[go: up one dir, main page]

CN108793830B - Water-soluble phenolic resin modified emulsified asphalt concrete, and preparation method and application thereof - Google Patents

Water-soluble phenolic resin modified emulsified asphalt concrete, and preparation method and application thereof Download PDF

Info

Publication number
CN108793830B
CN108793830B CN201710280513.6A CN201710280513A CN108793830B CN 108793830 B CN108793830 B CN 108793830B CN 201710280513 A CN201710280513 A CN 201710280513A CN 108793830 B CN108793830 B CN 108793830B
Authority
CN
China
Prior art keywords
water
phenolic resin
emulsified asphalt
soluble phenolic
solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN201710280513.6A
Other languages
Chinese (zh)
Other versions
CN108793830A (en
Inventor
曹东伟
张艳君
张海燕
贾晓鹏
夏磊
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing Zhonglu Gaoke Highway Technology Co ltd
Original Assignee
Beijing Zhonglu Gaoke Highway Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Beijing Zhonglu Gaoke Highway Technology Co ltd filed Critical Beijing Zhonglu Gaoke Highway Technology Co ltd
Priority to CN201710280513.6A priority Critical patent/CN108793830B/en
Publication of CN108793830A publication Critical patent/CN108793830A/en
Application granted granted Critical
Publication of CN108793830B publication Critical patent/CN108793830B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/02—Macromolecular compounds
    • C04B26/26—Bituminous materials, e.g. tar, pitch
    • 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
    • C08L95/005—Aqueous compositions, e.g. emulsions
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/0075—Uses not provided for elsewhere in C04B2111/00 for road construction
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Civil Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Phenolic Resins Or Amino Resins (AREA)
  • Road Paving Structures (AREA)

Abstract

The invention provides a water-soluble phenolic resin modified emulsified asphalt concrete, a preparation method and application thereof, wherein the modified emulsified asphalt concrete comprises mineral aggregate; water-soluble phenolic resin modified emulsified asphalt mixed and stirred with the mineral aggregate; wherein the weight ratio of the mineral aggregate to the water-soluble phenolic resin modified emulsified asphalt is 100: 5-40. The invention is obtained by adding water-soluble phenolic resin modified emulsified asphalt into mineral aggregate, stirring uniformly and curing. The water-soluble phenolic resin modified emulsified asphalt concrete prepared by the invention not only has the advantages of the traditional cold-mix asphalt concrete, but also has excellent mechanical property and stability, has excellent road performance, greatly prolongs the service life of a road surface, has short maintenance time, can open traffic within 1-3 days, and can be used for asphalt concrete paving materials, asphalt pavement patching materials, slurry seal for maintenance, micro-surfacing and preparation of asphalt mortar for high-speed railways.

Description

Water-soluble phenolic resin modified emulsified asphalt concrete, and preparation method and application thereof
Technical Field
The invention belongs to the field of road engineering, relates to emulsified asphalt concrete and a preparation method thereof, and particularly relates to water-soluble phenolic resin modified emulsified asphalt concrete and a preparation method thereof.
Background
The traditional cold-mix asphalt mixture can realize normal-temperature mixing construction to a certain extent and reduce energy consumption, but the cold-mix asphalt mixture has poor road performance, cannot meet the requirement of modern roads on asphalt materials, and can only be applied to paving low-quality roads or repairing in a small range.
The phenolic resin has the advantages of easily available raw materials, high mechanical strength, stable performance and excellent high-temperature resistance, and can maintain the structural integrity and the dimensional stability even at very high temperature. Is compatible with various organic and inorganic fillers and has good binding effect. The water-soluble phenolic resin has the advantages of environmental protection and low cost, meets the current economic and environmental development requirements, and has wide application prospect and good social value. At present, the water-soluble phenolic resin is widely applied to the manufacture of adhesives and coatings, and the research of the application of the water-soluble phenolic resin to roads is not reported yet.
The water-soluble phenolic resin emulsion serving as an asphalt modifier has excellent physical and chemical properties, can improve the acid resistance and alkali resistance of asphalt and the corrosion of an organic solvent to the asphalt, improve the high-temperature and low-temperature properties of the asphalt, reduce the sensitivity of the asphalt to temperature, increase the elasticity of the asphalt, reduce the aging tendency of the asphalt, improve the adhesion of the asphalt and stone, improve the fatigue resistance of the asphalt and comprehensively improve the pavement performance of emulsified asphalt.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a water-soluble phenolic resin modified emulsified asphalt concrete, a preparation method and application thereof. And the water-soluble phenolic resin plays roles of strengthening, permeability resistance and chemical resistance after being added, and does not crack.
The invention provides a water-soluble phenolic resin modified emulsified asphalt concrete, which comprises the following components:
mineral aggregate;
water-soluble phenolic resin modified emulsified asphalt mixed and stirred with the mineral aggregate;
wherein the weight ratio of the mineral aggregate to the water-soluble phenolic resin modified emulsified asphalt is 100:5-40, preferably 100:10-30, and more preferably 100: 20.
In particular, the mineral aggregate is basalt or limestone or other stone meeting the current technical standard specification.
In particular, the mineral aggregate consists of coarse aggregate, fine aggregate and filler in a weight ratio of 30-70:30-70:5-10, preferably 53:40: 7; the nominal particle size of the coarse aggregate is delta larger than 4.75mm, and the nominal particle size of the fine aggregate is as follows: delta is less than or equal to 4.75mm, and the nominal particle size of the filler is delta is less than or equal to 0.075 mm.
The water-soluble phenolic resin modified emulsified asphalt is prepared by the following steps:
A) preparation of soap solution
Mixing the cationic emulsifier with water, and stirring to obtain cationic soap solution;
B) preparation of water-soluble phenolic resin modified liquid
Adding phenolic compounds into the cationic soap liquid under the stirring state to prepare phenolic compound-cationic soap liquid mixed liquid; adding an acid catalyst and an aldehyde compound into the phenolic compound-cationic soap liquid mixed solution in 2 batches to perform polycondensation reaction for 2 times to obtain polycondensation reaction mixed solution; then adding an acidic pH regulator to prepare a water-soluble phenolic resin modified solution;
C) preparation of modified emulsified asphalt
And C, heating the asphalt, adding the heated asphalt into the water-soluble phenolic resin modified solution prepared in the step B, and uniformly mixing to prepare the water-soluble phenolic resin modified emulsified asphalt.
Wherein, the cationic emulsifier in the step A is one or more of dodecyl ammonium chloride, hexadecyl trimethyl ammonium bromide or hexadecyl pyridine bromide.
Particularly, the weight ratio of the cationic emulsifier to water is 2-8:100, preferably 4 to 5:100, namely the mass percent concentration of the soap solution is 2-8%, preferably 4-5%.
In particular, the stirring speed in the step A is 500-1000r/min, preferably 1000 r/min; the stirring temperature is 50-60 ℃.
Wherein, the phenolic compound in the step B is one or more of phenol, cresol, xylenol, tert-butyl phenol or resorcinol; the aldehyde compound is formaldehyde or furfural; the acid catalyst is selected from hydrochloric acid or oxalic acid; the acidic pH regulator is hydrochloric acid solution or oxalic acid solution.
Particularly, the weight ratio of the phenolic compound to the cationic soap solution is 1: 1.4-1.7; the molar ratio of the phenolic compound to the aldehyde compound is 1:07-1.02, preferably 1:0.75-1.00, more preferably 1: 0.78-0.97, and adjusting the pH of the polycondensation reaction mixed solution to 1.9-2.5 by adopting an acidic pH regulator.
In particular, the aldehyde compound is formaldehyde aqueous solution, preferably 40% formaldehyde aqueous solution in percentage by mass; the acid catalyst is selected from a hydrochloric acid solution with the concentration of 12 mol/L.
Wherein the molar ratio of the acid catalyst added in the first batch to the phenolic compound is 0.05-0.1: 1, preferably 0.07: 1; the molar ratio of the aldehyde compound added in the first batch to the phenolic compound is 0.6-0.85: 1, preferably 0.62 to 0.81: 1; the molar ratio of the acidic catalyst to the phenolic compound added in the second batch is 0.02-0.04: 1, preferably 0.03: 1; the molar ratio of the aldehyde compound to the phenolic compound added in the second batch is 0.15-0.17: 1, preferably 0.16: 1.
in particular, the temperature of the first polycondensation reaction is 60 to 70 ℃, preferably 65 ℃; the first polycondensation reaction time is 40-60min, preferably 50 min; the temperature of the second polycondensation reaction is 85-95 ℃, and the preferred temperature is 90 ℃; the second polycondensation reaction time is 10-40min, preferably 30 min.
In particular, after the second addition of the acidic catalyst, the mixture is stirred for 10 to 30min, preferably 20min, and then the second batch of the aldehyde compound is added.
In particular, the stirring rate during the polycondensation reaction is 700-1500r/min, preferably 1000 r/min.
Wherein, the water-soluble phenolic resin modified liquid is added after the asphalt is heated to the temperature of 100-150 ℃ in the step C.
Particularly, the water-soluble phenolic resin modification liquid is added after the asphalt is heated to the temperature of 140-150 ℃; the weight ratio of the asphalt to the water-soluble phenolic resin modified liquid is 100:10-200, preferably 100:50-70, more preferably 100: 60.
Particularly, the asphalt and the water-soluble phenolic resin modified liquid are mixed under the stirring state, and the stirring speed is 1000-3000r/min, preferably 1000 r/min; the mixing time is 2-5min, preferably 3 min.
The water-soluble phenolic resin modified emulsified asphalt is prepared by the following steps:
a) preparation of soap solution
Mixing anionic emulsifier with water, and stirring to obtain anionic soap solution;
b) preparation of water-soluble phenolic resin modified liquid
Adding phenolic compounds into the anionic soap liquid under the stirring state to prepare phenolic compound-anionic soap liquid mixed liquid; adding alkaline catalyst and aldehyde compound into the phenolic compound-anion soap liquid mixed solution in 2 batches, and carrying out polycondensation reaction for 2 times to obtain polycondensation reaction mixed solution; then adding an alkaline pH regulator to prepare a water-soluble phenolic resin modified solution;
c) preparation of modified emulsified asphalt
And (c) heating the asphalt, adding the heated asphalt into the water-soluble phenolic resin modified solution prepared in the step (b), and uniformly mixing to prepare the water-soluble phenolic resin modified emulsified asphalt.
Wherein, the anionic emulsifier in the step a) is one or more of sodium dodecyl sulfate, sodium dodecyl sulfate or sodium dodecyl benzene sulfonate.
Particularly, the weight ratio of the anionic emulsifier to water is 2-8:100, preferably 4 to 5:100, namely the mass percent concentration of the soap solution is 2-8%, preferably 4-5%; the stirring speed was 500 and 1000 rpm.
In particular, the stirring speed in the step a is 500-1000r/min, and is preferably 1000 r/min; the stirring temperature is 50-60 ℃.
Wherein, the phenolic compound in the step b) is one or more of phenol, cresol, xylenol, tert-butyl phenol or resorcinol; the aldehyde compound is formaldehyde or furfural; the alkaline catalyst is selected from sodium hydroxide, potassium hydroxide or ammonia water; the alkaline pH regulator is sodium hydroxide solution or potassium hydroxide solution; the stirring speed was 500 and 1000 rpm.
Particularly, the weight ratio of the phenolic compound to the anionic soap liquid is 1: 3-5; the molar ratio of the phenolic compound to the aldehyde compound is 1:2 to 4, preferably 1:2.6 to 3.75, and more preferably 1:3.02 to 3.46; and adjusting the pH of the polycondensation reaction mixed liquid to 11-12 by adopting an alkaline pH regulator.
In particular, the aldehyde compound is selected from an aqueous formaldehyde solution, preferably an aqueous formaldehyde solution with a mass percentage concentration of 40%.
Wherein the molar ratio of the basic catalyst added in the first batch to the phenolic compound is 0.05-0.1: 1, preferably 0.07: 1; the molar ratio of the aldehyde compound added in the first batch to the phenolic compound is 2-3: 1, preferably 2.4 to 2.75: 1; the molar ratio of the basic catalyst to the phenolic compound added in the second batch is 0.02-0.04: 1, preferably 0.03: 1; the molar ratio of the aldehyde compound to the phenolic compound added in the second batch is between 0.6 and 0.75: 1, preferably 0.62 to 0.71: 1.
in particular, the temperature of the first polycondensation reaction is 60 to 70 ℃, preferably 65 ℃; the first polycondensation reaction time is 40-60min, preferably 50 min; the temperature of the second polycondensation reaction is 85-95 ℃, and the preferred temperature is 90 ℃; the second polycondensation reaction time is 20-40min, preferably 30 min.
In particular, after the second addition of the basic catalyst, the mixture is stirred for 10 to 30min, preferably 20min, and then the second batch of the aldehyde compound is added.
In particular, the stirring rate during the polycondensation reaction is 700-1500r/min, preferably 1000 r/min.
Wherein, the asphalt is heated to the temperature of 100-150 ℃ in the step c, and then the water-soluble phenolic resin modification liquid is added.
Particularly, the water-soluble phenolic resin modification liquid is added after the asphalt is heated to the temperature of 140-150 ℃; the weight ratio of the asphalt to the water-soluble phenolic resin modified liquid is 100:10-200, preferably 100:50 to 70, more preferably 100: 60.
particularly, the asphalt and the water-soluble phenolic resin modified liquid are mixed under the stirring state, and the stirring speed is 1000-3000r/min, preferably 1000 r/min; the mixing time is 2-5min, preferably 3 min.
The water-soluble phenolic resin modified emulsified asphalt is prepared by the following steps:
1) preparation of soap solution
Mixing emulsifier and water, stirring well, and making into soap solution;
2) preparation of emulsified asphalt
Heating asphalt, adding into the soap solution prepared in the step 1), mixing, and emulsifying uniformly to prepare emulsified asphalt;
3) preparation of modified emulsified asphalt
And mixing the emulsified asphalt with the water-soluble phenolic resin solution under the stirring state, and uniformly stirring to prepare the water-soluble phenolic resin modified emulsified asphalt.
Wherein, the emulsifier in the step 1) is selected from cationic emulsifier and anionic emulsifier.
In particular, the cationic emulsifier is one or more of dodecyl ammonium chloride, hexadecyl trimethyl ammonium bromide or hexadecyl pyridine bromide; the anionic emulsifier is one or more of sodium dodecyl sulfate, sodium dodecyl sulfate or sodium dodecyl benzene sulfonate.
Particularly, the weight ratio of the cationic emulsifier to water is 2-8:100, preferably 4 to 5:100, namely the mass percent concentration of the cationic soap solution is 2-8%, preferably 4-5%; the weight ratio of the anionic emulsifier to water is 2-8:100, preferably 4 to 5:100, namely the mass percent concentration of the anionic soap liquid is 4-5%.
In particular, the stirring speed in the step 1) is 500-1000r/min, preferably 1000 r/min; the stirring temperature is 50-60 ℃.
Particularly, the method also comprises the steps of adding a pH regulator, regulating the pH value of the soap solution to be 5-6, and then adding the asphalt into the soap solution.
In particular, the pH regulator is selected from hydrochloric acid solution, preferably 6mol/L hydrochloric acid solution.
Wherein, the asphalt is heated to the temperature of 100-150 ℃ in the step 2), and then the soap liquid is added.
Particularly, the asphalt is heated to 140-150 ℃, and then the soap solution is added; the weight ratio of the asphalt to the soap liquid is 50-70: 100, preferably 60: 100.
particularly, the asphalt and the soap solution are mixed under the stirring state, and the stirring speed is 2000-3000r/min, preferably 2500 r/min; the mixing and emulsifying time is 2-5min, preferably 3 min.
Wherein the weight ratio of the emulsified asphalt to the water-soluble phenolic resin solution in the step 3) is 100:10-200, preferably 100:50 to 70, more preferably 100: 60.
in particular, the water-soluble phenolic resin solution has a solids content of 50 to 75%, preferably 50 to 55%.
In particular, the stirring speed is 2000-3000r/min, preferably 2500 r/min; the stirring time is 60 to 300s, preferably 90 to 110s, and more preferably 100 s.
The invention also provides a preparation method of the water-soluble phenolic resin modified emulsified asphalt concrete, which comprises the following steps in sequence:
A) preparing the soap solution
Mixing the cationic emulsifier with water, and stirring to obtain cationic soap solution;
B) preparing water-soluble phenolic resin modified liquid
Adding phenolic compounds into the cationic soap liquid under the stirring state to prepare phenolic compound-cationic soap liquid mixed liquid; adding an acid catalyst and an aldehyde compound into the phenolic compound-cationic soap liquid mixed solution in 2 batches to perform polycondensation reaction for 2 times to obtain polycondensation reaction mixed solution; then adding an acidic pH regulator to prepare a water-soluble phenolic resin modified solution;
C) preparing the modified emulsified asphalt
Heating asphalt, adding the heated asphalt into the water-soluble phenolic resin modified solution prepared in the step B), and uniformly mixing to prepare the water-soluble phenolic resin modified emulsified asphalt;
D) preparing the modified emulsified asphalt concrete
And (3) uniformly mixing the water-soluble phenolic resin modified emulsified asphalt and the mineral aggregate under the stirring state to obtain the modified emulsified asphalt.
Wherein, the stirring speed in the step A is 500-1000r/min, preferably 1000 r/min; the stirring temperature is 50-60 ℃.
And D, mixing the mineral aggregate and the water-soluble phenolic resin modified emulsified asphalt in the step D in a weight ratio of 100:5-40, preferably 100:10-30, more preferably 100: 20.
in particular, the mineral aggregate is basalt or limestone or other stone meeting the current technical standard specification.
In particular, the mineral aggregate consists of coarse aggregate, fine aggregate and filler in a weight ratio of 30-70:30-70:5-10, preferably 53:40: 7; the nominal particle size of the coarse aggregate is delta larger than 4.75mm, and the nominal particle size of the fine aggregate is as follows: delta is less than or equal to 4.75mm, and the nominal particle size of the filler is delta is less than or equal to 0.075 mm.
In particular, the stirring speed is 2000-3000r/min, preferably 2500 r/min; the stirring time is 60 to 300s, preferably 90 to 110s, and more preferably 100 s.
The invention provides a preparation method of water-soluble phenolic resin modified emulsified asphalt concrete, which comprises the following steps in sequence:
a) preparation of soap solution
Mixing anionic emulsifier with water, and stirring to obtain anionic soap solution;
b) preparation of water-soluble phenolic resin modified liquid
Adding phenolic compounds into the anionic soap liquid under the stirring state to prepare phenolic compound-anionic soap liquid mixed liquid; adding alkaline catalyst and aldehyde compound into the phenolic compound-anion soap liquid mixed solution in 2 batches, and carrying out polycondensation reaction for 2 times to obtain polycondensation reaction mixed solution; then adding an alkaline pH regulator to prepare a water-soluble phenolic resin modified solution;
c) preparation of modified emulsified asphalt
Heating asphalt, adding the heated asphalt into the water-soluble phenolic resin modified solution prepared in the step b), and uniformly mixing to prepare the water-soluble phenolic resin modified emulsified asphalt;
d) preparation of modified emulsified asphalt concrete
And (3) uniformly mixing the water-soluble phenolic resin modified emulsified asphalt and the mineral aggregate under the stirring state to obtain the modified emulsified asphalt.
Wherein, the stirring speed in the step a is 500-1000r/min, preferably 1000 r/min; the stirring temperature is 50-60 ℃.
In the step d, the weight ratio of the mineral aggregate to the water-soluble phenolic resin modified emulsified asphalt is 100:5-40, preferably 100:10-30, more preferably 100: 20.
in particular, the mineral aggregate is basalt or limestone or other stone meeting the current technical standard specification.
In particular, the mineral aggregate consists of coarse aggregate, fine aggregate and filler in a weight ratio of 30-70:30-70:5-10, preferably 53:40: 7; the nominal particle size of the coarse aggregate is delta larger than 4.75mm, and the nominal particle size of the fine aggregate is as follows: delta is less than or equal to 4.75mm, and the nominal particle size of the filler is delta is less than or equal to 0.075 mm.
In particular, the stirring rate is 2000-3000 rpm; the stirring time is 60 to 300s, preferably 90 to 110s, and more preferably 100 s.
The invention also provides a preparation method of the water-soluble phenolic resin modified emulsified asphalt concrete, which comprises the following steps in sequence:
1) preparation of soap solution
Mixing emulsifier and water, stirring well, and making into soap solution;
2) preparation of emulsified asphalt
Heating asphalt, adding into the soap solution prepared in the step 1), mixing, and emulsifying uniformly to prepare emulsified asphalt;
3) preparation of modified emulsified asphalt
Under the stirring state, mixing the emulsified asphalt with a water-soluble phenolic resin solution, and uniformly stirring to prepare the water-soluble phenolic resin modified emulsified asphalt;
4) preparation of modified emulsified asphalt concrete
And (3) uniformly mixing the water-soluble phenolic resin modified emulsified asphalt and the mineral aggregate under the stirring state to obtain the modified emulsified asphalt.
Wherein, the emulsifier in the step 1) is selected from cationic emulsifier and anionic emulsifier.
In particular, the cationic emulsifier is one or more of dodecyl ammonium chloride, hexadecyl trimethyl ammonium bromide or hexadecyl pyridine bromide; the anionic emulsifier is one or more of sodium dodecyl sulfate, sodium dodecyl sulfate or sodium dodecyl benzene sulfonate.
Particularly, the weight ratio of the cationic emulsifier to water is 2-8:100, preferably 4 to 5:100, namely the mass percent concentration of the cationic soap solution is 4-5%; the weight ratio of the anionic emulsifier to water is 2-8:100, preferably 4 to 5:100, namely the mass percent concentration of the anionic soap liquid is 4-5%.
In particular, the stirring speed in the step 1) is 500-1000r/min, preferably 1000 r/min; the stirring temperature is 50-60 ℃.
Wherein, the asphalt is heated to the temperature of 100-150 ℃ in the step 2), and then the soap liquid is added.
Particularly, the asphalt is heated to 140-150 ℃, and then the soap solution is added; the weight ratio of the asphalt to the soap liquid is 50-70: 100, preferably 60: 100.
particularly, the asphalt and the soap solution are mixed under the stirring state, and the stirring speed is 2000-3000r/min, preferably 2500 r/min; the mixing and emulsifying time is 2-5min, preferably 3 min.
Wherein the weight ratio of the emulsified asphalt to the water-soluble phenolic resin solution in the step 3) is 100:10 to 200, preferably 100:50 to 70, and more preferably 100: 60.
In particular, the water-soluble phenolic resin solution has a solids content of 50 to 75%, preferably 50 to 55%.
In particular, the stirring speed is 2000-3000r/min, preferably 2500 r/min; the stirring time is 60 to 300s, preferably 90 to 110s, and more preferably 100 s.
Wherein the weight ratio of the mineral aggregate to the water-soluble phenolic resin modified emulsified asphalt in the step 4) is 100:5-40, preferably 100:10-30, more preferably 100: 20.
in particular, the mineral aggregate is basalt or limestone or other stone meeting the current technical standard specification.
In particular, the mineral aggregate consists of coarse aggregate, fine aggregate and filler in a weight ratio of 30-70:30-70:5-10, preferably 53:40: 7; the nominal particle size of the coarse aggregate is delta larger than 4.75mm, and the nominal particle size of the fine aggregate is as follows: delta is less than or equal to 4.75mm, and the nominal particle size of the filler is delta is less than or equal to 0.075 mm.
The invention also provides a water-soluble phenolic resin modified emulsified asphalt concrete, which comprises mineral aggregate, a water-soluble phenolic resin solution and emulsified asphalt; wherein the weight ratio of the mineral aggregate to the water-soluble phenolic resin solution to the emulsified asphalt is 100:1-20:4-20, preferably 100:5-15:5-15, and more preferably 100:10: 10.
Wherein the mineral aggregate is basalt or limestone or other stones meeting the current technical standard specification; the solid content of the water-soluble phenolic resin solution is 50-75%, preferably 50-55%.
In particular, the mineral aggregate consists of coarse aggregate, fine aggregate and filler in a weight ratio of 30-70:30-70:5-10, preferably 53:40: 7; the nominal particle size of the coarse aggregate is delta larger than 4.75mm, and the nominal particle size of the fine aggregate is as follows: delta is less than or equal to 4.75mm, and the nominal particle size of the filler is delta is less than or equal to 0.075 mm.
The emulsified asphalt is prepared by the following steps:
I) preparation of soap solution
Mixing emulsifier and water, stirring well, and making into soap solution;
II) preparation of emulsified asphalt
Heating asphalt, adding into the soap solution prepared in the step 1), mixing, and emulsifying uniformly to prepare emulsified asphalt.
In particular, the emulsifier in the step I) is selected from cationic emulsifier and anionic emulsifier.
In particular, the cationic emulsifier is one or more of dodecyl ammonium chloride, hexadecyl trimethyl ammonium bromide or hexadecyl pyridine bromide; the anionic emulsifier is one or more of sodium dodecyl sulfate, sodium dodecyl sulfate or sodium dodecyl benzene sulfonate.
Particularly, the weight ratio of the cationic emulsifier to water is 2-8:100, preferably 4 to 5:100, namely the mass percent concentration of the cationic soap solution is 4-5%; the weight ratio of the anionic emulsifier to water is 2-8:100, preferably 4 to 5:100, namely the mass percent concentration of the anionic soap liquid is 4-5%.
In particular, the stirring speed in the step I is 500-1000r/min, preferably 1000 r/min; the stirring temperature is 50-60 ℃.
Wherein, the asphalt is heated to the temperature of 100-150 ℃ in the step II), and then the soap liquid is added.
Particularly, the asphalt is heated to 140-150 ℃, and then the soap solution is added; the weight ratio of the asphalt to the soap liquid is 50-70: 100, preferably 60: 100.
particularly, the asphalt and the soap solution are mixed under the stirring state, and the stirring speed is 2000-3000r/min, preferably 2500 r/min; the mixing and emulsifying time is 2-5min, preferably 3 min.
The invention also provides a preparation method of the water-soluble phenolic resin modified emulsified asphalt concrete, which comprises the following steps in sequence:
I) preparation of soap solution
Mixing emulsifier and water, stirring well, and making into soap solution;
II) preparation of emulsified asphalt
Heating asphalt, adding into the soap solution prepared in the step I), mixing, and emulsifying uniformly to prepare emulsified asphalt;
III) preparation of modified emulsified asphalt concrete
And (3) under the stirring state, uniformly mixing the emulsified asphalt, the water-soluble phenolic resin solution and the mineral aggregate to obtain the emulsified asphalt.
Wherein, the stirring speed in the step I is 500-1000r/min, preferably 1000 r/min; the stirring temperature is 50-60 ℃.
Wherein the weight ratio of the water-soluble phenolic resin solution, the emulsified asphalt and the mineral aggregate in the step III) is 1-20: 4-20: 100, preferably 10: 10: 100.
in particular, the water-soluble phenolic resin solution has a solids content of 50 to 75%, preferably 50 to 55%.
In particular, the stirring speed is 2000-3000r/min, preferably 2500 r/min; the stirring time is 60 to 300s, preferably 90 to 110s, and more preferably 100 s.
The invention further provides a method for preparing the water-soluble phenolic resin modified emulsified asphalt concrete for asphalt concrete paving materials, asphalt pavement patching materials, slurry seal for maintenance, micro-surfacing and high-speed railway asphalt mortar.
The invention uses the water-soluble phenolic resin to modify the emulsified asphalt, can improve the high-temperature and low-temperature performances of the asphalt, reduce the sensitivity of the asphalt to temperature, increase the elasticity of the asphalt, reduce the aging tendency of the asphalt, improve the adhesion of the asphalt and stone materials, and improve the fatigue resistance of the asphalt.
The invention has the advantages and beneficial technical effects as follows:
1. the water-soluble phenolic resin modified emulsified asphalt emulsion adopted for the first time has the advantages of simple process, no organic solvent, no pollution, safety, reliability, good compatibility, easy modification and the like.
2. The invention can form a high-performance composite asphalt system with a space network structure by utilizing the self-crosslinking function of the water-soluble phenolic resin, greatly improves the performance of the emulsified asphalt and has stable storage.
3. The water-soluble phenolic resin modified emulsified asphalt concrete prepared by the invention is a novel pavement environment-friendly material, not only has the advantages of the traditional cold-mixed asphalt concrete, but also has excellent mechanical property and stability, the pavement performance is excellent, the service life of the pavement is greatly prolonged, the maintenance time is shortened, and the traffic can be opened in 1-3 days.
4. The water-soluble phenolic resin modified emulsified asphalt concrete prepared by the invention can be used as cold-mixing cold-paving asphalt concrete, can be applied to paving or repairing asphalt pavements, can also be applied to cold-mixing materials, slurry sealing, micro-surfacing and the like, is simple to operate in production and construction, is wide in application, is not limited by conditions such as transportation, repairing and dispersion and the like, reduces energy consumption and emission of toxic and harmful gases in an asphalt heating process compared with the traditional hot-state technology of hot-mixing hot-paving mixtures, and realizes energy conservation and emission reduction.
Detailed Description
The invention will be further described with reference to specific embodiments, and the advantages and features of the invention will become apparent as the description proceeds. These examples are illustrative only and do not limit the scope of the present invention in any way. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention, and that such changes and modifications may be made without departing from the spirit and scope of the invention.
Example 1 (thermoplastic)
1. Preparation of soap solution
Adding dodecyl ammonium chloride serving as a cationic emulsifier into deionized water, uniformly stirring at 60 ℃ and at the speed of 1000r/min, and dissolving the dodecyl ammonium chloride in water to prepare cationic soap solution, wherein the mass ratio of the cationic emulsifier to the water is 4:100, namely the mass percent concentration of the cationic soap solution is 4 percent;
the dosage of the emulsifier in the embodiment of the invention is 2 g; the amount of deionized water was 50g and the resulting cationic soap solution was 52 g.
In this embodiment, the mass percentage concentration of the cationic soap solution is illustrated as 4% (i.e. the mass ratio of the emulsifier to the water is 4:100), and other cationic soap solutions with a concentration of 2-8% (preferably 4-5% (i.e. the mass ratio of the emulsifier to the water is 2-8:100) are suitable for the present invention. The cationic emulsifier in the present invention is exemplified by dodecylammonium chloride, and other cationic emulsifiers such as cetyltrimethylammonium bromide, cetylpyridinium bromide, etc. are suitable for use in the present invention in addition to dodecylammonium chloride.
2. Preparation of water-soluble phenolic resin modified liquid
2-1) dripping phenol (35g) which is a phenolic compound into the cationic soap solution prepared in the step 1), heating to 65 ℃, and dissolving phenol to prepare a phenolic compound-cationic soap solution mixed solution; then adding a first batch of catalyst hydrochloric acid solution (12 mol/L) and uniformly mixing; then under the condition of keeping the temperature at 65 ℃ in a stirring state, adding a first batch of formaldehyde aqueous solution (the mass percentage concentration is 40%) to perform a first polycondensation reaction, and reacting for 50min to obtain a first polycondensation reaction mixed solution; wherein the stirring speed is 1000 r/min; the weight ratio of the phenol compound phenol to the soap solution is 35: 52; the mole ratio of the hydrochloric acid in the first catalyst hydrochloric acid solution to the phenol compound is 0.07: 1 (typically 0.05-0.1: 1); the molar ratio of formaldehyde to phenol compound in the first formaldehyde aqueous solution is 0.81: 1;
2-2) adding a second catalyst hydrochloric acid solution (12mol// L) into the first polycondensation reaction mixed solution under the stirring state, stirring uniformly (about 20min), continuing to heat to enable the temperature of the mixed solution to reach and store 90 ℃, then adding a second formaldehyde aqueous solution (with the mass percentage concentration of 40%) to perform a second polycondensation reaction, and performing the second polycondensation reaction for 30min (usually 10-40min) to obtain a reddish brown second polycondensation reaction mixed solution, wherein the stirring speed is 1000 r/min; the molar ratio of the hydrochloric acid in the second batch of catalyst hydrochloric acid solution to the phenolic compound phenol is 0.03: 1 (typically 0.02-0.04: 1); the molar ratio of formaldehyde to phenol compound in the second formaldehyde aqueous solution is 0.16: 1;
2-3) adding a pH regulator hydrochloric acid solution into the reddish brown second polycondensation reaction mixed solution, and regulating the pH of the polycondensation reaction mixed solution to 1.9-2.5 to prepare a water-soluble phenolic resin modified solution; wherein the concentration of the pH regulator hydrochloric acid solution is 6 mol/L.
In the embodiment of the invention, hydrochloric acid solutions with the concentration of 12mol/L are selected as the first and second catalyst hydrochloric acid solutions, and other hydrochloric acid solutions with the concentration of 10-12mol/L are also suitable for the invention; the first and second formaldehyde aqueous solutions are 40% formaldehyde aqueous solutions by mass percent. In the embodiment of the invention, besides using the hydrochloric acid solution with the concentration of 6mol/L, other hydrochloric acid solutions with other concentrations, such as 5-8mol/L, are suitable for the invention; besides hydrochloric acid solutions, other acidic solutions such as sulfuric acid solutions, nitric acid solutions are suitable for use in the present invention;
in the example of the invention, 35g (0.37mol) of phenol, 52g of soap solution, 2.158ml of first catalyst hydrochloric acid solution, 18g of first formaldehyde aqueous solution (containing 0.3mol of formaldehyde), 0.925ml of second catalyst hydrochloric acid solution and 4.5g of second formaldehyde aqueous solution (containing 0.06mol of formaldehyde) are used to prepare 112.58g of water-soluble phenolic resin modified solution.
The molar ratio of the phenolic compound to the aldehyde compound in the process of preparing the water-soluble phenolic resin modified liquid is 1: 0.97.
3. preparation of modified emulsified asphalt
Heating the asphalt to 150 ℃ (usually 140 ℃ and 160 ℃, preferably 150 ℃), and then slowly adding the asphalt into the water-soluble phenolic resin modification liquid prepared in the step 2) under the stirring state; and uniformly mixing to obtain the water-soluble phenolic resin modified emulsified asphalt, wherein the weight ratio of the asphalt to the water-soluble phenolic resin modified solution is 100:60 (typically 100:10-200, preferably 100:50-70, and more preferably 100: 60), and a stirring rate of 2500r/min (typically 2000 and 3000 rpm); stirring for 3min (usually 2-5min, preferably 3 min);
in the embodiment of the invention, 100g of asphalt is heated to 150 ℃ and then added into 60g of modified water-soluble phenolic resin mixed solution, and the mixture is stirred for 3min at the speed of 2500r/min, so that the water-soluble phenolic resin modified emulsified asphalt is obtained.
4. Preparation of modified emulsified asphalt concrete
Under the stirring state, putting the water-soluble phenolic resin modified emulsified asphalt and mineral aggregate into a mixing pot, stirring for 150s, and uniformly mixing to obtain the modified emulsified asphalt concrete, wherein the weight ratio of the water-soluble phenolic resin modified emulsified asphalt to the mineral aggregate is 20:100 (typically 10-30:100, preferably 20: 100); the mineral aggregate is basalt; the aggregate comprises coarse aggregate, fine aggregate and filler, the weight ratio of the coarse aggregate to the fine aggregate to the filler is 53:40:7, and the nominal particle size of the coarse aggregate is as follows: is more than 4.75mm, and the nominal grain diameter of the fine aggregate is as follows: delta is less than or equal to 4.75mm, and the nominal particle size of the filler is delta is less than or equal to 0.075 mm;
in the embodiment of the invention, 100g of water-soluble phenolic resin modified emulsified asphalt is placed in a mixing pot, then 500g of mineral aggregate is added, and the mixture is stirred and mixed uniformly to obtain the modified emulsified asphalt concrete.
Example 2 (thermoplastic)
1. Preparation of soap solution
The same procedure was used to prepare the soap solution as in example 1.
2. Preparation of water-soluble phenolic resin modified liquid
2-1) dripping cresol (35g, 0.324mol) which is a phenolic compound into the cationic soap solution prepared in the step 1), heating to 65 +/-5 ℃, and dissolving phenol to prepare a phenolic compound-cationic soap solution mixed solution; then adding a first batch of catalyst hydrochloric acid solution, and uniformly mixing; then under the condition of keeping the temperature at 65 +/-5 ℃ under the stirring state, adding a first batch of formaldehyde aqueous solution to carry out a first polycondensation reaction, and obtaining a first polycondensation reaction mixed solution after reacting for 60min (usually 40-60min, preferably 50 min); wherein the stirring speed is 1000 r/min; the mass ratio of the phenol compound cresol to the soap liquid is 35: 52; the molar ratio of the hydrochloric acid in the first catalyst hydrochloric acid solution to the phenolic compound cresol is 0.07: 1 (typically 0.05-0.1: 1); the molar ratio of formaldehyde to the phenolic compound cresol in the first aqueous formaldehyde solution was 0.62: 1;
2-2) adding a second catalyst hydrochloric acid solution into the first polycondensation reaction mixed solution under the stirring state, stirring uniformly (usually 15-25min, preferably 20min), continuing to heat until the temperature of the mixed solution reaches 90 +/-5 ℃ (usually 90 ℃), then adding a second formaldehyde aqueous solution to perform a second polycondensation reaction, and performing the second polycondensation reaction for 30min to obtain a reddish brown second polycondensation reaction mixed solution, wherein the stirring speed is 1000 r/min; the molar ratio of the hydrochloric acid in the second batch of catalyst hydrochloric acid solution to the phenolic compound cresol is 0.03: 1 (typically 0.02-0.04: 1; the molar ratio of formaldehyde to the phenolic compound cresol in the second aqueous formaldehyde solution is 0.16: 1;
2-3) adding a pH regulator hydrochloric acid solution into the reddish brown second polycondensation reaction mixed solution, and regulating the pH of the polycondensation reaction mixed solution to 1.9-2.5 to prepare a water-soluble phenolic resin modified solution; wherein the concentration of the pH regulator hydrochloric acid solution is 6 mol/L.
In the examples of the present invention, the amount of cresol was 35g (0.324mol), the amount of soap solution prepared was 52g, the amount of first catalyst hydrochloric acid solution was 1.89ml, the amount of first aqueous formaldehyde solution was 15.5g (containing 0.20mol of formaldehyde), the amount of second catalyst hydrochloric acid solution was 0.81ml, and the amount of second aqueous formaldehyde solution was 4.0g (containing 0.053mol of formaldehyde), to obtain 109.2g of water-soluble phenol resin modified solution.
The molar ratio of the phenolic compound to the aldehyde compound in the process of preparing the water-soluble phenolic resin modified liquid is 1: 0.78.
3. preparation of modified emulsified asphalt
Heating the asphalt to 140 ℃ (usually 140 ℃ and 160 ℃, preferably 150 ℃), and then slowly adding the asphalt into the water-soluble phenolic resin modification liquid prepared in the step 2) under the stirring state; and uniformly mixing to obtain the water-soluble phenolic resin modified emulsified asphalt, wherein the weight ratio of the asphalt to the water-soluble phenolic resin modified solution is 100:50 (generally 100:10 to 200, preferably 100:50:70, and more preferably 100: 60), and a stirring rate of 2000 r/min; stirring for 5min (usually 2-5 min);
in the embodiment of the invention, 100g of asphalt is heated to 150 ℃, then added into 50g of water-soluble phenolic resin modified liquid, and stirred for 3min at the speed of 2500r/min, so as to obtain the water-soluble phenolic resin modified emulsified asphalt.
4. Preparation of modified emulsified asphalt concrete
Under the stirring state, the water-soluble phenolic resin modified emulsified asphalt and the mineral aggregate are placed in a mixing pot, stirred for 160s (usually 140-160s, preferably 150s) and uniformly mixed to obtain the modified emulsified asphalt concrete, wherein the weight ratio of the water-soluble phenolic resin modified emulsified asphalt to the mineral aggregate is 30:100 (typically 10-30:100, preferably 20: 100); the mineral aggregate is basalt; the mineral aggregate consists of coarse aggregate, fine aggregate and filler, the weight ratio of the coarse aggregate to the fine aggregate to the filler is 53:40:7, and the nominal particle size of the coarse aggregate is as follows: is more than 4.75mm, and the nominal grain diameter of the fine aggregate is as follows: delta is less than or equal to 4.75mm, and the nominal particle size of the filler is delta is less than or equal to 0.075 mm.
In the embodiment of the invention, 150g of water-soluble phenolic resin modified emulsified asphalt is placed in a mixing pot, and then 500g of mineral aggregate is added, stirred and mixed uniformly to obtain the modified emulsified asphalt concrete.
Example 2A (thermoplastic)
Except that the weight ratio of the asphalt to the water-soluble phenolic resin modified solution in the step 3 is 100: 200, namely, the same as in example 1 except that 50g of the asphalt was heated to 150 ℃ and added to 100g of the water-soluble phenol resin modified solution.
Example 3 (thermosetting)
1. Preparation of soap solution
Adding an anionic emulsifier sodium dodecyl sulfate into deionized water, uniformly stirring at the speed of 1000r/min and the temperature of 60 ℃ to dissolve the sodium dodecyl sulfate into the water to prepare an anionic soap solution, wherein the mass ratio of the anionic emulsifier to the water is 4.29:100, namely the mass percentage concentration of the soap liquid is 4.29 percent;
the dosage of the emulsifier in the embodiment of the invention is 3 g; the amount of deionized water was 70g and 73g of anionic soap solution was obtained.
In this embodiment, the percentage concentration by mass of the anionic soap solution is 4.29% (i.e. the ratio of the emulsifier to the water is 4.29:100), and other anionic soap solutions with a concentration of 2-8% (preferably 4-5% (i.e. the ratio of the emulsifier to the water is 2-8:100) are suitable for the present invention. The anionic emulsifier in the present invention is exemplified by sodium dodecyl sulfate, and other anionic emulsifiers such as sodium dodecyl sulfate or sodium dodecyl benzene sulfonate, etc. are suitable for use in the present invention in addition to sodium dodecyl sulfate.
2. Preparation of water-soluble phenolic resin modified liquid
2-1) accurately weighing 52g of the anionic soap liquid prepared in the step 1), dripping phenol compound into the anionic soap liquid, heating to 65 +/-5 ℃ to dissolve the phenol, and preparing a mixed liquid of the phenol compound and the anionic soap liquid; then adding a first batch of catalyst sodium hydroxide (usually dissolved by a small amount of deionized water), and uniformly mixing; then under the condition of keeping the temperature at 65 +/-5 ℃ under the stirring state, adding a first batch of formaldehyde aqueous solution to carry out a first polycondensation reaction, and reacting for 50min to obtain a first polycondensation reaction mixed solution; wherein the stirring speed is 1000 r/min; the weight ratio of the phenol compound phenol to the soap solution is 35: 52; the molar ratio of the first catalyst sodium hydroxide to the phenolic compound phenol was 0.07: 1 (typically 0.05-0.1: 1); the molar ratio of formaldehyde to phenol compound in the first aqueous formaldehyde solution was 2.41: 1;
2-2) adding a second batch of catalyst sodium hydroxide (usually dissolved by a small amount of deionized water) into the first polycondensation reaction mixed solution under the stirring state, stirring uniformly (usually 15-25min, preferably 20min), continuing to heat until the temperature of the mixed solution reaches and is preserved at 90 +/-5 ℃ (usually 90 ℃), then adding a second batch of formaldehyde aqueous solution to perform a second polycondensation reaction, and obtaining a reddish brown second polycondensation reaction mixed solution after 30min of the second polycondensation reaction, wherein the stirring speed is 1000 r/min; the molar ratio of the second batch of catalyst sodium hydroxide to the phenolic compound phenol was 0.03: 1 (typically 0.02-0.04: 1); the molar ratio of formaldehyde to phenol compound in the second formaldehyde aqueous solution was 0.62: 1;
2-3) adding a pH regulator sodium hydroxide solution into the reddish brown second polycondensation reaction mixed solution, and regulating the pH of the polycondensation reaction mixed solution to 11-12 to obtain a water-soluble phenolic resin modified solution; wherein, the concentration of the pH regulator sodium hydroxide solution is 1 percent.
In this example, the first and second formalin solutions were 40% by mass. In the embodiment of the invention, except for using 1% sodium hydroxide solution as the pH regulator, other 1% -5% sodium hydroxide solutions are suitable for the invention; besides sodium hydroxide solution, other alkaline solutions such as potassium hydroxide solution and the like are suitable for the pH regulator;
in the example of the invention, the amount of phenol was 35g (0.37mol), the amount of soap solution was 52g, the amount of sodium hydroxide in the first catalyst was 1.036g, the amount of aqueous formaldehyde solution in the first catalyst was 66.5g (containing 0.89mol of formaldehyde), the amount of sodium hydroxide in the second catalyst was 0.444g, and the amount of aqueous formaldehyde solution in the second catalyst was 17g (containing 0.23mol of formaldehyde), so that 171.98g of water-soluble phenolic resin modified solution was obtained.
The molar ratio of the phenolic compound to the aldehyde compound in the process of preparing the water-soluble phenolic resin modified liquid is 1: 3.03.
3. preparation of modified emulsified asphalt
Heating the asphalt to 150 ℃ (usually 140-; and uniformly mixing to obtain the water-soluble phenolic resin modified emulsified asphalt, wherein the weight ratio of the asphalt to the water-soluble phenolic resin modified solution is 100:60 (generally 100:10-200, preferably 100:50-70), and the stirring rate is 2500 r/min; stirring for 3 min;
in this example, 200g of asphalt was heated to 150 ℃ and then added to 120g of water-soluble phenol resin modified solution, and the mixture was stirred at 2500r/min for 3min to uniformly mix the asphalt with the water-soluble phenol resin modified solution, thereby obtaining water-soluble phenol resin modified emulsified asphalt.
4. Preparation of modified emulsified asphalt concrete
Under the stirring state, placing the water-soluble phenolic resin modified emulsified asphalt and mineral aggregate into a mixing pot, stirring for 150s (usually 140-: 100 (typically 10-30: 100); the mineral aggregate is basalt; the mineral aggregate consists of coarse aggregate, fine aggregate and filler, the weight ratio of the coarse aggregate to the fine aggregate to the filler is 53:40:7, and the nominal particle size of the coarse aggregate is as follows: is more than 4.75mm, and the nominal grain diameter of the fine aggregate is as follows: delta is less than or equal to 4.75mm, and the nominal particle size of the filler is delta is less than or equal to 0.075 mm.
In the embodiment of the invention, 200g of water-soluble phenolic resin modified emulsified asphalt is placed in a mixing pot, then 1000g of mineral aggregate is added, and the mixture is stirred and mixed uniformly to obtain the modified emulsified asphalt concrete.
Example 4 (thermosetting)
1. Preparation of soap solution
The same procedure as in example 3 was used to prepare the soap solution.
2. Preparation of water-soluble phenolic resin modified liquid
2-1) dripping cresol (35g) which is a phenolic compound into the anionic soap liquid prepared in the step 1), heating to 65 +/-5 ℃, and dissolving the cresol to prepare a phenolic compound-anionic soap liquid mixed solution; then adding a first batch of catalyst sodium hydroxide (usually dissolved by a small amount of deionized water), and uniformly mixing; then under the condition of keeping the temperature at 65 +/-5 ℃ under the stirring state, adding a first batch of formaldehyde aqueous solution to carry out a first polycondensation reaction, and reacting for 40min (usually 40-60min, preferably 50min) to obtain a first polycondensation reaction mixed solution; wherein the stirring speed is 1000 r/min; the weight ratio of the cresol of the phenolic compound to the soap solution is 35: 73; the molar ratio of the first catalyst sodium hydroxide to the phenolic compound cresol is 0.07: 1 (typically 0.05-0.1: 1); the molar ratio of formaldehyde to the phenolic compound cresol in the first aqueous formaldehyde solution was 2.75: 1;
2-2) adding a second batch of catalyst sodium hydroxide (usually dissolved by a small amount of deionized water) into the first polycondensation reaction mixed solution under the stirring state, stirring uniformly (usually 15-25min, preferably 20min), continuing to heat until the temperature of the mixed solution reaches 90 +/-5 ℃ (usually 90 ℃), then adding a second batch of formaldehyde aqueous solution, performing a second polycondensation reaction, and preparing a reddish brown second polycondensation reaction mixed solution after 40min (usually 20-40min, preferably 30min) of the second polycondensation reaction, wherein the stirring speed is 1000 r/min; the molar ratio of the second batch of catalyst sodium hydroxide to the phenolic compound cresol was 0.03: 1 (typically 0.02-0.04: 1); the molar ratio of formaldehyde to the phenolic compound cresol in the second formaldehyde aqueous solution is 0.71: 1;
2-3) adding a pH regulator sodium hydroxide solution into the reddish brown second polycondensation reaction mixed solution, and regulating the pH of the polycondensation reaction mixed solution to 11-12 to obtain a water-soluble phenolic resin modified solution; wherein, the concentration of the pH regulator sodium hydroxide solution is 1 percent.
In the examples of the present invention, the amount of cresol was 35g (0.324mol), the amount of soap solution prepared was 73g, the amount of sodium hydroxide in the first catalyst was 0.907g, the amount of aqueous formaldehyde solution in the first catalyst was 66.5g (containing 0.89mol of formaldehyde), the amount of sodium hydroxide in the second catalyst was 0.389g, and the amount of aqueous formaldehyde solution in the second catalyst was 17g (containing 0.23mol of formaldehyde), thereby obtaining 192.8-containing modified solution of water-soluble phenolic resin.
The molar ratio of the phenolic compound to the aldehyde compound in the process of preparing the water-soluble phenolic resin modified liquid is 1: 3.46.
3. preparation of modified emulsified asphalt
Heating the asphalt to 160 ℃ (usually 140-; and uniformly mixing to obtain the water-soluble phenolic resin modified emulsified asphalt, wherein the weight ratio of the asphalt to the water-soluble phenolic resin modified solution is 100: 70 (generally 100:10-200, preferably 100:50-70), and the stirring rate is 2500 r/min; stirring for 5 min;
in this example, 70g of asphalt was heated to 150 ℃ and then added to 100g of water-soluble phenol resin modified solution, and the mixture was stirred at 2500r/min for 5min to uniformly mix the asphalt and the water-soluble phenol resin modified solution, thereby obtaining water-soluble phenol resin modified emulsified asphalt.
4. Preparation of modified emulsified asphalt concrete
Under the stirring state, the water-soluble phenolic resin modified emulsified asphalt and the mineral aggregate are placed in a mixing pot, stirred for 140s (usually 140 and 160s, preferably 150s) and uniformly mixed, so as to obtain the modified emulsified asphalt concrete, wherein the weight ratio of the water-soluble phenolic resin modified emulsified asphalt to the mineral aggregate is 10: 100 (typically 10-30: 100); the mineral aggregate is basalt; the mineral aggregate consists of coarse aggregate, fine aggregate and filler, the weight ratio of the coarse aggregate to the fine aggregate to the filler is 53:40:7, and the nominal particle size of the coarse aggregate is as follows: is more than 4.75mm, and the nominal grain diameter of the fine aggregate is as follows: delta is less than or equal to 4.75mm, and the nominal particle size of the filler is delta is less than or equal to 0.075 mm.
In this embodiment, 100g of water-soluble phenolic resin modified emulsified asphalt is placed in a mixing pot, and then 1000g of mineral aggregate is added, and the mixture is stirred and mixed uniformly, so as to obtain the modified emulsified asphalt concrete.
Example 4A (thermosetting)
Except that the weight ratio of the asphalt to the water-soluble phenolic resin modified solution in the step 3 is 100: 200, namely, the same as in example 3 except that 50g of the asphalt was heated to 150 ℃ and added to 100g of the water-soluble phenol resin modified solution.
Example 5 (commercial thermoplastic 1)
1. Preparation of soap solution
Adding dodecyl ammonium chloride serving as a cationic emulsifier into deionized water, and stirring at 50 ℃ and 1000r/min to dissolve the dodecyl ammonium chloride into the water, wherein the mass ratio of the cationic emulsifier to the water is 5:100, respectively; then adding pH regulator hydrochloric acid solution (6mol/L), regulating pH of the mixed solution to 5-6, and making into soap solution;
the amount of emulsifier used in this example was 2 g; the amount of deionized water was 40g and the resulting soap solution was 42 g.
In this example, the mass ratio of the cationic emulsifier to water is 5:100, and other mixture ratios are 2-8:100 (preferably 4-5:100) are suitable for use in the present invention; the concentration of the hydrochloric acid solution for adjusting the pH of the soap solution is not limited to 6mol/L, but other concentrations, such as 5 to 8mol/L, are suitable for the present invention. In this example, cationic emulsifiers are used for illustration, and anionic emulsifiers such as sodium dodecylsulfate, sodium dodecylsulfate or sodium dodecylbenzenesulfonate are also suitable for use in the present invention.
2. Preparation of emulsified asphalt
Heating asphalt to 150 ℃ (usually 100-150 ℃, preferably 140-150 ℃), slowly adding the asphalt into the soap solution prepared in the step 1) under the stirring state, and uniformly stirring and emulsifying to prepare the emulsified asphalt, wherein the weight ratio of asphalt to soap solution is 60: 100 (usually 50-70: 100), stirring speed of 2500 r/min; stirring for 3min (usually 2-5 min);
in this example, 60g of asphalt was heated to 140 ℃ and then added to 100g of soap solution, and stirred and emulsified at 2500r/min for 3min to obtain emulsified asphalt.
3. Preparation of modified emulsified asphalt concrete
Under the stirring state, putting a water-soluble phenolic resin solution with the solid content of 55% (the solid content is generally 50-75%, preferably 50-55%), emulsified asphalt and mineral aggregate into a stirring pot, stirring for 100s (generally 60-300s, preferably 90-110s, further preferably 100s), and uniformly mixing to obtain the modified emulsified asphalt concrete, wherein the weight ratio of the water-soluble phenolic resin emulsion to the modified emulsified asphalt to the mineral aggregate is 10: 10: 100 (typically 5-15: 5-15: 100); the mineral aggregate is basalt; the aggregate comprises coarse aggregate, fine aggregate and filler, the weight ratio of the coarse aggregate to the fine aggregate to the filler is 53:40:7, and the nominal particle size of the coarse aggregate is as follows: is more than 4.75mm, and the nominal grain diameter of the fine aggregate is as follows: delta is less than or equal to 4.75mm, and the nominal particle size of the filler is delta is less than or equal to 0.075 mm; the water-soluble phenolic resin emulsion is a commercially available linear molecular type water-soluble phenolic resin emulsion, and the solid content of the water-soluble phenolic resin emulsion is 55%.
Example 6 (commercial thermoplastic 2)
1. Preparation of soap solution
Adding dodecyl ammonium chloride serving as a cationic emulsifier into deionized water, and stirring at 50 ℃ and 1000r/min to dissolve the dodecyl ammonium chloride into the water, wherein the mass ratio of the cationic emulsifier to the water is 5:100, respectively; then adding pH regulator hydrochloric acid solution (6mol/L), regulating pH of the mixed solution to 5-6, and making into soap solution;
the amount of emulsifier used in this example was 2 g; the amount of deionized water was 40g and the resulting soap solution was 42 g.
In this example, the mass ratio of the cationic emulsifier to water is 5:100, and other mixture ratios are 2-8:100 (preferably 4-5:100) are suitable for use in the present invention; the concentration of the hydrochloric acid solution for adjusting the pH of the soap solution is not limited to 6mol/L, but other concentrations, such as 5 to 8mol/L, are suitable for the present invention. In this example, cationic emulsifiers are used for illustration, and anionic emulsifiers such as sodium dodecylsulfate, sodium dodecylsulfate or sodium dodecylbenzenesulfonate are also suitable for use in the present invention.
2. Preparation of emulsified asphalt
Heating the asphalt to 140 ℃ (usually 100-150 ℃, preferably 140-150 ℃), slowly adding the asphalt into the soap solution prepared in the step 1) in a stirring state, and uniformly stirring and emulsifying to prepare the emulsified asphalt, wherein the weight ratio of the asphalt to the soap solution is 70: 100 (usually 50-70: 100), stirring speed of 2500 r/min; stirring for 2-5min (usually 3min is preferred);
in the examples of the present invention, 70g of asphalt was heated to 140 ℃ and then added to 100g of soap solution, and stirred and emulsified at 2500r/min for 5min (usually 2-5min, preferably 3min) to obtain emulsified asphalt.
3. Preparation of modified emulsified asphalt
Under the stirring state, putting a water-soluble phenolic resin solution with the solid content of 50% (the solid content is generally 50-75%, preferably 50-55%) and emulsified asphalt into a stirring pot, stirring for 100s (generally 90-110s), and uniformly mixing to obtain the modified emulsified asphalt, wherein the mass ratio of the emulsified asphalt to the water-soluble phenolic resin solution is 100:10-200, preferably 100:60, adding a solvent to the mixture; the water-soluble phenolic resin emulsion is a commercially available linear molecular type water-soluble phenolic resin emulsion, and the solid content of the water-soluble phenolic resin emulsion is 50 percent;
in the embodiment of the invention, 100g of emulsified asphalt and 60g of water-soluble phenolic resin emulsion are mixed, stirred for 100 seconds at normal temperature and modified to prepare the modified emulsified asphalt. The solids content of the water-soluble phenolic resin emulsion is illustrated by way of example at 50%, other solids contents, such as 50-75%, are suitable for use in the present invention.
4. Preparation of modified emulsified asphalt concrete
And (2) putting the modified emulsified asphalt and the mineral aggregate into a mixing pot under the stirring state, stirring for 90-110s (preferably 100s), and uniformly mixing to obtain the modified emulsified asphalt concrete, wherein the weight ratio of the modified emulsified asphalt to the mineral aggregate is 20:100 (typically 5-40:100, preferably 10-30: 100); the mineral aggregate is basalt; the aggregate comprises coarse aggregate, fine aggregate and filler, the weight ratio of the coarse aggregate to the fine aggregate to the filler is 53:40:7, and the nominal particle size of the coarse aggregate is as follows: is more than 4.75mm, and the nominal grain diameter of the fine aggregate is as follows: delta is less than or equal to 4.75mm, and the nominal particle size of the filler is delta is less than or equal to 0.075 mm.
Example 6A (thermoplastic)
Except that the weight ratio of the asphalt to the water-soluble phenolic resin solution in the step 3 is 100: 200, namely, 100g of pitch was heated to 150 ℃ and added to 200g of the water-soluble phenol resin solution, the same procedure as in example 6 was repeated.
Comparative example 1
The same as example 1 was conducted except that the soap solution prepared in step 1) was directly mixed with asphalt to prepare emulsified asphalt, and then the emulsified asphalt was mixed with mineral aggregates.
Comparative example 2
The same as example 3 was conducted except that the soap solution prepared in step 1) was directly mixed with asphalt to prepare emulsified asphalt, and then the emulsified asphalt was mixed with mineral aggregates.
Comparative example 3
Heating asphalt to 150 ℃, slowly adding the asphalt into mineral aggregate in a stirring pot under the stirring state, stirring for 150s at normal temperature, and uniformly mixing to obtain the hot-mix asphalt concrete, wherein the weight ratio of the asphalt to the mineral aggregate is 5:100, respectively; the mineral aggregate is basalt; the aggregate comprises coarse aggregate, fine aggregate and filler, the weight ratio of the coarse aggregate to the fine aggregate to the filler is 50:43:7, and the nominal particle size of the coarse aggregate is as follows: is more than 4.75mm, and the nominal grain diameter of the fine aggregate is as follows: delta is less than or equal to 4.75mm, and the nominal particle size of the filler is delta is less than or equal to 0.075 mm.
Test examples
The water-soluble phenol resin modified emulsified asphalt concrete prepared in examples 1 to 6 and the asphalt concrete prepared in comparative examples 1 to 4 were subjected to test piece molding, curing and Marshall performance test according to Standard test procedures for asphalt and asphalt mixtures for road engineering (JTJ E20-2011). The test results are shown in table 1.
TABLE 1 Marshall Performance test results
Figure BDA0001279371320000231
Note 1: the technical requirements are determined according to test specification for road engineering asphalt and asphalt mixture (JTJ E20-2011) T0709
As can be seen from Table 1, the emulsified asphalt concretes prepared in the comparative examples 1 and 2 have low strength, the Marshall stability index does not meet the technical requirements, and even trabecular sample strips can not be cut and prepared for testing, and the emulsified asphalt concretes can not be used for road paving; the water-soluble phenolic resin emulsified asphalt concrete prepared in the examples 1-6A has greatly improved Marshall stability which is more than 3 times that of the water-soluble phenolic resin emulsified asphalt concrete prepared in the comparative examples 1 and 2 under the modification action of the water-soluble phenolic resin, has excellent high and low temperature performances and meets the requirements of roads;
comparative example 3 is a conventional hot-mix asphalt concrete, and it can be seen from table 1 that the indexes of the water-soluble phenol resin emulsified asphalt concrete of the present invention are close to or even exceed those of the hot-mix asphalt concrete.
In conclusion, the water-soluble phenolic resin emulsified asphalt concrete prepared by the invention has high strength and excellent mechanical property, achieves the technical effect of hot-mixed asphalt concrete by a cold mixing process through the modification effect of the water-soluble phenolic resin, is a pavement material with excellent pavement performance, and can be widely applied to asphalt concrete paving materials, asphalt pavement repairing materials, slurry sealing for maintenance, micro-surfacing and preparation of asphalt mortar for high-speed railways.

Claims (9)

1. The water-soluble phenolic resin modified emulsified asphalt concrete is characterized by comprising the following components:
mineral aggregate;
water-soluble phenolic resin modified emulsified asphalt mixed and stirred with the mineral aggregate; wherein: the weight ratio of the mineral aggregate to the water-soluble phenolic resin modified emulsified asphalt is 100: 5-40;
the water-soluble phenolic resin modified emulsified asphalt is prepared by the following steps:
A) preparation of soap solution
Mixing the cationic emulsifier with water, and stirring to obtain cationic soap solution;
B) preparation of water-soluble phenolic resin modified liquid
Adding phenolic compounds into the cationic soap liquid under the stirring state to prepare phenolic compound-cationic soap liquid mixed liquid; adding an acid catalyst and an aldehyde compound into the phenolic compound-cationic soap liquid mixed solution in 2 batches to perform polycondensation reaction for 2 times to obtain polycondensation reaction mixed solution; then adding an acidic pH regulator to prepare a water-soluble phenolic resin modified solution;
C) preparation of modified emulsified asphalt
Heating the asphalt, adding the heated asphalt into the water-soluble phenolic resin modified solution prepared in the step B), and uniformly mixing to prepare the water-soluble phenolic resin modified emulsified asphalt.
2. The water-soluble phenolic resin modified emulsified asphalt concrete is characterized by comprising the following components:
mineral aggregate;
water-soluble phenolic resin modified emulsified asphalt mixed and stirred with the mineral aggregate; wherein: the weight ratio of the mineral aggregate to the water-soluble phenolic resin modified emulsified asphalt is 100: 5-40;
the water-soluble phenolic resin modified emulsified asphalt is prepared by the following steps:
a) preparation of soap solution
Mixing anionic emulsifier with water, and stirring to obtain anionic soap solution;
b) preparation of water-soluble phenolic resin modified liquid
Adding phenolic compounds into the anionic soap liquid under the stirring state to prepare phenolic compound-anionic soap liquid mixed liquid; adding alkaline catalyst and aldehyde compound into the phenolic compound-anion soap liquid mixed solution in 2 batches, and carrying out polycondensation reaction for 2 times to obtain polycondensation reaction mixed solution; then adding an alkaline pH regulator to prepare a water-soluble phenolic resin modified solution;
c) preparation of modified emulsified asphalt
And (c) heating the asphalt, adding the heated asphalt into the water-soluble phenolic resin modified solution prepared in the step (b), and uniformly mixing to prepare the water-soluble phenolic resin modified emulsified asphalt.
3. The water-soluble phenolic resin modified emulsified asphalt concrete is characterized by comprising the following components:
mineral aggregate;
water-soluble phenolic resin modified emulsified asphalt mixed and stirred with the mineral aggregate; wherein: the weight ratio of the mineral aggregate to the water-soluble phenolic resin modified emulsified asphalt is 100: 5-40;
the water-soluble phenolic resin modified emulsified asphalt is prepared by the following steps:
1) preparation of soap solution
Mixing emulsifier and water, stirring well, and making into soap solution;
2) preparation of emulsified asphalt
Heating asphalt, adding into the soap solution prepared in the step 1), mixing, and emulsifying uniformly to prepare emulsified asphalt;
3) preparation of modified emulsified asphalt
And (2) mixing the emulsified asphalt with a water-soluble phenolic resin solution under a stirring state, and uniformly stirring to prepare the water-soluble phenolic resin modified emulsified asphalt, wherein the solid content of the water-soluble phenolic resin solution is 50-75%.
4. The preparation method of the water-soluble phenolic resin modified emulsified asphalt concrete is characterized by comprising the following steps of:
A) preparing the soap solution
Mixing the cationic emulsifier with water, and stirring to obtain cationic soap solution;
B) preparing water-soluble phenolic resin modified liquid
Adding phenolic compounds into the cationic soap liquid under the stirring state to prepare phenolic compound-cationic soap liquid mixed liquid; adding an acid catalyst and an aldehyde compound into the phenolic compound-cationic soap liquid mixed solution in 2 batches to perform polycondensation reaction for 2 times to obtain polycondensation reaction mixed solution; then adding an acidic pH regulator to prepare a water-soluble phenolic resin modified solution;
C) preparing the modified emulsified asphalt
Heating asphalt, adding the heated asphalt into the water-soluble phenolic resin modified solution prepared in the step B), and uniformly mixing to prepare the water-soluble phenolic resin modified emulsified asphalt;
D) preparing the modified emulsified asphalt concrete
And (3) uniformly mixing the water-soluble phenolic resin modified emulsified asphalt and the mineral aggregate under the stirring state to obtain the modified emulsified asphalt.
5. The preparation method of the water-soluble phenolic resin modified emulsified asphalt concrete is characterized by comprising the following steps of:
a) preparation of soap solution
Mixing anionic emulsifier with water, and stirring to obtain anionic soap solution;
b) preparation of water-soluble phenolic resin modified liquid
Adding phenolic compounds into the anionic soap liquid under the stirring state to prepare phenolic compound-anionic soap liquid mixed liquid; adding alkaline catalyst and aldehyde compound into the phenolic compound-anion soap liquid mixed solution in 2 batches, and carrying out polycondensation reaction for 2 times to obtain polycondensation reaction mixed solution; then adding an alkaline pH regulator to prepare a water-soluble phenolic resin modified solution;
c) preparation of modified emulsified asphalt
Heating asphalt, adding the heated asphalt into the water-soluble phenolic resin modified solution prepared in the step b), and uniformly mixing to prepare the water-soluble phenolic resin modified emulsified asphalt;
d) preparation of modified emulsified asphalt concrete
And (3) uniformly mixing the water-soluble phenolic resin modified emulsified asphalt and the mineral aggregate under the stirring state to obtain the modified emulsified asphalt.
6. The preparation method of the water-soluble phenolic resin modified emulsified asphalt concrete is characterized by comprising the following steps of:
1) preparation of soap solution
Mixing emulsifier and water, stirring well, and making into soap solution;
2) preparation of emulsified asphalt
Heating asphalt, adding into the soap solution prepared in the step 1), mixing, and emulsifying uniformly to prepare emulsified asphalt;
3) preparation of modified emulsified asphalt
Under the stirring state, mixing the emulsified asphalt with a water-soluble phenolic resin solution, and uniformly stirring to prepare the water-soluble phenolic resin modified emulsified asphalt, wherein the solid content of the water-soluble phenolic resin solution is 50-75%;
4) preparation of modified emulsified asphalt concrete
And (3) uniformly mixing the water-soluble phenolic resin modified emulsified asphalt and the mineral aggregate under the stirring state to obtain the modified emulsified asphalt.
7. The water-soluble phenolic resin modified emulsified asphalt concrete is characterized by comprising mineral aggregate, a water-soluble phenolic resin solution and emulsified asphalt; wherein the weight ratio of the mineral aggregate to the water-soluble phenolic resin to the emulsified asphalt is 100:1-20: 4-20; wherein the solid content of the water-soluble phenolic resin solution is 50-75%; the emulsified asphalt is prepared by the following steps:
I) preparation of soap solution
Mixing emulsifier and water, stirring well, and making into soap solution;
II) preparation of emulsified asphalt
Heating asphalt, adding into the soap solution prepared in the step 1), mixing, and emulsifying uniformly to prepare emulsified asphalt.
8. The preparation method of the water-soluble phenolic resin modified emulsified asphalt concrete is characterized by comprising the following steps of:
I) preparation of soap solution
Mixing emulsifier and water, stirring well, and making into soap solution;
II) preparation of emulsified asphalt
Heating asphalt, adding into the soap solution prepared in the step 1), mixing, and emulsifying uniformly to prepare emulsified asphalt;
III) preparation of modified emulsified asphalt concrete
And (2) uniformly mixing the emulsified asphalt, the water-soluble phenolic resin solution and the mineral aggregate under the stirring state to obtain the water-soluble phenolic resin composite material, wherein the solid content of the water-soluble phenolic resin solution is 50-75%.
9. The water-soluble phenol resin modified emulsified asphalt concrete as claimed in claim 1 or 7, which is used for preparing asphalt concrete pavements, asphalt pavement patching materials, slurry seals for curing, micro-surfacing and high-speed railway asphalt mortar.
CN201710280513.6A 2017-04-26 2017-04-26 Water-soluble phenolic resin modified emulsified asphalt concrete, and preparation method and application thereof Expired - Fee Related CN108793830B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710280513.6A CN108793830B (en) 2017-04-26 2017-04-26 Water-soluble phenolic resin modified emulsified asphalt concrete, and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710280513.6A CN108793830B (en) 2017-04-26 2017-04-26 Water-soluble phenolic resin modified emulsified asphalt concrete, and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN108793830A CN108793830A (en) 2018-11-13
CN108793830B true CN108793830B (en) 2021-05-18

Family

ID=64069141

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710280513.6A Expired - Fee Related CN108793830B (en) 2017-04-26 2017-04-26 Water-soluble phenolic resin modified emulsified asphalt concrete, and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN108793830B (en)

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6103000A (en) * 1997-12-31 2000-08-15 Saramco, Inc. Polyphenolic surfactant compositions as universal bitumen/water emulsifiers
US7446139B2 (en) * 2005-05-02 2008-11-04 Innophos, Inc. Modified asphalt binder material using crumb rubber and methods of manufacturing a modified asphalt binder
CN101348614B (en) * 2008-08-23 2012-10-17 惠海红 Phenolic resin modified emulsified bitumen
CN101831281B (en) * 2010-05-19 2013-04-24 濮阳市诚信钻采助剂有限公司 High-dispersion modified asphalt powder and preparation method thereof
CN106348655B (en) * 2015-07-17 2019-03-15 交通运输部公路科学研究所 A kind of preparation method and use of water-based acrylic resin emulsified asphalt concrete
CN104176985B (en) * 2014-08-11 2016-05-18 交通运输部公路科学研究所 A kind of aqueous polyurethane emulsified bitulith and its production and use
CN105439496B (en) * 2014-08-26 2018-11-13 北京建筑大学 A kind of aqueous epoxy resins micro-surfacing emulsified bitumen mixture and preparation method thereof

Also Published As

Publication number Publication date
CN108793830A (en) 2018-11-13

Similar Documents

Publication Publication Date Title
CN104176985B (en) A kind of aqueous polyurethane emulsified bitulith and its production and use
CN112897937B (en) A kind of composite modified cold patch asphalt mixture and preparation method thereof
CN102618045A (en) Waterborne epoxy resin modified emulsified asphalt and preparation and application thereof
CN103614104B (en) Low-temperature epoxy adhesive for embedded steel bars and preparation method of adhesive
CN102675890A (en) Demulsifying slow breaking and quick setting modified emulsified asphalt by microwave heating and preparation method thereof
CN102765915A (en) Resin emulsion mortar resistant to seepage, cracking and sulfate corrosion
CN114213060A (en) Low-activity steel slag asphalt mixture and preparation method thereof
CN117247253B (en) High-temperature-resistant rutting-resistant asphalt concrete and preparation method thereof
CN109517395A (en) A kind of flame-retardant high-strength asphalt additive and preparation method thereof
CN108559289B (en) Nano modified emulsified asphalt and preparation and use methods thereof
CN106348655A (en) Preparation method and application of water-borne acrylic resin emulsified asphalt concrete
CN104861673A (en) A kind of asphalt binder mixed with surface-treated basalt fiber and waste tire rubber powder
CN105713402A (en) Compound early strength agent for cold-recycling of emulsified asphalt and preparation method and application of compound early strength agent
CN113652055B (en) Preparation method of asphalt modifier
CN102276993B (en) High-toughness composite SBR modified asphalt for warm-mixed asphalt technology, and preparation method thereof
CN108793830B (en) Water-soluble phenolic resin modified emulsified asphalt concrete, and preparation method and application thereof
CN114573277A (en) Steel slag cement concrete with excellent durability and mechanical properties and preparation process thereof
CN109809742B (en) Cold-mix colorful asphalt mixture and preparation method and application thereof
CN118206325A (en) Low-epoxy-doped pure steel slag asphalt mixture and preparation method thereof
CN103773310A (en) Hot-melted asphalt adhesive with stable heat storage performance and preparation method for hot-smelted asphalt adhesive
CN110591397A (en) High-strength toughened fast-curing chemically modified resin asphalt for permeable pavement and preparation method thereof
KR20210103288A (en) A modified aspalt binder composition comprising a latex and modified aspalt mixture comprising the same
CN113307546B (en) Durable ultrathin wearing layer and preparation method thereof
CN115650636A (en) Composite modified asphalt mixture and preparation method thereof
CN104559917A (en) Recyclable asphalt-base building facing adhesive and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20210518