CN108341930A - A kind of modified epoxy and its preparation method and application - Google Patents
A kind of modified epoxy and its preparation method and application Download PDFInfo
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- CN108341930A CN108341930A CN201810187988.5A CN201810187988A CN108341930A CN 108341930 A CN108341930 A CN 108341930A CN 201810187988 A CN201810187988 A CN 201810187988A CN 108341930 A CN108341930 A CN 108341930A
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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
- C08G59/62—Alcohols or phenols
- C08G59/64—Amino alcohols
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/04—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reaction of ammonia or amines with olefin oxides or halohydrins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
Abstract
The present invention provides a kind of preparation methods of modified epoxy, using hexamethylene diamine as raw material, are modified it using single functionality glycidol ether type organic so that the solidification agent molecule of generation is that only there are one the binary secondary amine of active hydrogen for band on each N atoms；And each secondary amine group is merely able to react with an epoxy group, therefore the curing agent that each molecular modification obtains only is reacted with two molecule epoxy groups, the microstructure of two-dimentional threadiness can finally be formed, so that the modified epoxy generated has thermoplasticity, it can soften and flow in a heated state.The present invention provides a kind of modified epoxies, have secondary curing property, after being used as road surface bonding layer material, during pavement construction, when pave above the adhesive layer hot-laid mixture when, the epoxy resin after solidification can be heated thawing, and upper layer of material and subsurface material is well-bonded.
Description
Technical field
The present invention relates to epoxy resin modification technical field more particularly to a kind of modified epoxy and preparation method thereof and
Using.
Background technology
In the construction on bituminous highway road surface, the intensity of asphalt is mainly by between the cohesive force of asphalt material and aggregate
Internal friction provide.However between the burnishing surface layer that two processes roll, the internal friction between aggregate has substantially reduced, this
When face interlayer mainly by sticking material provide binding force.
Currently used bonding layer material is emulsified asphalt and high adhered modification emulsified asphalt, and the U.S. mainly uses slow breaking breast
Change pitch as sticking material, French then major part uses splits type cationic emulsified bitumen soon, Japanese then newborn using modified rubber
Change pitch and does adhesion coating.But in the construction process, when asphalt paving vehicle traveling is on the sticking layer oil dispensed, part is had
Sticking layer oil is attached on vehicle tyre, and sticking layer oil is caused to be unevenly distributed, and may influence its bond effect, is also easy to produce interlayer cunning
It moves, and then crescent crescent cracking occurs, road surface early damage is finally caused under load and rainwater effect.Therefore, it is badly in need of grinding
Study carefully a kind of novel bonding layer material and replaces emulsified asphalt class bonding layer material.
Epoxy resin makes them as a kind of common adhesive due to containing active epoxy group in molecular structure
It can be crosslinked with a plurality of types of curing agent and react and formed and do not melt insoluble high polymer, have construction technology simple, solidification
The various advantage of mode, the epoxy resin after solidification have good physical and chemical properties.However, having heat cured epoxy
Change in physical state no longer occurs after solidification for resin, and quality is hard, also no longer softens insoluble in solvent, heating,
The direct decomposition if temperature is excessively high.It newly paves if being dispensed the epoxy resin behind road surface, solidification and will be unable to cohesive upper layer
Hot-laid mixture.
Invention content
The purpose of the present invention is to provide a kind of modified epoxy and its preparation method and application, the modified epoxy tree
There is good thermoplasticity in a period of time of fat after hardening, can be used as bonding layer material.
In order to achieve the above-mentioned object of the invention, the present invention provides following technical scheme：
The present invention provides a kind of preparation methods of modified epoxy, comprise the following steps：
Addition reaction is carried out after single functionality glycidol ether type organic, hexamethylene diamine and absolute ethyl alcohol are mixed, is obtained
Curing agent；
The curing agent and epoxy source material system is mixing cured, obtain modified epoxy.
Preferably, the single functionality glycidol ether type organic is that phenyl glycidyl ether and/or butyl shrink are sweet
Oily ether.
Preferably, the mass ratio of the single functionality glycidol ether type organic, hexamethylene diamine and absolute ethyl alcohol be (60~
75):(20~35):(150~200).
Preferably, the temperature of the addition reaction is 50~70 DEG C, and the time of the addition reaction is 1~8h.
Preferably, the epoxy source material system includes epoxy source material and reactive diluent.
Preferably, the reactive diluent is polypropylene glycol diglycidyl ether.
Preferably, mass content of the reactive diluent in epoxy source material system is 10~30%.
Preferably, the curing agent and the mass ratio of epoxy source material system are (0.5~1.5):(0.5~1.5).
The present invention provides the modified epoxies that preparation method obtains described in a kind of above-mentioned technical proposal, linear in two dimension
Microstructure.
The present invention also provides application of the modified epoxy as binding material described in a kind of above-mentioned technical proposal.
The present invention provides a kind of preparation methods of modified epoxy to be contracted using single functionality using hexamethylene diamine as raw material
Water glycerin ether type organic modifies it so that the solidification agent molecule of generation is that only there are one living for band on each N atoms
Sprinkle the binary secondary amine of hydrogen；And each secondary amine group is merely able to react with an epoxy group, therefore each molecular modification obtains
Curing agent only reacted with two molecule epoxy groups, the microstructure of two-dimentional threadiness can be finally formed, so that raw
At modified epoxy have thermoplasticity, can soften and flow in a heated state.
The present invention provides a kind of modified epoxies, have secondary curing property, after being used as road surface bonding layer material,
During pavement construction, when pave above the adhesive layer hot-laid mixture when, the epoxy resin after solidification can be heated thawing,
Upper layer of material and subsurface material is well-bonded.In addition, the modified epoxy also has good water resistance, tension
Performance, shear behavior and extension at break performance etc..By embodiment record it is found that modified epoxy provided by the invention it is low
Temperature, in mild Testing Tensile Strength at Elevated Temperature be able to reach 5.47MPa, 6.71MPa and 6.11MPa, low, medium and high temperature shearing resistance
Intensity is able to reach 26.99MPa, 5.55MPa and 1.81MPa, and elongation at break bonds coagulating cement up to 146.3%
For tensile strength after soil-cement concrete up to 1.21MPa, the shear strength bonded after cement concrete-bituminous concrete can
Up to 1.12MPa.
Specific implementation mode
The present invention provides a kind of preparation methods of modified epoxy, comprise the following steps：
Addition reaction is carried out after single functionality glycidol ether type organic, hexamethylene diamine and absolute ethyl alcohol are mixed, is obtained
Curing agent；
The curing agent and epoxy source material system is mixing cured, obtain modified epoxy.
The present invention to all raw materials applied in the preparation method without particular/special requirement, using those skilled in the art institute
Well known commercial product.
It is anti-that the present invention carries out addition after mixing single functionality glycidol ether type organic, hexamethylene diamine and absolute ethyl alcohol
It answers, obtains curing agent.Hexamethylene diamine is preferably first dissolved in the ethanol solution that hexamethylene diamine is obtained in absolute ethyl alcohol by the present invention, so
The ethanol solution of single functionality glycidol ether type organic and hexamethylene diamine is mixed again afterwards.In the present invention, institute
The temperature for stating dissolving is preferably 50~70 DEG C, more preferably 55~65 DEG C, most preferably 60~62 DEG C.The present invention is to the dissolving
Specific implementation mode there is no particular/special requirement, can carry out fully dissolve.The present invention is preferably by single functionality glycidol
Ethers organic matter is added dropwise in the ethanol solution of hexamethylene diamine and is mixed, and the rate of the dropwise addition is preferably 30~40mL/
H, more preferably 32~38mL/h, most preferably 35~36mL/h.
In the present invention, the single functionality glycidol ether type organic is preferably phenyl glycidyl ether and/or fourth
Base glycidol ether.In the present invention, the single functionality glycidol ether type organic includes phenyl glycidyl ether simultaneously
When with butyl glycidyl ether, the mass ratio of the phenyl glycidyl ether and butyl glycidyl ether can be 55:16、38:
33 or 20:50.In the present invention, the mass ratio of the single functionality glycidol ether type organic, hexamethylene diamine and absolute ethyl alcohol
Preferably (60~75):(20~35):(150~200), more preferably (62~68):(21~24):(160~190), it is optimal
It is selected as (64~66):(22~23):(170~180).
In the present invention, the temperature of the addition reaction is preferably 50~70 DEG C, more preferably 55~65 DEG C, most preferably
60~62 DEG C；The time of the addition reaction is preferably 1~8h, more preferably 2~6h, most preferably 3~5h.
In the present invention, described to add when the single functionality glycidol ether type organic is phenyl glycidyl ether
It is shown in formula I at reaction, it obtains being that phenyl glycidyl ether is modified hexamethylene diamine curing agent.
In the present invention, described to add when the single functionality glycidol ether type organic is butyl glycidyl ether
At reaction as shown in Formula II, obtain being butylglycidylether modified hexamethylene diamine curing agent.
In the present invention, when the single functionality glycidol ether type organic is that phenyl glycidyl ether and butyl shrink
When the mixture of glycerin ether, obtain be phenyl glycidyl ether be modified hexamethylene diamine curing agent, it is butylglycidylether modified oneself
Diamine curing agent, phenyl glycidyl ether and butyl glycidyl ether are modified the mixture of hexamethylene diamine curing agent jointly.Wherein, institute
It states phenyl glycidyl ether and butyl glycidyl ether and is modified the reaction process of hexamethylene diamine curing agent jointly as shown in formula III.
In the present invention, after the addition reaction, the present invention preferably post-processes obtained product system, with
Obtain pure curing agent.In the present invention, the post-processing preferably comprises following steps：
Remove the anhydrous ethanol solvent in the addition compound product system；
Product system after removal anhydrous ethanol solvent is mixed with chloroform, then sequentially uses water and saturated salt solution
It is washed；
Processing is dried to the organic phase obtained after the washing；
The chloroform in the siccative for being dried and obtaining is removed, pure curing agent is obtained.
The present invention removes the anhydrous ethanol solvent in the addition compound product system first, and the present invention is preferably to the product body
System is evaporated processing, removes anhydrous ethanol solvent therein.The present invention is not any to the embodiment of the evaporation process
Particular/special requirement, using ethanol evaporation well-known to those skilled in the art method carry out.
The present invention mixes the product system after removing anhydrous ethanol solvent with chloroform, then sequentially uses water and saturation
Saline solution is washed.The present invention to the additive amount of the chloroform without particular/special requirement, can be complete by all product systems
Dissolving.The present invention does not have particular/special requirement to the method for the water and saturated common salt water washing, using those skilled in the art
The common washing methods of institute carries out.In the present invention, the washing and saturated common salt water washing can wash away water-soluble
Remain hexamethylene diamine.
After the washing, processing is dried to obtained organic phase in the present invention.In the present invention, the drying is excellent
It is selected as being dried using anhydrous magnesium sulfate.The present invention does not require the specific implementation mode that the anhydrous magnesium sulfate is dried,
It can realize dry purpose.
After the drying process, the present invention removes the chloroform in the siccative for being dried and obtaining, and obtains pure
Curing agent；The present invention preferably carries out distillation processing to the obtained siccative that is dried, and is obtained after removing chloroform pure
Net curing agent.The present invention does not have particular/special requirement to the embodiment of the distillation processing, ripe using those skilled in the art institute
The distillating method known can realize the technical purpose of distillation removal chloroform.
After obtaining curing agent, the present invention is mixing cured by the curing agent and epoxy source material system, obtains modified ring
Oxygen resin.In the present invention, the epoxy source material system preferably comprises epoxy source material and reactive diluent；The work
Property diluent is preferably polypropylene glycol diglycidyl ether, and the number-average molecular weight of the polypropylene glycol diglycidyl ether is preferably
620~660, more preferably 630~650, most preferably 635~645；The epoxy source material is preferably bisphenol type epoxy
Resin, more preferably E-44.The addition of reactive diluent can reduce asphalt mixtures modified by epoxy resin in epoxy source material system of the present invention
The viscosity of fat raw material increases its contact with curing agent, and then improves curing uniformity.
In the present invention, mass content of the reactive diluent in epoxy source material system be preferably 10~
30%, more preferably 15~25%.
In the present invention, the curing agent and the mass ratio of epoxy source material system are preferably (0.5~1.5):(0.5
~1.5), more preferably (0.8~1.2):(0.8~1.2), most preferably 1:1.
In the present invention, operation is heated or cooled without additional in the solidification, spontaneous can carry out at room temperature；It is described
The cured time is preferably 4~10h, more preferably 5~7h.In the curing reaction, the ring in epoxy source material system
Oxygen groups are reacted with solidification agent molecule there are one the secondary amine group of active hydrogen, and the microcosmic of two-dimentional threadiness can be finally formed
Structure can soften and flow in a heated state so that the modified epoxy generated has thermoplasticity.In the present invention
In, in each epoxy source material preferably there are two epoxy group participate in reaction, and two epoxy groups preferably from it is different
Solidification agent molecule is reacted；The degree of polymerization of the modified epoxy of the linear microstructure of two dimension is preferably 30~35.
The present invention provides the modified epoxies that preparation method obtains described in a kind of above-mentioned technical proposal, linear in two dimension
Microstructure, have thermoplasticity, can soften and flow in a heated state, be used as road surface bonding layer material after, applied on road surface
During work, when pave above the adhesive layer hot-laid mixture when, the epoxy resin after solidification can be heated thawing, by upper layer
Material and subsurface material are well-bonded.
The present invention also provides application of the modified epoxy as binding material described in a kind of above-mentioned technical proposal.This hair
The bright application method to the modified epoxy as bonding layer material does not have particular/special requirement, and it is to be bonded to be positioned in both sides
It carries out bonding between layer.The modified epoxy is preferably used for deck paving bonding layer material by the present invention.In this hair
In bright, when the modified epoxy is as bonding layer material, construction dosage is preferably 0.4~0.6kg/m2, more preferably
0.5~0.55kg/m2。
Modified epoxy provided by the invention and its preparation method and application is carried out with reference to embodiment detailed
Illustrate, but they cannot be interpreted as limiting the scope of the present invention.
In all embodiments of the invention, in the case of no specified otherwise, all parts are all mass parts.
Embodiment 1
28 parts of hexamethylene diamines are dissolved in 150 parts of absolute ethyl alcohols, after being stirred and heated to 60 DEG C, by 72 parts of phenyl glycidyls
Ether is slowly dropped into the ethanol solution of hexamethylene diamine and continues to stir, and control rate of addition is added dropwise in 2h, under the conditions of 60 DEG C
4h is reacted, alcohol solvent is evaporated off after reaction, chloroform is added and all dissolves product, tap water and saturation is used to eat respectively
Salt water washing, anhydrous magnesium sulfate dry organic phase, filter and be evaporated under reduced pressure remove chloroform obtain curing agent PTC-1.
100 parts of epoxy source materials are dilute in 620~660 polypropylene glycol diglycidyl ether with 20 parts of molecular weight distributions
It releases, then with obtained mixing cured 4h of PTC-1, obtains modified epoxy.
The present invention carries out performance detection to obtained modified epoxy, tensile strength and shearing strength basis respectively《It applies
The measuring method-of layer adhesive force pulls open method》(GB 5210-85) and Japan《Shearing conjugation test piece》(JIS 6850-2) is carried out
Test, low temperature, room temperature and hot conditions are respectively -10 DEG C, 25 DEG C and 60 DEG C.As a result as follows：
Tension, the shearing strength of 1 modified epoxy of table
From the data in table 1, it can be seen that the modified epoxy that the present embodiment obtains meets People's Republic of China's building trade mark
It is accurate《Bridge water-repellent paint》Requirement in (JCT 975-2005).
Embodiment 2
29 parts of hexamethylene diamines are dissolved in 150 parts of absolute ethyl alcohols, after being stirred and heated to 60 DEG C, by 55 parts of phenyl glycidyls
Ether and 16 parts of butyl glycidyl ethers are slowly dropped into the ethanol solution of hexamethylene diamine and continue to stir, and control rate of addition is in 2h drops
It adds complete, reacts 4h under the conditions of 60 DEG C, alcohol solvent is evaporated off after reaction, chloroform is added and all dissolves product,
Tap water and saturated common salt water washing, anhydrous magnesium sulfate is used to dry organic phase, filter and be evaporated under reduced pressure removing chloroform respectively
Obtain curing agent PTC-2.
100 parts of epoxy source materials are dilute in 620~660 polypropylene glycol diglycidyl ether with 20 parts of molecular weight distributions
It releases, then with obtained mixing cured 4h of PTC-2, obtains modified epoxy.
The present invention carries out performance detection to obtained modified epoxy, tensile strength and shearing strength basis respectively《It applies
The measuring method-of layer adhesive force pulls open method》(GB 5210-85) and Japan《Shearing conjugation test piece》(JIS 6850-2) is carried out
Test, low temperature, room temperature and hot conditions are respectively -10 DEG C, 25 DEG C and 60 DEG C.As a result as follows：
2 adhesion coating resin tension of table, shearing strength
From the data in table 2, it can be seen that the modified epoxy that the present embodiment obtains meets People's Republic of China's building trade mark
It is accurate《Bridge water-repellent paint》Requirement in (JCT 975-2005).
Embodiment 3
29 parts of hexamethylene diamines are dissolved in 150 parts of absolute ethyl alcohols, after being stirred and heated to 60 DEG C, by 38 parts of phenyl glycidyls
Ether and 33 parts of butyl glycidyl ethers are slowly dropped into the ethanol solution of hexamethylene diamine and continue to stir, and control rate of addition is in 2h drops
It adds complete, reacts 4h under the conditions of 60 DEG C, alcohol solvent is evaporated off after reaction, chloroform is added and all dissolves product,
Tap water and saturated common salt water washing, anhydrous magnesium sulfate is used to dry organic phase, filter and be evaporated under reduced pressure removing chloroform respectively
Obtain curing agent PTC-3.
100 parts of epoxy source materials are dilute in 620~660 polypropylene glycol diglycidyl ether with 20 parts of molecular weight distributions
It releases, then with obtained mixing cured 4h of PTC-3, obtains modified epoxy.
The present invention carries out performance detection to obtained modified epoxy, tensile strength and shearing strength basis respectively《It applies
The measuring method-of layer adhesive force pulls open method》(GB 5210-85) and Japan《Shearing conjugation test piece》(JIS 6850-2) is carried out
Test, low temperature, room temperature and hot conditions are respectively -10 DEG C, 25 DEG C and 60 DEG C.As a result as follows：
3 adhesion coating resin tension of table, shearing strength
From the data in table 3, it can be seen that the modified epoxy that the present embodiment obtains meets People's Republic of China's building trade mark
It is accurate《Bridge water-repellent paint》Requirement in (JCT 975-2005).
Embodiment 4
30 parts of hexamethylene diamines are dissolved in 150 parts of absolute ethyl alcohols, after being stirred and heated to 60 DEG C, by 20 parts of phenyl glycidyls
Ether and 50 parts of butyl glycidyl ethers are slowly dropped into the ethanol solution of hexamethylene diamine and continue to stir, and control rate of addition is in 2h drops
It adds complete, reacts 4h under the conditions of 60 DEG C, alcohol solvent is evaporated off after reaction, chloroform is added and all dissolves product,
Tap water and saturated common salt water washing, anhydrous magnesium sulfate is used to dry organic phase, filter and be evaporated under reduced pressure removing chloroform respectively
Obtain curing agent PTC-4.
100 parts of epoxy source materials are dilute in 620~660 polypropylene glycol diglycidyl ether with 20 parts of molecular weight distributions
It releases, then with obtained mixing cured 4h of PTC-4, obtains modified epoxy.
The present invention carries out performance detection to obtained modified epoxy, tensile strength and shearing strength basis respectively《It applies
The measuring method-of layer adhesive force pulls open method》(GB 5210-85) and Japan《Shearing conjugation test piece》(JIS 6850-2) is carried out
Test, low temperature, room temperature and hot conditions are respectively -10 DEG C, 25 DEG C and 60 DEG C.As a result as follows：
4 adhesion coating resin tension of table, shearing strength
From the data in table 4, it can be seen that the modified epoxy that the present embodiment obtains meets People's Republic of China's building trade mark
It is accurate《Bridge water-repellent paint》Requirement in (JCT 975-2005).
Embodiment 5
31 parts of hexamethylene diamines are dissolved in 150 parts of absolute ethyl alcohols, after being stirred and heated to 60 DEG C, by 69 parts of butyl glycidyls
Ether is slowly dropped into the ethanol solution of hexamethylene diamine and continues to stir, and control rate of addition is added dropwise in 2h, under the conditions of 60 DEG C
4h is reacted, alcohol solvent is evaporated off after reaction, chloroform is added and all dissolves product, tap water and saturation is used to eat respectively
Salt water washing, anhydrous magnesium sulfate dry organic phase, filter and be evaporated under reduced pressure remove chloroform obtain curing agent PTC-5.
100 parts of epoxy source materials are dilute in 620~660 polypropylene glycol diglycidyl ether with 20 parts of molecular weight distributions
It releases, then with obtained mixing cured 4h of PTC-5, obtains modified epoxy.
The present invention carries out performance detection to obtained modified epoxy, tensile strength and shearing strength basis respectively《It applies
The measuring method-of layer adhesive force pulls open method》(GB 5210-85) and Japan《Shearing conjugation test piece》(JIS 6850-2) is carried out
Test, low temperature, room temperature and hot conditions are respectively -10 DEG C, 25 DEG C and 60 DEG C.As a result as follows：
5 adhesion coating resin tension of table, shearing strength
From the data in table 5, it can be seen that the modified epoxy that the present embodiment obtains meets People's Republic of China's building trade mark
It is accurate《Bridge water-repellent paint》Requirement in (JCT 975-2005).
Embodiment 6
100 parts of epoxy source materials are dilute in 620~660 polypropylene glycol diglycidyl ether with 20 parts of molecular weight distributions
It releases, tri- kinds of mixing cured 4h of curing agent of PTC-1, PTC-3 and the PTC-5 then obtained respectively with above-described embodiment, according to Japan
Industrial standard《The stretching test method of plastic material》The method of (JIS K 7113) carries out the test of material elongation at break, knot
Fruit is as follows.
The elongation at break of material after the different curing agent moldings of 6 three kinds of table
In table 6 E-44 represent in the market certain by 650 polyamides cure E-44 product.
Although ordinary epoxy resin excellent in mechanical performance, material brittleness itself is larger, is easily broken, in the application
Modified epoxy have the tension failure performance more excellent than ordinary epoxy resin.In practical engineering application, work as road surface
When cracking, which, which can guarantee, has preferable crack tracing ability.
Embodiment 7
100 parts of epoxy source materials are dilute in 620~660 polypropylene glycol diglycidyl ether with 20 parts of molecular weight distributions
It releases, tri- kinds of curing agent of PTC-1, PTC-3 and the PTC-5 then obtained respectively with above-described embodiment mix, and are coated on 4cm × 4cm
C40 cement concrete test blocks on (coating coating weight 0.5kg/m2), and be bonded in C40 cement concrete substrates, it rises
Temperature to room temperature is down to after 140 DEG C naturally again, with the velocity test tensile strength of 2mm/min under conditions of 25 DEG C after 7d, as a result
It is as follows.
Cement concrete-cement concrete tensile strength of the different curing agent of 7 three kinds of table
Jiangsu Province's provincial standard《Cement concrete bridge deck water-base epoxy asphalt waterproofing adhesive layer construction technique normalizing》
Tensile strength need to be more than 0.40MPa under the conditions of requiring 25 DEG C in (DB32/T 2285-2012), using PTC-1, PTC-3 and
The modified epoxy that PTC-5 is modified can meet above-mentioned code requirement.
Embodiment 8
100 parts of epoxy source materials are dilute in 620~660 polypropylene glycol diglycidyl ether with 20 parts of molecular weight distributions
It releases, is then mixed with PTC-3, obtain resin compound.
Resin compound is coated on the C40 cement concrete slabs of 30cm × 30cm × 5cm and (applies by construction simulation process
Layer coating weight 0.5kg/m2), it waits for that its surface drying overlays the hot-mix asphalt mixture of 30cm × 30cm × 5cm on upper layer later, rolls
7d is placed after molding at room temperature, is drilled throughCore sample with the speed of 50mm/min shear under the conditions of 25 DEG C it is strong
Degree test, test result are higher by similar-type products about 14%.
8 adhesion coating resin cement concrete of table-asphalt concrete shearing intensity
Jiangsu Province's provincial standard《Cement concrete bridge deck water-base epoxy asphalt waterproofing adhesive layer construction technique normalizing》
Shearing strength need to be more than 0.50MPa under the conditions of requiring 25 DEG C in (DB32/T 2285-2012), use the adhesion coating resin of PTC-3
It is not single to meet code requirement, while there is the cutting performance more excellent than similar product.
As seen from the above embodiment, the present invention provides a kind of preparation methods of modified epoxy, are original with hexamethylene diamine
Material, modifies it using single functionality glycidol ether type organic so that the solidification agent molecule of generation is each N atoms
On all only band there are one active hydrogen binary secondary amine；And every part of binary secondary amine is all merely able to react with a epoxy group, therefore
The curing agent that each molecular modification obtains only is reacted with two molecule epoxy groups, and the microcosmic of two-dimentional threadiness can be finally formed
Structure can soften and flow in a heated state so that the modified epoxy generated has thermoplasticity.
The present invention provides a kind of modified epoxies, have secondary curing property, after being used as road surface bonding layer material,
During pavement construction, when pave above the adhesive layer hot-laid mixture when, the epoxy resin after solidification can be heated thawing,
Upper layer of material and subsurface material is well-bonded.In addition, the modified epoxy also has good water resistance, tension
Performance, shear behavior and extension at break performance etc..By embodiment record it is found that modified epoxy provided by the invention it is low
Temperature, in mild Testing Tensile Strength at Elevated Temperature be able to reach 5.47MPa, 6.71MPa and 6.11MPa, low, medium and high temperature shearing resistance
Intensity is able to reach 26.99MPa, 5.55MPa and 1.81MPa, and elongation at break bonds coagulating cement up to 146.3%
For tensile strength after soil-cement concrete up to 1.21MPa, the shear strength bonded after cement concrete-bituminous concrete can
Up to 1.12MPa.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of modified epoxy, comprises the following steps：
Addition reaction is carried out after single functionality glycidol ether type organic, hexamethylene diamine and absolute ethyl alcohol are mixed, is cured
Agent；
The curing agent and epoxy source material system is mixing cured, obtain modified epoxy.
2. preparation method according to claim 1, which is characterized in that the single functionality glycidol ether type organic is
Phenyl glycidyl ether and/or butyl glycidyl ether.
3. preparation method according to claim 1 or 2, which is characterized in that the single functionality glycidol ethers are organic
The mass ratio of object, hexamethylene diamine and absolute ethyl alcohol is (60~75):(20~35):(150~200).
4. preparation method according to claim 3, which is characterized in that the temperature of the addition reaction is 50~70 DEG C, institute
The time for stating addition reaction is 1~8h.
5. preparation method according to claim 1, which is characterized in that the epoxy source material system includes epoxy resin
Raw material and reactive diluent.
6. preparation method according to claim 1 or 5, which is characterized in that the reactive diluent contracts for polypropylene glycol two
Water glycerin ether.
7. preparation method according to claim 6, which is characterized in that the reactive diluent is in epoxy source material system
In mass content be 10~30%.
8. preparation method according to claim 1 or claim 7, which is characterized in that the curing agent and epoxy source material system
Mass ratio be (0.5~1.5):(0.5~1.5).
9. the modified epoxy that preparation method obtains described in claim 1~8 any one, in the linear microcosmic knot of two dimension
Structure.
10. application of the modified epoxy described in claim 9 as binding material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| CN112411372A (en) * | 2020-11-25 | 2021-02-26 | 上海浦兴路桥建设工程有限公司 | Thin-layer epoxy polymer concrete suitable for steel box girder bridge floor and preparation method thereof |
| WO2022110549A1 (en) * | 2020-11-25 | 2022-06-02 | 中路交科科技股份有限公司 | Second-order epoxy adhesive layer oil, preparation method therefor and application method thereof |
| CN115651585A (en) * | 2022-10-18 | 2023-01-31 | 保利长大工程有限公司 | Hot-melt epoxy resin binder and preparation method thereof |
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