CN107151419A - A kind of high tenacity cold mixing bituminous epoxy binding agent and preparation method thereof - Google Patents
A kind of high tenacity cold mixing bituminous epoxy binding agent and preparation method thereof Download PDFInfo
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- CN107151419A CN107151419A CN201710540037.7A CN201710540037A CN107151419A CN 107151419 A CN107151419 A CN 107151419A CN 201710540037 A CN201710540037 A CN 201710540037A CN 107151419 A CN107151419 A CN 107151419A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/44—Amides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Road Paving Structures (AREA)
Abstract
The present invention provides a kind of high tenacity cold mixing bituminous epoxy binding agent and preparation method thereof.Cold mixing bituminous epoxy binding agent includes component A and component B, and component A is mainly made up of epoxy resin, diluent and toughener, and component B is mainly made up of curing agent, pitch, diluent, compatilizer and defoamer.The cold mixing bituminous epoxy binding agent of the present invention can be mixed and stirred and constructed under normal temperature, low-carbon environment-friendly and construction technology is simple.3 D stereo network structure is formed after epoxy bitumen material solidification, with good heat endurance and adhesion strength.Branched nbr carboxyl terminal is used for toughener, it is ensured that the excellent pliability of bituminous epoxy solidfied material.The present invention is mainly suitable for the bonding on the road surfaces such as Steel Bridge Deck, urban viaduct, cement concrete bridge deck, tunnel, highway and waterproof.
Description
Technical field
The present invention relates to road and bridge construction material and preparation method thereof, and in particular to a kind of high tenacity cold mixing epoxy drip
Blue or green binder material and preparation method thereof.
Background technology
During deck paving, set water-proof tack coat be to ensure that deck installation structure durability important measures it
One.During deck paving, in order to prevent reinforcing bar or steel bridge deck in moisture infiltration bridge floor, corrosion concrete, bridge is threatened
Floorings and pave-load layer are bonded to an entirety by safety beam, water-proof tack coat of mating formation, and not only improve floorings and pave-load layer
Stressing conditions, additionally it is possible to prevent moisture from penetrating into.
Material for paving steel bridge deck tack coat mainly has heat molten type binding material, solvent-borne type binding material and thermosetting
Binding material.Heat molten type binding material fills resin (such as rosin) and various high polymer materials (such as ethylene-acetate second by pitch
Alkene (vinyl acetate) ester copolymer, polyethylene and butadiene-styrene rubber etc.) composition.Heat molten type binding material has certain deformation energy
Power, has follow-up capability to steel plate deformed, it may have good waterproof action.However, such a material easily softens at high temperature,
Cohesive force declines.Moreover, heat molten type material must fully melt before construction, stirred after being warming up to defined temperature, then
Uniformly dispensed with pitch truck spreader, difficulty of construction is relatively large.Preheating before construction can also reduce the viscous of heat molten type binding material
Tie effect.Solvent-borne type binding material typically refers to emulsified asphalt and soluble rubber asphalt more, and it has the disadvantage that high temperature easily softens, and material
Material is internal to contain heat-sensitive substance, and gas can be discharged when paving high temperature by meeting, so that pave-load layer produces bubble.
Thermoset binder material refers to bituminous epoxy.Bituminous epoxy be one kind with thermosetting epoxy resin modified asphalt material,
Thermoplastic pitch is fundamentally changed into thermosets, assign the excellent mechanical strength of bituminous epoxy, pliability, resistance to tired
The features such as labor performance, resistance to elevated temperatures and corrosion resistance.No matter bituminous epoxy is in cohesive force, deformability or in heat
In terms of stability, all with significant advantage.Epoxy bitumen material is expensive, and especially import bituminous epoxy price is generally in 5-
60000 yuan/ton.Moreover, thermosetting epoxy asphalt complicated construction technique, need use special sprinkling for (190 DEG C or so) at high temperature
Equipment is constructed.Therefore, it is necessary to develop can be mixed and stirred in normal temperature construction bituminous epoxy binding agent be used for road and bridge waterproof with
Bond.
The content of the invention
It is an object of the invention to propose a kind of high tenacity cold mixing bituminous epoxy binding agent and preparation method thereof, the cold mixing ring
Oxygen asphalt material have excellent adhesive property, mechanical strength, pliability, can the features such as room temperature mixes and stirs construction, curing time is short,
Bridge deck water-proof tack coat is primarily adapted for use in mat formation.
The present invention proposes a kind of high tenacity cold mixing bituminous epoxy binding agent, including component A and component B, component A include ring
Oxygen tree fat, diluent and toughener, component B include curing agent, pitch, diluent, compatilizer and defoamer.
Each component parts by weight are in component A：
100 parts of epoxy resin
5-20 parts of toughener
10-30 parts of diluent
Each component parts by weight are in component B：
Wherein, component A and component B mass ratio are 100：110-100：200.
It is preferred that, described epoxy resin is liquid bisphenol A type tetraglycidel ether epoxy resin.
It is preferred that, described toughener is branched nbr carboxyl terminal (b-CTBN), and structural formula is as follows：
It is preferred that, described curing agent is low molecular polyamides, and its structural formula is as follows：
It is preferred that, described pitch is SBS modified pitch.
It is preferred that, described component B diluents are the good solvent of pitch, including acetone, toluene, dimethylbenzene, dichloropropane,
One or more of mixtures in tetrachloro-ethylene, dibutyl phthalate, dioctyl phthalate.
It is preferred that, described compatilizer is big for stearic acid or stearate containing epoxy radicals and fatty long-chain, including epoxy
Soya-bean oil, epoxystearic acid, epoxy stearate, epoxyoleic acid, Epoxy oil acid esters, epoxy linoleic acid, epoxy linoleate and poly-
One or more of mixtures in oxirane stearic acid.
It is preferred that, described defoamer is polysiloxane defoaming agent.
The invention also discloses a kind of method for preparing above-mentioned high tenacity cold mixing bituminous epoxy binding agent, including following step
Suddenly：
Component A preparation：By epoxy resin, diluent and toughener mix, be heated to 40-60 DEG C, with 200-500 turn/
The speed of minute is stirred 1-6 hours, is cooled to the component A that room temperature obtains high tenacity cold mixing bituminous epoxy binding agent.
Component B preparation：Pitch is heated to 110-135 DEG C of melting.Weigh pitch and diluent and mix, with 200-
500 revs/min of speed is stirred 0.5-2 hours and is completely dissolved to pitch.Less than 40 DEG C are cooled to, curing agent, compatilizer is added
And defoamer, stirred 1-4 hours with 200-500 revs/min of speed, obtain the component of high tenacity cold mixing bituminous epoxy binding agent
B。
A kind of concrete application method of high tenacity cold mixing bituminous epoxy binding agent, it is to mix component A in room temperature with component B
Close, stirred rapidly 3-5 minutes with 500~900 revs/min of speed, obtain the mixture of high tenacity cold mixing bituminous epoxy.
It is preferred that, the preparation method of toughener is in component A：Using trimethylolpropane as core, by end carboxyl butyronitrile rubber
Glue, trimethylolpropane, catalyst and hexamethylene are mixed, and the mol ratio of wherein trimethylolpropane and nbr carboxyl terminal is
3:4, back flow reaction 1-8 hours is reacted after terminating by vacuum distillation desolvation.Washed using ether and pass through surname extraction
Residual solvent, small molecule by-product and unreacted monomer are removed, finally extract is placed in vacuum drying oven and dried, b- is obtained
CTBN。
Beneficial effect produced by the present invention includes：
(1) construction technology is simple, and using low molecular polyamides as curing agent, construction, energy-conserving and environment-protective can be mixed and stirred at normal temperatures；
(2) good mechanical performance, using branched nitrile rubber flexibilizing epoxy pitch, is ensureing epoxy bitumen material intensity
On the basis of significantly improve the pliability of epoxy bitumen material；
(3) it is applied widely, it is applicable not only to Steel Bridge Deck water-proof tack coat and mats formation, it may also be used for urban viaduct, cement
The bonding and waterproof on the road surfaces such as concrete bridge deck, tunnel, highway.
Embodiment
The present invention is further illustrated with example below, but protection scope of the present invention is not limited in examples of implementation.To this
The other changes and modifications that the technical staff in field makes in the case of without departing from the spirit and scope of protection of the present invention
It is included within the scope of the present invention.
Toughener b-CTBN preparation method is as follows：
Embodiment 1：
Using trimethylolpropane as core, by nbr carboxyl terminal, trimethylolpropane, catalyst for esterification reaction and molten
Agent hexamethylene is mixed, and wherein the mol ratio of trimethylolpropane and nbr carboxyl terminal is 3:4, catalyst amount is end ring oxygen
The 1% of base nitrile rubber and trimethylolpropane quality sum, the quality of hexamethylene is nbr carboxyl terminal and trihydroxy methyl
10 times of propane quality sum, back flow reaction 3h, reacts and removes hexamethylene by vacuum distillation after terminating under mechanical stirring.It is cold
But to being washed 3 times using ether after room temperature, by sediment by surname extraction 24h to remove solvent, the small molecule by-product of residual
Thing and unreacted monomer.Extract is placed in vacuum drying oven and dried, b-CTBN is obtained.
The preparation method of high tenacity cold mixing bituminous epoxy binding agent is as follows：
Embodiment 2：
Weigh 100 parts of (mass parts, similarly hereinafter) liquid bisphenol A type tetraglycidel ether epoxy resins (E51), 5 parts of b-CTBN, 15
Part octyl glycidyl ether, is heated to 40 DEG C, is stirred 2 hours with 300 revs/min of speed, is cooled to room temperature, obtains high tenacity
The component A of cold mixing bituminous epoxy binding agent.
SBS modified pitch is placed in convection oven, melted 2 hours in 110 DEG C of heating.Weigh 90 parts of SBS modified pitch
With 35 parts of dichloropropanes, stirred 2 hours with 300 revs/min of speed.Less than 40 DEG C are cooled to, 100 parts of low molecule amounts is added and gathers
Acid amides, 30 parts of epoxystearic acids and 1 part of polysiloxanes, are stirred 1 hour with 300 revs/min of speed, obtain high tenacity cold mixing ring
The component B of oxygen pitch binder.
100 parts of component A and 150 parts of component B are mixed at room temperature, is stirred 5 minutes, obtained with 800 revs/min of speed
The mixture of high tenacity cold mixing bituminous epoxy binding agent.Said mixture is taken to pour into Teflon mould, normal temperature cure 36
Hour, cold mixing bituminous epoxy solidfied material dumbbell shape sample is obtained after the demoulding, for Mechanics Performance Testing.Mechanics Performance Testing condition
For 23 ± 2 DEG C, rate of extension is 10mm/min.Adhesion strength is tested using drawing instrument.Stretching and pull-out test result are seen attached list
1。
Embodiment 3：
100 parts of E51,12 parts of b-CTBN and 10 part of butyl glycidyl ethers are weighed, 60 DEG C are heated to, with 300 revs/min
Speed is stirred 2 hours, is cooled to room temperature, is obtained the component A of high tenacity cold mixing bituminous epoxy binding agent.
SBS modified pitch is placed in convection oven, melted 1.5 hours in 120 DEG C of heating.Weigh 60 parts of SBS and be modified drip
Blue or green and 25 parts of dioctyl phthalates, are stirred 2 hours with 200 revs/min of speed.Less than 40 DEG C are cooled to, 100 parts are added
Low molecular polyamides, 15 parts of epoxidized soybean oils and 0.5 part of polysiloxanes, are stirred 1 hour with 500 revs/min of speed, obtained
The component B of high tenacity cold mixing bituminous epoxy binding agent.
100 parts of component A and 200 parts of component B are mixed at room temperature, is stirred 5 minutes, obtained with 500 revs/min of speed
The mixture of high tenacity cold mixing bituminous epoxy binding agent.Said mixture is taken to pour into Teflon mould, normal temperature cure 24
Hour, cold mixing bituminous epoxy solidfied material dumbbell shape sample is obtained after the demoulding, for Mechanics Performance Testing.Mechanics Performance Testing condition
For 23 ± 2 DEG C, rate of extension is 10mm/min.Adhesion strength is tested using drawing instrument.Stretching and pull-out test result are seen attached list
1。
Embodiment 4：
Weigh 100 parts of E51,20 parts of b-CTBN and 30 part of 12-14 alkyl glycidyl ethers, be heated to 50 DEG C, with 200 turns/
The speed of minute is stirred 6 hours, is cooled to room temperature, is obtained the component A of high tenacity cold mixing bituminous epoxy binding agent.
SBS modified pitch is placed in convection oven, melted 1 hour in 135 DEG C of heating.Weigh 150 parts of SBS modified pitch
With 70 parts of dioctyl phthalates, stirred 0.5 hour with 500 revs/min of speed.Less than 40 DEG C are cooled to, 100 parts are added
Low molecular polyamides, 55 parts of epoxy stearates and 2 parts of polysiloxanes, are stirred 4 hours with 200 revs/min of speed, obtained
The component B of high tenacity cold mixing bituminous epoxy binding agent.
100 parts of component A and 110 parts of component B are mixed at room temperature, is stirred 3 minutes, obtained with 900 revs/min of speed
The mixture of high tenacity cold mixing bituminous epoxy binding agent.Said mixture is taken to pour into Teflon mould, normal temperature cure 24
Hour, cold mixing bituminous epoxy solidfied material dumbbell shape sample is obtained after the demoulding, for tensile property test.Tensile property test condition
For 23 ± 2 DEG C, rate of extension is 10mm/min.Adhesion strength is tested using drawing instrument.Stretching and pull-out test result are seen attached list
1。
Embodiment 5：
100 parts of E51,10 parts of b-CTBN and 30 part of octyl glycidyl ethers are weighed, 40 DEG C are heated to, with 400 revs/min
Speed is stirred 3 hours, is cooled to room temperature, is obtained the component A of high tenacity cold mixing bituminous epoxy binding agent.
SBS modified pitch is placed in convection oven, melted 1.5 hours in 120 DEG C of heating.Weigh 120 parts of SBS and be modified drip
Blue or green and 50 parts of tetrachloro-ethylenes, are stirred 2 hours with 300 revs/min of speed.Less than 40 DEG C are cooled to, 100 parts of low molecule amounts are added
Polyamide, 40 parts of Epoxy oil acid esters and 1.5 parts of polysiloxanes, are stirred 2 hours with 300 revs/min of speed, obtain high tenacity cold
The component B of mixed epoxy bitumen binding agent.
100 parts of component A and 120 parts of component B are mixed at room temperature, is stirred 3 minutes, obtained with 900 revs/min of speed
The mixture of high tenacity cold mixing bituminous epoxy binding agent.Said mixture is taken to pour into Teflon mould, normal temperature cure 24
Hour, cold mixing bituminous epoxy solidfied material dumbbell shape sample is obtained after the demoulding, for tensile property test.Tensile property test condition
For 23 ± 2 DEG C, rate of extension is 10mm/min.Adhesion strength is tested using drawing instrument.Stretching and pull-out test result are seen attached list
1。
The mechanical property of the high tenacity cold mixing bituminous epoxy binding agent of subordinate list 1
Claims (8)
1. a kind of high tenacity cold mixing bituminous epoxy binding agent, it is characterised in that：Including component A and component B, the component A and group
The mass ratio for dividing B is 100：110-100：200；
The component A includes the material of following parts by weight：
100 parts of epoxy resin
5-20 parts of toughener
10-30 parts of diluent
The component B includes the material of following parts by weight：
Toughener in the component A is that the curing agent in branched nitrile rubber, the component B is low molecular polyamides.
2. high tenacity cold mixing bituminous epoxy binding agent according to claim 1, it is characterised in that：Epoxy in the component A
Resin is liquid bisphenol A type tetraglycidel ether epoxy resin, and diluent is reactive epoxies diluent.
3. high tenacity cold mixing bituminous epoxy binding agent according to claim 1 or 2, it is characterised in that：The increasing of the component A
Tough dose is branched nbr carboxyl terminal.
4. high tenacity cold mixing bituminous epoxy binding agent according to claim 1, it is characterised in that：Pitch in the component B
For SBS modified pitch, diluent is the good solvent of pitch, and compatilizer is stearic acid or stearic acid containing epoxy radicals and fatty long-chain
Ester, defoamer is polysiloxane defoaming agent.
5. the high tenacity cold mixing bituminous epoxy binding agent according to claim 1 or 4, it is characterised in that：The component B's is dilute
Releasing agent includes acetone, toluene, dimethylbenzene, dichloropropane, tetrachloro-ethylene, dibutyl phthalate, dioctyl phthalate
In one or more of mixtures.
6. the high tenacity cold mixing bituminous epoxy binding agent according to claim 1 or 4, it is characterised in that：The phase of the component B
Holding agent includes epoxidized soybean oil, epoxystearic acid, epoxy stearate, epoxyoleic acid, Epoxy oil acid esters, epoxy linoleic acid, ring
One or more of mixtures in oxygen linoleate and PEO stearic acid.
7. a kind of preparation method for preparing high tenacity cold mixing bituminous epoxy binding agent described in claim 1, it is characterised in that：
Component A preparation：Epoxy resin, diluent and toughener are mixed in mass ratio, 40-60 DEG C is heated to, with 200-500
Rev/min speed stir 1-6 hours, be cooled to room temperature, obtain the component A of high tenacity cold mixing bituminous epoxy binding agent；
Component B preparation：Pitch is heated to 110-135 DEG C of melting.Mix asphalt and diluent and stirring extremely drip in mass ratio
Green grass or young crops is completely dissolved, and cools down and adds curing agent, compatilizer and defoamer, is stirred 1-4 hours with 200-500 revs/min of speed,
Obtain the B component of high tenacity cold mixing bituminous epoxy binding agent；
Component A is mixed with component B, is stirred rapidly 3-5 minutes and is made with 500-900 revs/min of speed.
8. the preparation method of high tenacity cold mixing bituminous epoxy binding agent according to claim 7, it is characterised in that：Described
Toughener in component A is made by following steps：
A. using trimethylolpropane as core, nbr carboxyl terminal, trimethylolpropane, catalyst and hexamethylene are mixed,
Wherein the mol ratio of trimethylolpropane and nbr carboxyl terminal carboxyl is 3:4, back flow reaction 1-8 hours；
B. by vacuum distillation desolvation, washed using ether and residual solvent, small molecule by-product are removed by surname extraction
Thing and unreacted monomer；
C. extract is placed in vacuum drying oven and dried, obtain the toughener of high tenacity cold mixing bituminous epoxy binding agent.
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| CN108914737A (en) * | 2018-06-10 | 2018-11-30 | 重庆诚邦路面材料有限公司 | A kind of fine antiskid wearing layer of cement pavement EAP and construction method |
| CN109337297A (en) * | 2018-10-17 | 2019-02-15 | 河海大学 | A kind of road and bridge mat formation with high bitumen content cold mixing bituminous epoxy and the preparation method and application thereof |
| CN109797648A (en) * | 2019-03-21 | 2019-05-24 | 河南省交通规划设计研究院股份有限公司 | Bridge Surface Paving by Cement water-proof binding layer material |
| CN110372834A (en) * | 2019-07-31 | 2019-10-25 | 文山州广那高速公路投资建设开发有限公司 | Cold mixing type colour epoxy pitch, compatilizer and preparation method |
| CN113773800A (en) * | 2021-09-16 | 2021-12-10 | 南京朝科路桥工程技术有限公司 | Environment-friendly epoxy asphalt binder and preparation method thereof |
| CN117624919A (en) * | 2023-11-20 | 2024-03-01 | 北京建筑大学 | Cold-mixing cold-paving vegetable oil-based epoxy asphalt and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108914737A (en) * | 2018-06-10 | 2018-11-30 | 重庆诚邦路面材料有限公司 | A kind of fine antiskid wearing layer of cement pavement EAP and construction method |
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| CN110372834A (en) * | 2019-07-31 | 2019-10-25 | 文山州广那高速公路投资建设开发有限公司 | Cold mixing type colour epoxy pitch, compatilizer and preparation method |
| CN113773800A (en) * | 2021-09-16 | 2021-12-10 | 南京朝科路桥工程技术有限公司 | Environment-friendly epoxy asphalt binder and preparation method thereof |
| CN117624919A (en) * | 2023-11-20 | 2024-03-01 | 北京建筑大学 | Cold-mixing cold-paving vegetable oil-based epoxy asphalt and preparation method thereof |
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|---|---|
| CN107151419B (en) | 2019-11-15 |
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