CN110240865B - Spraying emulsified asphalt rubber base layer treating agent and preparation method thereof - Google Patents
Spraying emulsified asphalt rubber base layer treating agent and preparation method thereof Download PDFInfo
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- CN110240865B CN110240865B CN201910518555.8A CN201910518555A CN110240865B CN 110240865 B CN110240865 B CN 110240865B CN 201910518555 A CN201910518555 A CN 201910518555A CN 110240865 B CN110240865 B CN 110240865B
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- agent
- stirring
- asphalt
- emulsified asphalt
- base layer
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 123
- 239000011387 rubberized asphalt concrete Substances 0.000 title claims abstract description 30
- 238000005507 spraying Methods 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims description 18
- 239000010426 asphalt Substances 0.000 claims abstract description 87
- 239000000839 emulsion Substances 0.000 claims abstract description 59
- 229920001971 elastomer Polymers 0.000 claims abstract description 35
- 239000005060 rubber Substances 0.000 claims abstract description 35
- 125000000129 anionic group Chemical group 0.000 claims abstract description 23
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- 239000003063 flame retardant Substances 0.000 claims abstract description 22
- 230000002745 absorbent Effects 0.000 claims abstract description 17
- 239000002250 absorbent Substances 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims description 73
- -1 rare earth chloride Chemical class 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 22
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 18
- 230000004048 modification Effects 0.000 claims description 17
- 238000012986 modification Methods 0.000 claims description 17
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 13
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 12
- 229910052708 sodium Inorganic materials 0.000 claims description 12
- 239000003607 modifier Substances 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- 239000003945 anionic surfactant Substances 0.000 claims description 10
- 239000011159 matrix material Substances 0.000 claims description 10
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 9
- 239000007921 spray Substances 0.000 claims description 9
- 239000002562 thickening agent Substances 0.000 claims description 9
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 8
- 229920000459 Nitrile rubber Polymers 0.000 claims description 8
- 239000004115 Sodium Silicate Substances 0.000 claims description 8
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 8
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 8
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 8
- 229940077388 benzenesulfonate Drugs 0.000 claims description 8
- 239000003431 cross linking reagent Substances 0.000 claims description 8
- 239000003995 emulsifying agent Substances 0.000 claims description 8
- OFUAIAKLWWIPTC-UHFFFAOYSA-L magnesium;naphthalene-2-carboxylate Chemical compound [Mg+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 OFUAIAKLWWIPTC-UHFFFAOYSA-L 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 229920002379 silicone rubber Polymers 0.000 claims description 8
- 239000004945 silicone rubber Substances 0.000 claims description 8
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 8
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 8
- DEIGXXQKDWULML-UHFFFAOYSA-N 1,2,5,6,9,10-hexabromocyclododecane Chemical compound BrC1CCC(Br)C(Br)CCC(Br)C(Br)CCC1Br DEIGXXQKDWULML-UHFFFAOYSA-N 0.000 claims description 7
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 7
- 229920002125 Sokalan® Polymers 0.000 claims description 7
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 claims description 7
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 7
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 7
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 7
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical group Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 7
- 239000004584 polyacrylic acid Substances 0.000 claims description 7
- 229920000728 polyester Polymers 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000005062 Polybutadiene Substances 0.000 claims description 6
- 229910017059 organic montmorillonite Inorganic materials 0.000 claims description 6
- 229920002857 polybutadiene Polymers 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 239000012874 anionic emulsifier Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 230000001804 emulsifying effect Effects 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 239000000084 colloidal system Substances 0.000 claims description 4
- 238000004945 emulsification Methods 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- 229910000077 silane Inorganic materials 0.000 claims description 4
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 3
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 3
- 150000002910 rare earth metals Chemical class 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 23
- 239000011248 coating agent Substances 0.000 abstract description 21
- 230000000694 effects Effects 0.000 abstract description 11
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000008033 biological extinction Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 45
- 239000012943 hotmelt Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000003973 paint Substances 0.000 description 7
- 230000035882 stress Effects 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 229920000126 latex Polymers 0.000 description 6
- 239000006224 matting agent Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 230000002411 adverse Effects 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 229920001084 poly(chloroprene) Polymers 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- 238000010345 tape casting Methods 0.000 description 3
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000009974 thixotropic effect Effects 0.000 description 2
- OCKGFTQIICXDQW-ZEQRLZLVSA-N 5-[(1r)-1-hydroxy-2-[4-[(2r)-2-hydroxy-2-(4-methyl-1-oxo-3h-2-benzofuran-5-yl)ethyl]piperazin-1-yl]ethyl]-4-methyl-3h-2-benzofuran-1-one Chemical compound C1=C2C(=O)OCC2=C(C)C([C@@H](O)CN2CCN(CC2)C[C@H](O)C2=CC=C3C(=O)OCC3=C2C)=C1 OCKGFTQIICXDQW-ZEQRLZLVSA-N 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D195/00—Coating compositions based on bituminous materials, e.g. asphalt, tar, pitch
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/48—Stabilisers against degradation by oxygen, light or heat
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a spraying emulsified asphalt rubber base layer treating agent, which comprises modified anionic emulsified asphalt, compound rubber emulsion, a delustering agent, a flame retardant, a defoaming and leveling agent, an accelerating agent and an ultraviolet absorbent; the invention also provides a production method of the base layer treating agent. The invention has the beneficial effects that: the stress relaxation performance is good, and the integral waterproof effect is durable; the processing capacity of detail nodes is good, and the waterproof weak point is eliminated; the coating has less oil seepage and good compatibility with adjacent materials; the low-temperature flexibility effect is good; the flame retardant effect is good; the anti-ultraviolet effect is good; the extinction effect is good.
Description
Technical Field
The invention relates to the field of waterproof base layer treating agents, in particular to a spraying emulsified asphalt rubber base layer treating agent.
Background
The emulsified asphalt base layer treating agent belongs to one kind of waterproof coating, and is one kind of coating capable of preventing rain water or underground water from permeating through the sprayed film. The existing waterproof paint can be divided into the following parts according to the state and the form of the paint: emulsion, solvent, reactive and asphalt.
At present, asphalt is widely used in the field of building waterproofing due to its special hydrophobicity and excellent cohesiveness, and the main products at present are asphalt coiled materials, spray rubber asphalt and various modified asphalt coatings. Unlike the construction application of asphalt coiled materials, the construction method of emulsified asphalt paint is generally divided into spraying and brushing. Common asphalt modification methods include a hot melt method and a normal temperature method, wherein the normal temperature method is to dissolve asphalt and modified resin into a proper mixed solvent together and add a filler to obtain a solvent-based waterproof coating system; the hot-melt method is to obtain a mixed modified system of asphalt and a modifier by primary or secondary hot mixing, such as neoprene latex modified asphalt paint meeting the road and bridge waterproof requirement prepared by the secondary hot mixing method, neoprene and SBR rubber modified asphalt for spraying construction prepared by the primary hot mixing method, acrylic ester and SBR latex modified asphalt waterproof paint prepared by the primary hot mixing method, and the like.
CN109401624A discloses a thixotropic aqueous modified asphalt waterproof coating and a preparation method thereof, wherein the method comprises the steps of emulsifying 70# asphalt by an anionic emulsifier, and mixing with a certain amount of chloroprene rubber to obtain the thixotropic aqueous modified asphalt waterproof coating. The method has the following defects: under a long-term high-temperature environment, the stress relaxation performance of the coating is poor, and the overall waterproof performance is influenced; the coating has more oil seepage amount, is easy to generate physical and chemical reactions with adjacent contact layers and has poor compatibility; the waterproof detail node treatment strength is not high, the smoothness is poor, and the waterproof weak point exists.
CN107043598A discloses a spray-coating quick-setting rubber asphalt waterproof paint and a preparation method thereof, and the method mixes anionic emulsified asphalt with vulcanized rubber latex, unvulcanized rubber latex and additives to prepare the waterproof paint of the invention. The method has the following defects: the coating has more oil seepage amount, is easy to generate physical and chemical reactions with adjacent contact layers and has poor compatibility; the waterproof detail node treatment strength is not high, the smoothness is poor, and the waterproof weak point exists.
The existing emulsified asphalt rubber waterproof base layer treating agent has the following technical problems:
(1) under a long-term high-temperature environment, the stress relaxation performance of the coating is poor, the elasticity is easy to lose, and the integral waterproof performance is influenced;
(2) the coating has more oil seepage amount, is easy to generate physical and chemical reactions with adjacent contact layers and has poor compatibility;
(3) the waterproof detail node treatment strength is not high, the smoothness is poor, and the waterproof weak point exists.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a spraying emulsified asphalt rubber base layer treating agent and a preparation method thereof, so as to realize the following purposes:
(1) the anti-relaxation performance of the waterproof base layer treating agent is improved, the elastic loss of the coating is inhibited, and the integral waterproof performance is improved;
(2) the oil seepage amount of the waterproof base layer treating agent is reduced, and the compatibility with adjacent materials is improved;
(3) the processing capacity of the detail nodes of the waterproof base layer processing agent is improved, and the strength and smoothness of the waterproof base layer processing agent are improved.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a treating agent for the sprayed emulsified asphalt rubber base layer comprises modified anionic emulsified asphalt, compound rubber emulsion, a delustering agent, a flame retardant, a defoaming and leveling agent, an accelerating agent and an ultraviolet absorber.
The weight percentage of each raw material is as follows: 40 to 65 percent of modified anionic emulsified asphalt, 30 to 55 percent of compound rubber emulsion, 0.1 to 1.5 percent of flatting agent, 0.2 to 1 percent of flame retardant, 0.1 to 1.5 percent of defoaming and leveling agent, 0.2 to 1.5 percent of accelerating agent and 0.1 to 1 percent of ultraviolet absorbent.
A preparation method of modified anionic emulsified asphalt is characterized by comprising the following steps: modification treatment, emulsion premixing, asphalt emulsification and post-treatment.
The modification treatment comprises the steps of putting matrix asphalt and rare earth chloride into a modification stirrer, heating the modification stirrer to 90 ℃, starting stirring, wherein the stirring speed is 200RPM, and the stirring time is 20 min; adding an SBS modifier, increasing the stirring speed of the modification stirrer to 500-600 RPM, and stirring for 40min to prepare modified asphalt; the matrix asphalt comprises the following components: rare earth chloride: the SBS modifier comprises (75-78)% (0.5-2)% and (20-25)%.
The rare earth chloride is cerium chloride and/or zirconium chloride, preferably, the ratio of cerium chloride: the weight ratio of zirconium chloride is 1: 3.
Premixing the emulsion, namely adding water, an anionic surfactant, a cross-linking agent and a thickening agent into a premixing stirrer, stirring at the rotating speed of 100RPM, heating to 70-80 ℃, preserving heat, and stirring for 20min to obtain an anionic emulsifier;
the anionic surfactant comprises sodium alkyl benzene sulfonate, sodium amino acid and magnesium naphthenate, wherein the ratio of the sodium alkyl benzene sulfonate: sodium amino acid: the ratio of the magnesium naphthenate to the magnesium naphthenate is 1:1: 2;
the cross-linking agent is a titanate compound and/or a silane compound;
the thickener is at least one of the following: organic montmorillonite, polyvinyl alcohol and potassium carbonate.
Emulsifying the asphalt, mixing the modified asphalt prepared by modification treatment with 60% of emulsifier, heating to 100-120 ℃, keeping the temperature, stirring at the speed of 400-600 RPM, adding the rest of emulsifier in the heat preservation process, and stirring for 40 min; adjusting the pH value to 7-9, and continuing stirring for 20 min;
and (3) carrying out post-treatment, namely shearing the modified emulsified asphalt emulsified by the asphalt by a colloid mill for 2-4 times to prepare the modified anionic emulsified asphalt.
The compound rubber emulsion comprises 30-40% of styrene-butadiene rubber emulsion, 20-35% of butadiene acrylonitrile rubber emulsion and 5-15% of methyl silicone rubber emulsion by mass percentage;
the flatting agent is polymethyl urea resin flatting agent and/or pure polyester flatting agent;
the flame retardant is at least one of: hexabromocyclododecane, ammonium polyphosphate and aluminum hydroxide;
the defoaming and leveling agent is polyacrylic acid and/or carboxymethyl cellulose;
the accelerator is at least one of the following: sodium carbonate, sodium silicate, alumina;
the ultraviolet absorbent is UV-326 and/or UV-329.
The compound rubber emulsion comprises 32 mass percent of styrene-butadiene rubber emulsion, 29 mass percent of butadiene rubber emulsion, 26 mass percent of butadiene-acrylonitrile rubber emulsion and 13 mass percent of methyl silicone rubber emulsion.
A preparation method of a spraying emulsified asphalt rubber base layer treating agent comprises the following steps:
(1) putting the modified anionic emulsified asphalt into a stirrer, adding the compound rubber emulsion, the defoaming and leveling agent and the accelerating agent, stirring, heating to 60-75 ℃, and keeping the temperature, wherein the stirring speed is 300-400 RPM;
(2) putting a delustering agent, a flame retardant and an ultraviolet absorber into the stirrer, heating to 90 ℃, preserving heat, stirring at the speed of 600-700 RPM, and stirring for 20 minutes;
(3) freely cooling the materials in the stirrer, and reversely stirring for 30min at the stirring speed of 600-700 RPM;
(4) the emulsified asphalt spraying rubber base layer treating agent is prepared.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention provides a spraying emulsified asphalt rubber base layer treating agent, which is prepared from raw materials and a forming process method, has good anti-relaxation performance in a high-temperature environment lasting for 80 ℃, can keep better stress relaxation performance, has stress relaxation parameters reaching 33.6-35.2 percent, and has lasting integral waterproof effect;
(2) the invention provides a spraying emulsified asphalt rubber base layer treating agent, which comprises raw materials and a forming process method, has good processing capacity of detail nodes, effectively improves the strength and smoothness of the detail nodes, has tight coating of the node coatings, does not crack or bulge, and eliminates the weak point of water resistance;
(3) the invention provides a spraying emulsified asphalt rubber base layer treating agent, which comprises the raw materials and a forming process method, wherein a coating layer is almost free of oil leakage, does not generate unfavorable physical and chemical reactions with adjacent materials, and has good compatibility with the adjacent materials;
(4) the invention provides a spraying emulsified asphalt rubber base layer treating agent, the raw material composition and the forming process thereof, and the coating still has good low-temperature flexibility at minus 45 ℃, thereby being better adapted to severe cold environment, and the specific expression is as follows:
(5) the base layer treating agent coating has strong flame retardant capability, and open fire cannot ignite the treating agent coating, so that fire hazard is eliminated;
(6) the base layer treating agent coating has strong ultraviolet resistance and can effectively prevent ultraviolet aging;
(7) the surface of the base layer treating agent coating of the invention has no reflection, the extinction effect is good, and the light pollution is eliminated.
Detailed Description
In order to more clearly understand the technical features, objects, and effects of the present invention, specific embodiments of the present invention will now be described.
Example 1A spray-coated emulsified asphalt rubber-based treating agent
The spraying emulsified asphalt rubber base layer treating agent comprises the following raw materials in percentage by mass:
60 percent of modified anion emulsified asphalt,
30 percent of compound rubber latex,
1.5 percent of the delustering agent,
1 percent of flame retardant,
1.5 percent of defoaming and leveling agent,
0.6 percent of accelerating agent,
0.4 percent of ultraviolet absorbent.
The compound rubber emulsion comprises 40% of styrene-butadiene rubber emulsion, 35% of butadiene rubber emulsion, 20% of butadiene-acrylonitrile rubber emulsion and 5% of methyl silicone rubber emulsion in percentage by mass.
The flatting agent is polymethyl urea resin flatting agent.
The flame retardant is hexabromocyclododecane.
The defoaming and leveling agent is polyacrylic acid.
The accelerating agent is sodium carbonate.
The ultraviolet absorbent is UV-326.
Example 2A spray-coated emulsified asphalt rubber-based treating agent
The spraying emulsified asphalt rubber base layer treating agent comprises the following raw materials in percentage by mass:
40 percent of modified anion emulsified asphalt,
55 percent of compound rubber emulsion,
1 percent of the delustering agent,
0.5 percent of flame retardant,
1 percent of defoaming and leveling agent,
1.5 percent of accelerating agent,
1% of ultraviolet absorbent.
The compound rubber emulsion comprises 30% of styrene-butadiene rubber emulsion, 35% of butadiene rubber emulsion, 20% of butadiene-acrylonitrile rubber emulsion and 15% of methyl silicone rubber emulsion in percentage by mass.
The matting agent is a pure polyester matting agent.
The flame retardant comprises ammonium polyphosphate and aluminum hydroxide, wherein the ammonium polyphosphate: the weight ratio of aluminum hydroxide is 1: 1.
The defoaming and leveling agent is carboxymethyl cellulose.
The accelerating agent is sodium carbonate and sodium silicate, wherein the sodium carbonate: the weight ratio of the sodium silicate is 1: 1.
The ultraviolet absorbent is UV-326 and UV-329, and the ratio of UV-326: the UV-329 weight ratio was 1: 1.
Example 3A spray emulsified asphalt rubber-based treating agent
The spraying emulsified asphalt rubber base layer treating agent comprises the following raw materials in percentage by mass:
50 percent of modified anionic emulsified asphalt,
44 percent of compound rubber emulsion,
1 percent of the delustering agent,
1 percent of flame retardant,
1.5 percent of defoaming and leveling agent,
1.5 percent of accelerating agent,
1% of ultraviolet absorbent.
The compound rubber emulsion comprises 32 mass percent of styrene-butadiene rubber emulsion, 29 mass percent of butadiene rubber emulsion, 26 mass percent of butadiene-acrylonitrile rubber emulsion and 13 mass percent of methyl silicone rubber emulsion.
The flatting agent comprises a polymethylurea resin flatting agent and a pure polyester flatting agent, wherein the polymethylurea resin flatting agent comprises the following components in percentage by weight: the weight ratio of the pure polyester flatting agent is 1: 1.
The flame retardant comprises: hexabromocyclododecane, ammonium polyphosphate, aluminum hydroxide, hexabromocyclododecane: ammonium polyphosphate: the weight ratio of the aluminum hydroxide is 1:1: 1.
The defoaming and leveling agent is polyacrylic acid and carboxymethyl cellulose, and the ratio of polyacrylic acid: the weight ratio of the carboxymethyl cellulose is 1: 1.
The accelerator comprises: sodium carbonate, sodium silicate, alumina, sodium carbonate: sodium silicate: the weight ratio of alumina is 1:1: 1.
The ultraviolet absorbent is UV-326 and UV-329, and the ratio of UV-326: the UV-329 weight ratio was 1: 1.
Example 4A spray-coated emulsified asphalt rubber-based treating agent
The spraying emulsified asphalt rubber base layer treating agent comprises the following raw materials in percentage by mass:
50 percent of modified anionic emulsified asphalt,
48 percent of compound rubber latex,
0.3 percent of the delustering agent,
0.5 percent of flame retardant,
0.8 percent of defoaming and leveling agent,
0.2 percent of accelerating agent,
0.2 percent of ultraviolet absorbent.
The compound rubber emulsion comprises 32 mass percent of styrene-butadiene rubber emulsion, 29 mass percent of butadiene rubber emulsion, 26 mass percent of butadiene-acrylonitrile rubber emulsion and 13 mass percent of methyl silicone rubber emulsion.
The matting agent comprises a polymethylurea resin matting agent or a pure polyester matting agent, and the polymethylurea resin matting agent: the weight ratio of the pure polyester flatting agent is 1: 1.
The flame retardant comprises: hexabromocyclododecane, ammonium polyphosphate, aluminum hydroxide, hexabromocyclododecane: ammonium polyphosphate: the weight ratio of the aluminum hydroxide is 1:1: 1.
The defoaming and leveling agent is polyacrylic acid and carboxymethyl cellulose, and the ratio of polyacrylic acid: the weight ratio of the carboxymethyl cellulose is 1: 1.
The accelerating agent is sodium carbonate, sodium silicate, aluminum oxide, and the mass ratio of sodium carbonate: sodium silicate: the weight ratio of alumina is 1:1: 1.
The ultraviolet absorbent is UV-326.
Example 5 preparation of modified anionic emulsified asphalt according to examples 1 to 4
A preparation method of modified anionic emulsified asphalt comprises the following steps: modification treatment, emulsion premixing, asphalt emulsification and post-treatment.
The modification treatment comprises the following steps: adding the matrix asphalt and the rare earth chloride into a modified stirrer, heating the stirrer to 90 ℃, stirring at the stirring speed of 200RPM for 20 min; adding the SBS modifier while stirring, after the SBS modifier is added, increasing the stirring speed to 500RPM, and stirring for 40min to obtain the modified asphalt. The matrix asphalt comprises the following components: rare earth chloride: the SBS modifier accounts for 75 percent to 0.5 percent to 20 percent by mass.
The matrix asphalt is 70# asphalt, 90# asphalt and 100# asphalt, and the ratio of 70# asphalt: asphalt No. 90: the ratio of 100# asphalt to 1:1 by weight.
The rare earth chloride is zirconium chloride.
The emulsion premixing comprises the following steps: adding water, anionic surfactant, cross-linking agent and thickener into a premixing stirrer, stirring at 100RPM, heating to 70 deg.C, and stirring for 20min to obtain anionic emulsifier.
The anionic surfactant comprises sodium alkyl benzene sulfonate, sodium amino acid and magnesium naphthenate, and the weight ratio of the anionic surfactant to the magnesium alkyl benzene sulfonate is 1:1: 2.
The cross-linking agent is titanate compound and silane compound, titanate compound: the ratio of the weight parts of the silane compounds is 1: 1.
The thickening agent is organic montmorillonite and potassium carbonate, wherein the weight ratio of organic montmorillonite: the weight ratio of the potassium carbonate is 2: 1.
And (2) emulsifying the asphalt, which comprises the steps of mixing the modified asphalt with 60% of emulsifier, heating to 100 ℃, keeping the temperature, adding the rest 40% of emulsifier in the heat preservation process at the stirring speed of 400RPM, stirring for 40min, adjusting the pH value to 7, and continuing to stir for 20 min.
And the post-treatment comprises the step of shearing the uniformly stirred modified emulsified asphalt at a high speed for 2 times by a colloid mill to prepare the modified anionic emulsified asphalt.
Example 6 preparation of modified anionic emulsified asphalt according to examples 1 to 4
A preparation method of modified anionic emulsified asphalt comprises the following steps: modification treatment, emulsion premixing, asphalt emulsification and post-treatment.
The modification treatment comprises the following steps: adding the matrix asphalt and the rare earth chloride into a modified stirrer, heating the stirrer to 90 ℃, stirring at the stirring speed of 200RPM for 20 min; adding the SBS modifier while stirring, after the SBS modifier is added, increasing the stirring speed to 600RPM, and stirring for 40min to obtain the modified asphalt. The matrix asphalt comprises the following components: rare earth chloride: the SBS modifier comprises 78 wt% and 2 wt% and 24 wt%.
The matrix asphalt is 100# asphalt.
The rare earth chloride is cerium chloride and zirconium chloride, wherein the weight ratio of cerium chloride: the mass ratio of zirconium chloride is 1: 3.
The emulsion premixing comprises the following steps: adding water, anionic surfactant, cross-linking agent and thickener into a premixing stirrer, stirring at 100RPM, heating to 80 deg.C, and stirring for 20min to obtain anionic emulsifier.
The anionic surfactant comprises sodium alkyl benzene sulfonate, sodium amino acid and magnesium naphthenate, and the weight ratio of the anionic surfactant to the magnesium alkyl benzene sulfonate is 1:1: 2.
The cross-linking agent is titanate compound and silane compound, titanate compound: the ratio of the weight parts of the silane compounds is 1: 1.
The thickening agent is organic montmorillonite, polyvinyl alcohol and potassium carbonate, wherein the thickening agent is organic montmorillonite: polyvinyl alcohol: the weight ratio of the potassium carbonate is 1:1: 1.
And (2) emulsifying the asphalt, which comprises the steps of mixing the modified asphalt with 60% of emulsifier, heating to 120 ℃, keeping the temperature, adding the rest 40% of emulsifier in the heat preservation process at the stirring speed of 600RPM, stirring for 40min, adjusting the pH value to 7, and continuing to stir for 20 min.
And the post-treatment comprises the step of shearing the uniformly stirred modified emulsified asphalt at a high speed for 4 times by a colloid mill to prepare the modified anionic emulsified asphalt.
Example 7 preparation method of spray-coated emulsified asphalt rubber base layer treating agent
The preparation method of the sprayed emulsified asphalt rubber base layer treating agent comprises the following steps:
(1) putting a certain amount of the modified anionic emulsified asphalt of example 5 into a stirrer, adding the compound rubber emulsion, the defoaming and leveling agent and the accelerating agent at the same time, stirring, heating to 60 ℃, and stirring at the speed of 300 RPM;
(2) adding the delustering agent, the flame retardant and the ultraviolet absorbent into a stirrer, continuously stirring, heating to 90 ℃, keeping the temperature, stirring at the speed of 600RPM, and stirring for 20 minutes;
(3) freely cooling the materials in the stirrer, and reversely stirring for 30min at the stirring speed of 600 RPM;
(4) the emulsified asphalt spraying rubber base layer treating agent is prepared.
Base layer treating agent oil permeability test: 5 pieces of medium-speed qualitative filter paper with the diameter of about 180mm are subjected to hot-melt knife coating to form a sample, the area of the sample is about 50mmx50mm, the thickness of the sample is (2.0 +/-0.2 mm), 1 piece of glass plate with the thickness of about 6mm and the same size is placed on the sample, the sample is placed into an oven adjusted to the specified temperature of heat resistance, the temperature is kept for 5h +/-15 min, the sample is taken out and placed for 1h under the standard test condition, and then the number of oil seepage sheets is checked, and 3 samples are tested in total. In particular, see the following table:
the base layer treating agent has less oil leakage after being sprayed, has good contact compatibility with other materials, can prevent adverse physical and chemical reactions from being generated, and prevents the treatment effect of the treating agent from being reduced.
Base layer treatment agent stress relaxation test: three samples were hot-melt knife-coated onto a 120mm × 50mm × 3mm aluminum plate with a coating thickness of 2.0mm, another aluminum plate was pressed onto the adhesive surface with an adhesive area of 50mm × 50mm, and after adhesion, the sample was centered and pressurized with a 1kg weight for 10min, and then placed at a constant temperature of 80 ℃ for 168 h.
And (3) placing the test piece into a clamp of a tensile machine and clamping the test piece, wherein the distance between the clamps is about 150mm, the tensile speed is 10mm/min, starting the tensile machine, continuing to stretch until the tensile force is reduced to 95% of the maximum force after the test piece is stretched to the maximum force Fmax, stopping stretching, keeping the tensile state, timing, and recording the ratio of F5min to Fmax when the test piece is 5 min.
| Item | Sample No. 1 | Sample No. 2 | Sample No. 3 |
| Numerical value | 33.6％ | 34.2％ | 34.9％ |
Example 8 preparation method of spray-coated emulsified asphalt rubber base layer treating agent
The preparation method of the sprayed emulsified asphalt rubber base layer treating agent comprises the following steps:
(1) putting a certain amount of the modified anionic emulsified asphalt of example 6 into a stirrer, adding the compound rubber emulsion, the defoaming and leveling agent and the accelerating agent at the same time, stirring, heating to 60 ℃, and stirring at the speed of 300 RPM;
(2) adding the delustering agent, the flame retardant and the ultraviolet absorbent into a stirrer, continuously stirring, heating to 90 ℃, keeping the temperature, stirring at the speed of 600RPM, and stirring for 20 minutes;
(3) freely cooling the materials in the stirrer, and reversely stirring for 30min at the stirring speed of 600 RPM;
(4) the emulsified asphalt spraying rubber base layer treating agent is prepared.
Base layer treating agent oil permeability test: 5 pieces of medium-speed qualitative filter paper with the diameter of about 180mm are subjected to hot-melt knife coating to form a sample, the area of the sample is about 50mmx50mm, the thickness of the sample is (2.0 +/-0.2 mm), 1 piece of glass plate with the thickness of about 6mm and the same size is placed on the sample, the sample is placed into an oven adjusted to the specified temperature of heat resistance, the temperature is kept for 5h +/-15 min, the sample is taken out and placed for 1h under the standard test condition, and then the number of oil seepage sheets is checked, and 3 samples are tested in total. In particular, see the following table:
the base layer treating agent has less oil leakage after being sprayed, has good contact compatibility with other materials, can prevent adverse physical and chemical reactions from being generated, and prevents the treatment effect of the treating agent from being reduced.
Base layer treatment agent stress relaxation test: three samples were hot-melt knife-coated onto a 120mm × 50mm × 3mm aluminum plate with a coating thickness of 2.0mm, another aluminum plate was pressed onto the adhesive surface with an adhesive area of 50mm × 50mm, and after adhesion, the sample was centered and pressurized with a 1kg weight for 10min, and then placed at a constant temperature of 80 ℃ for 168 h.
And (3) placing the test piece into a clamp of a tensile machine and clamping the test piece, wherein the distance between the clamps is about 150mm, the tensile speed is 10mm/min, starting the tensile machine, continuing to stretch until the tensile force is reduced to 95% of the maximum force after the test piece is stretched to the maximum force Fmax, stopping stretching, keeping the tensile state, timing, and recording the ratio of F5min to Fmax when the test piece is 5 min.
| Item | Sample No. 1 | Sample No. 2 | Sample No. 3 |
| Numerical value | 34.6％ | 34.1％ | 34.8％ |
Example 9 preparation method of spray emulsified asphalt rubber base layer treating agent
The preparation method of the sprayed emulsified asphalt rubber base layer treating agent comprises the following steps:
(1) putting a certain amount of the modified anionic emulsified asphalt of example 6 into a stirrer, adding the compound rubber emulsion, the defoaming and leveling agent and the accelerating agent at the same time, stirring, heating to 75 ℃, and stirring at the speed of 400 RPM;
(2) adding the flatting agent, the flame retardant and the ultraviolet absorbent into a stirrer, continuously stirring, heating to 90 ℃, keeping the temperature, stirring at the speed of 700RPM, and stirring for 20 minutes;
(3) freely cooling the materials in the stirrer, and reversely stirring for 30min at the stirring speed of 700 RPM;
(4) the emulsified asphalt spraying rubber base layer treating agent is prepared.
Base layer treating agent oil permeability test: 5 pieces of medium-speed qualitative filter paper with the diameter of about 180mm are subjected to hot-melt knife coating to form a sample, the area of the sample is about 50mmx50mm, the thickness of the sample is (2.0 +/-0.2 mm), 1 piece of glass plate with the thickness of about 6mm and the same size is placed on the sample, the sample is placed into an oven adjusted to the specified temperature of heat resistance, the temperature is kept for 5h +/-15 min, the sample is taken out and placed for 1h under the standard test condition, and then the number of oil seepage sheets is checked, and 3 samples are tested in total. In particular, see the following table:
the base layer treating agent has almost no oil leakage after being sprayed, has good contact compatibility with other materials, can prevent adverse physical and chemical reactions from being generated, and prevents the treatment effect of the treating agent from being reduced.
Base layer treatment agent stress relaxation test: three samples were hot-melt knife-coated onto a 120mm × 50mm × 3mm aluminum plate with a coating thickness of 2.0mm, another aluminum plate was pressed onto the adhesive surface with an adhesive area of 50mm × 50mm, and after adhesion, the sample was centered and pressurized with a 1kg weight for 10min, and then placed at a constant temperature of 80 ℃ for 168 h.
And (3) placing the test piece into a clamp of a tensile machine and clamping the test piece, wherein the distance between the clamps is about 150mm, the tensile speed is 10mm/min, starting the tensile machine, continuing to stretch until the tensile force is reduced to 95% of the maximum force after the test piece is stretched to the maximum force Fmax, stopping stretching, keeping the tensile state, timing, and recording the ratio of F5min to Fmax when the test piece is 5 min.
| Item | Sample No. 1 | Sample No. 2 | Sample No. 3 |
| Numerical value | 34.6％ | 35.2％ | 34.9％ |
All percentages used in the present invention are mass percentages unless otherwise indicated.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (3)
1. The sprayed emulsified asphalt rubber base layer treating agent is characterized in that raw materials of the sprayed emulsified asphalt rubber base layer treating agent comprise modified anionic emulsified asphalt, compound rubber emulsion, a delustering agent, a flame retardant, a defoaming and leveling agent, an accelerating agent and an ultraviolet absorbent;
the weight percentage of each raw material is as follows: 40-65% of modified anionic emulsified asphalt, 30-55% of compound rubber emulsion, 0.1-1.5% of flatting agent, 0.2-1% of flame retardant, 0.1-1.5% of defoaming and leveling agent, 0.2-1.5% of accelerating agent and 0.1-1% of ultraviolet absorbent;
the preparation method of the modified anionic emulsified asphalt comprises the following steps: modification treatment, emulsion premixing, asphalt emulsification and post-treatment;
the modification treatment comprises the steps of putting matrix asphalt and rare earth chloride into a modification stirrer, heating the modification stirrer to 90 ℃, starting stirring, wherein the stirring speed is 200RPM, and the stirring time is 20 min; adding an SBS modifier, increasing the stirring speed of the modification stirrer to 500-600 RPM, and stirring for 40min to prepare modified asphalt;
the matrix asphalt, the chlorinated rare earth and the SBS modifier are 75-78 wt%, 0.5-2 wt% and 20-25 wt%;
the rare earth chloride is cerium chloride and/or zirconium chloride;
when the rare earth chloride is cerium chloride and zirconium chloride, the ratio of cerium chloride: the weight part ratio of zirconium chloride is 1: 3;
premixing the emulsion, namely adding water, an anionic surfactant, a cross-linking agent and a thickening agent into a premixing stirrer, stirring at the rotating speed of 100RPM, heating to 70-80 ℃, preserving heat, and stirring for 20min to obtain an anionic emulsifier;
the anionic surfactant comprises sodium alkyl benzene sulfonate, sodium amino acid and magnesium naphthenate, wherein the ratio of the sodium alkyl benzene sulfonate: sodium amino acid: the ratio of the magnesium naphthenate to the magnesium naphthenate is 1:1: 2;
the cross-linking agent is a titanate compound and/or a silane compound;
the thickener is at least one of the following: organic montmorillonite, polyvinyl alcohol and potassium carbonate;
emulsifying the asphalt, mixing the modified asphalt prepared by modification treatment with 60% of emulsifier, heating to 100-120 ℃, keeping the temperature, stirring at the speed of 400-600 RPM, adding the rest of emulsifier in the heat preservation process, and stirring for 40 min; adjusting the pH value to 7-9, and continuing stirring for 20 min;
the post-treatment is to shear the modified emulsified asphalt emulsified by the asphalt through a colloid mill for 2 to 4 times to prepare modified anionic emulsified asphalt;
the compound rubber emulsion comprises 30-40% of styrene-butadiene rubber emulsion, 20-35% of nitrile-butadiene rubber emulsion and 5-15% of methyl silicone rubber emulsion in percentage by mass;
the flatting agent is polymethyl urea resin flatting agent and/or pure polyester flatting agent;
the flame retardant is at least one of: hexabromocyclododecane, ammonium polyphosphate and aluminum hydroxide;
the defoaming and leveling agent is polyacrylic acid and/or carboxymethyl cellulose;
the accelerator is at least one of the following: sodium carbonate, sodium silicate, alumina;
the ultraviolet absorbent is UV-326 and/or UV-329.
2. The spray emulsified asphalt rubber base layer treating agent as claimed in claim 1, wherein the compound rubber emulsion comprises 32% of styrene-butadiene rubber emulsion, 29% of butadiene rubber emulsion, 26% of butadiene-acrylonitrile rubber emulsion and 13% of methyl silicone rubber emulsion by mass.
3. The method of preparing a sprayed emulsified asphalt rubber-based treating agent according to claim 1, comprising:
(1) adding the modified anionic emulsified asphalt into a stirrer, adding the compound rubber emulsion, the defoaming and leveling agent and the accelerating agent, stirring, heating to 60-75 ℃, and keeping the temperature, wherein the stirring speed is 300-400 RPM;
(2) putting a delustering agent, a flame retardant and an ultraviolet absorber into the stirrer, heating to 90 ℃, preserving heat, stirring at the speed of 600-700 RPM, and stirring for 20 minutes;
(3) freely cooling the materials in the stirrer, and reversely stirring for 30min at the stirring speed of 600-700 RPM;
(4) the emulsified asphalt spraying rubber base layer treating agent is prepared.
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| CN103788662A (en) * | 2012-10-29 | 2014-05-14 | 中国石油化工股份有限公司 | Emulsified asphalt, a preparation method thereof, applications thereof, a water-proof coating material and a water-proof coating |
| CN105153719A (en) * | 2015-10-23 | 2015-12-16 | 王新航 | Rare-earth modified asphalt and preparation method thereof |
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| CN105348547A (en) * | 2015-10-26 | 2016-02-24 | 北京东方雨虹防水技术股份有限公司 | Anionic SBS emulsion, preparation method and application thereof |
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| CN103788662A (en) * | 2012-10-29 | 2014-05-14 | 中国石油化工股份有限公司 | Emulsified asphalt, a preparation method thereof, applications thereof, a water-proof coating material and a water-proof coating |
| CN105153719A (en) * | 2015-10-23 | 2015-12-16 | 王新航 | Rare-earth modified asphalt and preparation method thereof |
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