss of epoxy and curing agent is reduced simultaneously, performance that can be achieved is adjustable, energy-saving, save the cost, stable storing, is convenient for the purpose of preparing, is more environmentally-friendly, and has the remarkable result of performance improvement.Epoxy modified asphalt lotion prepared by the present invention is suitable for the protection works such as all kinds of civil construction projects, waterproof and anti-corrosion as structural material and functional material.
Description
Technical field
The present invention relates to field of asphalt modification, in particular to a kind of preparation of core-shell structure epoxy resin modified asphalt lotion
Method.
Background technique
Epoxy resin modification is the technological means for improving emulsified asphalt performance, and the prior art is generally first by epoxy resin water
Property, then the method with emulsified asphalt mixture, remain shortcoming.The method of modifying multiplicity of epoxy-modified emulsified asphalt, such as:
Patent CN1441032, CN102010607, CN1903941 first prepare emulsified asphalt, and emulsified asphalt then is added in epoxy latex
In be uniformly mixed；CN105462273 uses bicomponent system, and component A is emulsified asphalt, SBS latex, curing agent；B component
For epoxy resin, diluent, solvent, emulsifier；CN102010609 enters emulsification drip using hydrophilic matrix tablets aqueous solution mixture
It realizes and is modified in blueness.The prior art is characterized in that pitch individually emulsifies and is mixed again with epoxy modifying agent.Due to most asphalt mixtures modified by epoxy resin
Rouge and curing agent are oiliness object, need first (to emulsify or chemical modification is water-soluble epoxy resin and curing agent progress Water-borne modification processing
Change), epoxy modifying agent is made, then blended emulsified asphalt, finishing operations are more convenient.But the prior art, which is appointed, so has many
Deficiency specifically includes: the epoxy modified asphalt material two-phase dispersion after 1. film forming solidify is irregular, and performance is lower than expection: heat emulsification
The usual partial size of asphalt emulsion grain be 2-10 microns, much larger than most of latex of emulsion polymerization；At room temperature, the asphalt mixtures modified by epoxy resin matched is mixed
Rouge (polarity is strong) cannot diffuse into pitch (polarity is weak) during demulsification, film forming, and have tendency of itself reuniting；Asphalt mixtures modified by epoxy resin
Rouge is different from the emulsifier system of emulsified asphalt, and the two demulsification is almost impossible to be carried out simultaneously, and one in front and one in back demulsification causes respectively
Single-phase isolation, thus in the dry asphalt membrane formed of modified emulsion, epoxy resin with biggish agglomerate in island be independently distributed in
Wherein；Epoxy continuous phase could be formed by only increasing content of epoxy resin, reach higher performance；Pitch is individually at phase, temperature
Degree sensibility is not effectively improved, hot mastication, low-temperature embrittleness.2. curing agent loss is big, curing efficiency is not high: Water-borne modification
Curing agent no matter be mixed into system in which way, can all spread and be lost with water, be gathered materials or the consumption such as filling adsorption；Only
Curing reaction is just participated in into the part of epoxy resin, epoxy resin cure is incomplete, it is difficult to give full play to its modifying function.Cause
This, these deficiencies cause epoxy-modified effect that cannot reach expected, or must increase epoxy resin to reach superior performance
Additive amount, cost are soaring.3. there are certain emission pollution problems: soluble epoxide is easily lost with water body with waterborne curing agent
Diffusion pollutes；Epoxy need to be emulsified individually, additionally increase emulsifier, and water-soluble emulsifier likewise suffers from centainly
Environmental pollution.In addition, the hydrophilic modification of epoxy resin is handled, it will usually a part of active group is consumed, it is bad to a certain degree
Change the performance after raw material epoxy resin solidifies.It can be seen that the prior art is not perfect, there are biggish rooms for promotion.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of preparation sides of core-shell structure epoxy resin modified asphalt lotion
Method can reduce heated bitumen viscosity convenient for emulsification, while reduce the partial size of modified emulsifying asphalt latex, and epoxy resin is in pitch
It can achieve the dispersion effect of micron-nanometer degree, while reducing the loss of epoxy and curing agent.
The preparation method of core-shell structure epoxy resin modified asphalt lotion of the invention, comprising the following steps: by asphalt mixtures modified by epoxy resin
Rouge emulsifies again after mixing with heated bitumen, asphalt emulsion is made, the asphalt emulsion is that emulsion particle kernel is pitch, outer layer covers ring
The core-shell structure of oxygen resin；
Further, the heated bitumen is the pitch being heated in flow regime；
Further, pitch is heated to viscosity≤0.4Pa.s；
Further, adjusting temperature makes uniformly mixed mixture viscosity≤0.3Pa.s；
Further, the epoxy resin and heated bitumen mass ratio are 100:5~100:50；
It further, further include auxiliary agent, the auxiliary agent, epoxy resin emulsify again after mixing with heated bitumen；
Further, the auxiliary agent is surfactant；
Further, the epoxy resin is one or more of self-emulsifying epoxy resin, oiliness epoxy resin；
Further, the surfactant be alkyl phenol polyoxyethylene ether, hexadecyltrimethylammonium chloride, polysorbas20,
One or more of lauryl sodium sulfate, sorbester p17, OP-10.
Beneficial effects of the present invention: the preparation method of core-shell structure epoxy resin modified asphalt lotion of the invention uses
Self-emulsifying epoxy resin is evenly mixed in heated bitumen, a small amount of emulsifier of supplement may be selected in soap lye, by common emulsified asphalt
Process disposably emulsified, obtain epoxy resin modified emulsified asphalt, emulsion particle kernel is pitch, outer layer covers
Epoxy resin has significant core-shell structure feature.This method has the following characteristics that
1. reducing heated bitumen viscosity convenient for emulsification, while reducing the partial size of modified emulsifying asphalt latex: asphalt emulsification temperature
Usually at 130 DEG C or so, viscosity is very low at this temperature for epoxy resin, and heated bitumen viscosity can be reduced by being added into pitch, same
Deng mechanical shearing emulsification under, can get smaller latex particle size；Emulsifying temperature condition can also be suitably reduced simultaneously, is convenient for
Preparation manipulation is also beneficial to the improvement of stability of emulsion.
2. epoxy resin is evenly distributed after modified emulsion film forming, the performance after film forming solidifies: hydrophilic self-emulsifying is promoted
Epoxy resin plays the role of emulsifier, oiliness pitch particle outer surface is wrapped in emulsion process, film thickness is in nano-micrometre
Range forms core-shell structure；Surfactant is only added on a small quantity, can be obtained the modified milk micelle of stable suspersion.Core after demulsification
Shell emulsion particle melts and forms a film, and epoxy resin is evenly distributed and is easily formed continuous phase；After curing agent participates in reaction, it is cured as net
Network structure and to filler, gather materials, substrate formed cohesive force.Suitable control curing rate can prevent pitch and epoxy in film forming
Isolation, reaches the dispersion effect of epoxy resin micron-nanometer degree in pitch.Its homogeneity can give full play to epoxy resin
Modified effect improves the performance after film forming solidifies by a relatively large margin.
3. curing reaction is abundant and reduces the loss of epoxy and curing agent: since epoxy resin is located at the table of modified milk micelle
Face, in emulsion breaking drying process, waterborne curing agent is first contacted with epoxy resin, and curing reaction occurs, and can prevent asphalt mixtures modified by epoxy resin
Rouge is spread with water；It is different from and is adsorbed in matrix pitch emulsion particle for partially cured dose in the prior art, it is solid to be not engaged in epoxy resin
Change reaction, causes curing agent loss, slow curing, solidification to be not thorough etc. unfavorable.
4. performance is controllable: this method can also add common oiliness epoxy resin in self-emulsifying epoxy resin, preparation
Technique is constant, obtain kernel pitch, secondary outer layer oiliness epoxy, three layers of fine structure of superficial layer self-emulsifying epoxy emulsion particle, lead to
The type for changing oiliness epoxy resin, volume are crossed, the epoxy-modified emulsified asphalt of core-shell structure of property wider range is obtained, is convenient for
Adapt to all kinds of different purposes.
5. applicability, economy and the feature of environmental protection: since the epoxy resin overwhelming majority is oiliness, and and self-emulsifying epoxy resin
With compatibility, therefore the present invention expands the optional range of epoxy source material, so that final product performance variable range
Also expand, it is widely applicable；Disposable emulsification procedure is only needed, preparation path is shortened；Self-emulsifying epoxy resin is instead of major part
Emulsifier reduces the consumption of emulsifier；Since performance boost, material loss reduce, the addition content of epoxy resin can be reduced, is taken
Obtain preferable economy；Without individually carrying out Water-borne modification processing to epoxy resin, cost can also be reduced；And at the same time reducing existing
Have a technology can the exhaust emission of the hydrotrope and epoxy emulsifier in the environment.
In short, method of the invention, carry out the preparation and its application of epoxy modified asphalt lotion, applicability, convenience,
Quality stability, economy, feature of environmental protection etc. can all obtain apparent effect.
Specific embodiment
For the effect for comparing following embodiment, parallel preparation is referring to sample: the prior art is pressed, directly by self-emulsifying epoxy resin
Lotion is first made, then blends the emulsified asphalt of same matrix pitch preparation, common epoxy-modified emulsified asphalt, curing agent is made
It using identical waterborne curing agent, is made in parallel referring to sample test specimen, carries out the test pair of drawing adhesive strength by national standard GB/T9779
Compare performance.
Embodiment one
Using the modified 70# emulsified asphalt of self-emulsifying epoxy resin, raw material ratio is pitch: self-emulsifying epoxy resin: alkane
Base phenol polyethenoxy ether=100:10:0.2,
Preparation process are as follows: pitch is first heated to viscosity≤0.4Pa.s and is allowed in flow regime, by self-emulsifying epoxy tree
Rouge, alkyl phenol polyoxyethylene ether investment heated bitumen stir evenly, and according to viscosity reducing effect, adjust temperature to viscosity≤0.3Pa.s, press
Emulsification procedure is carried out according to the method for plain asphalt, the control of soap lye temperature implements emulsification in 60 ± 5 DEG C of ranges to get core-shell structure
Epoxy modified asphalt lotion.
The lotion average grain diameter for surveying the preparation of this patent method reduces 43% relative to referring to sample；Adhesive strength test result
Display improves 58% using the core-shell emulsion adhesive strength of this patent preparation relative to referring to sample intensity 0.28Mpa.
Embodiment two
Self-emulsifying epoxy resin adds E44 epoxy resin modification 90# emulsified asphalt: raw material ratio is pitch: E44: from
Emulsion epoxy resin: auxiliary agent=100:10:5:0.5, the auxiliary agent are hexadecyltrimethylammonium chloride, alkylphenol-polyethenoxy
Ether in 1:2 ratio mixture.
Preparation process are as follows: pitch is first heated to viscosity≤0.4Pa.s and is allowed in flow regime, by self-emulsifying epoxy tree
Rouge, auxiliary agent investment heated bitumen stir evenly, and according to viscosity reducing effect, adjust temperature to viscosity≤0.3Pa.s, according to plain asphalt
Method carries out emulsification procedure, and the control of soap lye temperature implements emulsification in 60 ± 5 DEG C of ranges to get core-shell structure epoxy modified asphalt
Lotion.
It surveys lotion average grain diameter manufactured in the present embodiment and reduces 48% relative to referring to sample；Adhesive strength test result is aobvious
Show, relative to referring to sample intensity 0.56Mpa, improves 94% using the core-shell emulsion adhesive strength of this patent preparation.
Embodiment three
Self-emulsifying epoxy resin adds E51 epoxy resin modification 200# emulsified asphalt: raw material ratio is pitch: E51: from
Emulsion epoxy resin: auxiliary agent=100:15:5:1, the auxiliary agent is cetyl trimethylammonium bromide, polysorbas20, alkyl phenol are poly-
Ethylene oxide ether in 1:1:1 ratio mixture.
Preparation process are as follows: pitch is first heated to viscosity≤0.4Pa.s and is allowed in flow regime, by self-emulsifying epoxy tree
Rouge, E51, auxiliary agent investment heated bitumen stir evenly, and according to viscosity reducing effect, adjust temperature to viscosity≤0.3Pa.s, according to common drip
Green method carries out emulsification procedure, and the control of soap lye temperature implements emulsification in 60 ± 5 DEG C of ranges, epoxy-modified to get core-shell structure
Asphalt emulsion.
It surveys lotion average grain diameter manufactured in the present embodiment and reduces 53% relative to referring to sample；Adhesive strength test result is aobvious
Show, relative to referring to sample intensity 0.82Mpa, improves 104% using the core-shell emulsion adhesive strength of this patent preparation.
Example IV
Self-emulsifying epoxy resin adds E51 epoxy resin modification 200# emulsified asphalt: raw material ratio is pitch: E51: from
Emulsion epoxy resin: auxiliary agent=100:35:5:0.8, the auxiliary agent are that the auxiliary agent is lauryl sodium sulfate, alkyl phenol polyoxy
Vinethene in 2:1 ratio mixture.
Preparation process are as follows: pitch is first heated to viscosity≤0.4Pa.s and is allowed in flow regime, by self-emulsifying epoxy tree
Rouge, E51, auxiliary agent investment heated bitumen stir evenly, and according to viscosity reducing effect, adjust temperature to viscosity≤0.3Pa.s, according to common drip
Green method carries out emulsification procedure, and the control of soap lye temperature implements emulsification in 60 ± 5 DEG C of ranges, epoxy-modified to get core-shell structure
Asphalt emulsion.
It surveys lotion average grain diameter manufactured in the present embodiment and reduces 76% relative to referring to sample；Adhesive strength test result is aobvious
Show, relative to referring to sample intensity 1.34Mpa, improves 121% using the core-shell emulsion adhesive strength of this patent preparation.
Embodiment five
Using the modified 70# emulsified asphalt of self-emulsifying epoxy resin, raw material ratio is pitch: self-emulsifying epoxy resin: department
Disk 80:OP-10=100:5:0.2:0.1.
Preparation process are as follows: pitch is first heated to viscosity≤0.4Pa.s and is allowed in flow regime, by self-emulsifying epoxy tree
Rouge, sorbester p17, OP-10 investment heated bitumen stir evenly, and according to viscosity reducing effect, adjust temperature to viscosity≤0.3Pa.s, according to general
The method of logical pitch carries out emulsification procedure, and the control of soap lye temperature implements emulsification, in 60 ± 5 DEG C of ranges to get core-shell structure epoxy
Modified pitch emulsion.
The lotion average grain diameter for surveying the preparation of this patent method reduces 45% relative to referring to sample；Adhesive strength test result
Display improves 59% using the core-shell emulsion adhesive strength of this patent preparation relative to referring to sample intensity 0.22Mpa.
Embodiment six
Using the modified 70# emulsified asphalt of self-emulsifying epoxy resin, raw material ratio is pitch: self-emulsifying epoxy resin: ten
Sodium dialkyl sulfate: OP-10=100:10:0.2:0.2.
Preparation process are as follows: pitch is first heated to viscosity≤0.4Pa.s and is allowed in flow regime, by self-emulsifying epoxy tree
Rouge, lauryl sodium sulfate, OP-10 investment heated bitumen stir evenly, according to viscosity reducing effect, adjust temperature to viscosity≤
0.3Pa.s carries out emulsification procedure according to the method for plain asphalt, and the control of soap lye temperature implements emulsification in 60 ± 5 DEG C of ranges, i.e.,
Obtain core-shell structure epoxy modified asphalt lotion.
The lotion average grain diameter for surveying the preparation of this patent method reduces 82% relative to referring to sample；Adhesive strength test result
Display improves 72% using the core-shell emulsion adhesive strength of this patent preparation relative to referring to sample intensity 0.28Mpa.
In above-described embodiment, it is to add auxiliary agent and epoxy resin in heated bitumen after mixing, can also throws respectively
Enter in heated bitumen.
Finally, it is stated that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to compared with
Good embodiment describes the invention in detail, those skilled in the art should understand that, it can be to skill of the invention
Art scheme is modified or replaced equivalently, and without departing from the objective and range of technical solution of the present invention, should all be covered at this
In the scope of the claims of invention.
Claims (8)
1. a kind of preparation method of core-shell structure epoxy resin modified asphalt lotion, it is characterised in that: the following steps are included: by ring
Oxygen resin emulsifies again after mixing with heated bitumen, asphalt emulsion is made, the asphalt emulsion is that emulsion particle kernel is pitch, outer layer packet
Wrap up in the core-shell structure of epoxy resin.
2. the preparation method of core-shell structure epoxy resin modified asphalt lotion according to claim 1, it is characterised in that: institute
Stating heated bitumen is the pitch being heated in flow regime.
3. the preparation method of core-shell structure epoxy resin modified asphalt lotion according to claim 2, it is characterised in that: will
Pitch is heated to viscosity≤0.4Pa.s.
4. the preparation method of core-shell structure epoxy resin modified asphalt lotion according to claim 3, it is characterised in that: adjust
Section temperature makes uniformly mixed mixture viscosity≤0.3Pa.s.
5. the preparation method of core-shell structure epoxy resin modified asphalt lotion according to claim 1, it is characterised in that: institute
It states heated bitumen and epoxy resin mass ratio is 100:5~100:50.
6. the preparation method of core-shell structure epoxy resin modified asphalt lotion according to claim 1, it is characterised in that: also
Including auxiliary agent, the auxiliary agent, epoxy resin emulsify again after mixing with heated bitumen.
7. the preparation method of core-shell structure epoxy resin modified asphalt lotion according to claim 6, it is characterised in that: institute
Stating auxiliary agent is surfactant.
8. the preparation method of core-shell structure epoxy resin modified asphalt lotion according to claim 7, it is characterised in that: institute
Stating epoxy resin is one or more of self-emulsifying epoxy resin, oiliness epoxy resin.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111592770A (en) * | 2020-04-21 | 2020-08-28 | 同济大学 | Emulsified asphalt and preparation method thereof |
| CN112321201A (en) * | 2020-11-25 | 2021-02-05 | 宁波东兴沥青制品有限公司 | High-density asphalt concrete and preparation method thereof |
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