CN106280277B - A kind of preparation method and application of environmental protection low viscosity high-strength epoxy base grouting material - Google Patents
A kind of preparation method and application of environmental protection low viscosity high-strength epoxy base grouting material Download PDFInfo
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- CN106280277B CN106280277B CN201610665279.4A CN201610665279A CN106280277B CN 106280277 B CN106280277 B CN 106280277B CN 201610665279 A CN201610665279 A CN 201610665279A CN 106280277 B CN106280277 B CN 106280277B
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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
- C08G59/50—Amines
- C08G59/5006—Amines aliphatic
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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
- C08G59/50—Amines
- C08G59/56—Amines together with other curing agents
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- Medicinal Chemistry (AREA)
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- Epoxy Resins (AREA)
Abstract
The present invention discloses a kind of preparation method of environmentally friendly low viscosity high-strength epoxy base grouting material, comprising the following steps: 1) 50~80 parts of epoxy resin and 20~50 parts of crosslinking diluents is mixed to get A liquid；2) 5~10 parts of curing agent and 1~5 part of promotor are mixed to get B liquid；3) 1~10 part of initiator is separately formed C component；4) first A liquid and B liquid are mixed evenly when using, C component is then added, obtains environmentally friendly low viscosity high-strength epoxy base grouting material after mixing evenly.The filling material component is nontoxic, to human body and environmental-friendly；The viscosity of initial slurry is low, and concrete castability is excellent, has drainage, can solidify in water；Slurries shrinking percentage when being gelled solidification is small, solidifies volume stability, and solidfied material excellent mechanical；Grout coordinate ratio is simple, is easy to grasp, and raw material are easy to buy.The grouting material can be applied to the anti-Seepage of plate, the reinforcing of beam or rod structure distress in concrete and the concrete crack of water conservancy project.
Description
Technical field:
The present invention relates to a kind of environmentally friendly low viscosity high-strength epoxy base grouting material based on epoxy resin, in particular to use
It is reinforced in the structural concretes crack strengthening such as plate, beam, column and the environmentally friendly low viscosity of the concrete crack of water conservancy project anti-Seepage is high-strength
The preparation method of type ring oxygroup grouting material.
Background technique:
Epoxide resin grouting material is after sticky epoxy resin is reduced viscosity with diluent, to be aided with curing agent, toughening
The auxiliary agents such as agent and surfactant and obtain Multi component grouting material.In chemical grouting material family, epoxy resin is filled
Pulp material is become in the engineerings such as ground base enforcement and structure repair with its good base's adaptability, excellent mechanical strength
Leading chemical grouting material.
The slurry material is grouped as by two groups of A, B, and component A is made of epoxy resin and diluent, and B component is generally solidified body
System.Epoxy resin requires its slurries to have lesser viscosity and suitable operating time, common ring first as grouting material
Oxygen resin viscosity itself is larger, therefore critical issue is to reduce its viscosity as far as possible, while solidfied material must be made to have institute again
The various performances needed, in general, being classified as three categories by the difference of diluent used in epoxide resin grouting material: (1) nonactive
The component of the epoxy grouting material of diluent system, this epoxy grouting material is simple, generally nonactive by acetone, dimethylbenzene etc.
Diluent and epoxy resin mixing composition.This kind of River Bank Stability is simple, and viscosity is lower, but joined and be largely not involved in instead
The solvent answered, causes physical property to decline, and solidfied material is shunk greatly, has currently been rarely employed；(2) furfural-acetone diluted system
Epoxide resin grouting material, the ratio used at present in China is wide, it can be solidified under alkaline environment according to furfural-acetone
Furane resins are formed, the latter forms entirety with inierpeneirating network structure and epoxy resin cured product, thus considerably reduces acetone
Volatilization, have both the excellent performance of epoxy resin and furane resins, high mechanical strength is secured with rock and concrete binding,
Water-fast, acidproof, alkaline-resisting, resistant to salt corrosion, ageing-resistant performance spy is excellent, with the development of China's polymer chemistry industry, curable epoxide
The type of agent is increasing, and the epoxide resin grouting material studied at present has more excellent physical property and high infiltration
Property, even if being perfused in crack (containing circulating water is pressed) under water, good mechanical property can be also obtained under suitable process conditions
Can and bonding viscosity, but this kind of grouting material is disadvantageous in that and has used that highly toxic furfural, the slurries feature of environmental protection is not good enough, in addition
Solvent volatilization, the problems such as frequently resulting in that construction site air environment is severe, and grout curing thermal discharge is big, be easy to appear " implode ".
(3) epoxy grouting material of reactive diluent system (no-solvent type), this epoxy grouting material are generally shunk with low molecular weight
Glycerin ether or glycidol esters compound are that diluent contains in structure in addition since this kind of compound viscosity itself is very low
It can participate in the epoxy group of curing agent reaction, commonly known as reactive diluent.Non-activated thinner is replaced with reactive diluent,
Due to overcoming the volatilization of solvent, slurry material is with good performance, and the viscosity of existing reactive diluent itself is generally all than non-live
Property diluent is big, and dilution effect is not satisfactory, therefore the concrete castability of slurries is subject to certain restrictions, and dosage will affect solidfied material too much
Crosslink density.
Therefore, seek reasonable component in the ocean of chemical material, the epoxy base grouting material for solving the prior art is deposited
The problem of become that there is an urgent need to can push CHEMICAL GROUTING TECHNOLGY to play bigger effectiveness in engineering construction field.
Summary of the invention:
The primary purpose of the present invention is that overcome existing epoxide resin grouting material the feature of environmental protection and mechanical property not
Foot, provides that a kind of environment-friendly type initial viscosity is low, solidfied material intensity is high, concrete castability is good and can solidify under water and keep good
The preparation method of the environmentally friendly low viscosity high-strength epoxy base grouting material of mechanical property.
The second object of the present invention is to provide the application range of the environmentally friendly low viscosity high-strength epoxy grouting material.
Above-mentioned purpose of the invention can be achieved through the following technical solutions:
A kind of preparation method of environment-friendly, high-intensity type ring oxygroup chemical grouting material, comprising the following steps:
1) the crosslinking diluent of 50~80 parts of epoxy resin and 20~50 parts is mixed to get A liquid；
2) 5~10 parts of curing agent and 1~5 part of promotor are mixed to get B liquid；
3) 1~10 part of initiator is separately formed C component；
4) first A liquid and B liquid are mixed evenly when using, C component is then added, obtains environment-friendly, high-intensity after mixing evenly
Type ring oxygroup chemical grouting material.
Epoxy resin described in step 1 is bisphenol A type epoxy resin.
Bisphenol A type epoxy resin described in step 1 is E-35 type epoxy resin, E-44 type epoxy resin or E-51 type ring
One of oxygen resin or at least two.
Crosslinking diluent described in step 1 is one kind of methyl methacrylate, butyl acrylate or hy-droxybutyl
Or at least two.
Curing agent described in step 2 is one of diethylenetriamine, triethylene tetramine or tetraethylenepentamine or at least two
Kind.
Promotor described in step 2 is N, one of N dimethyl aniline, ethyl imidazol(e) or methylimidazole.
Initiator described in step 3 is prepared by following steps: by peroxide and atent solvent according to mass ratio (50
~80): the proportion mixing of (20~50) is sufficiently dehydrated acquisition initiator after standing 24 hours.
The peroxide is benzoyl peroxide, cyclohexanone peroxide, dilauroyl peroxide, t-butylperbenzoate
One of or at least two；The inertia solution is dibutyl phthalate.
Above-mentioned environmentally friendly low viscosity high-strength epoxy base grouting material adds in the reinforcement of plate, beam or rod structure distress in concrete
Gu and the application in the anti-Seepage of the concrete crack of water conservancy project.
Above-mentioned environmentally friendly low viscosity high-strength epoxy base grouting material can be used as the contact between concrete and metal material
Grouting material.
The present invention has the following advantages and effects with respect to the prior art:
1, the preparation method of environmentally friendly low viscosity high-strength epoxy base grouting material of the present invention, grout coordinate ratio letter
It is single, it is easy to grasp, and raw material are easy to buy, is convenient for storage and transportation.
2, the present invention selects crosslinking diluent instead of furfural-acetone series reactive diluent and to sacrifice injection material
Expect that mechanical property is the glycidol ether diluent of cost, component does not include the volatile material such as formaldehyde, acetone, to human body and
It is environmental-friendly, meet Green Development theory.
3, the viscosity of the initial slurry of epoxy base grouting material of the present invention is low, and concrete castability is excellent, has drainage, can
Solidify in water；When being gelled solidification, shrinking percentage is small, solidifies volume stability, and solidfied material excellent mechanical.
4, environmentally friendly low viscosity high-strength epoxy group chemical grouting material of the present invention can be applied to plate, beam or rod structure
The reinforcing of distress in concrete and the anti-Seepage of the concrete crack of water conservancy project；Also it can be used as connecing between concrete and metal material
Touch grouting material.
Specific embodiment:
Present invention is further described in detail by way of example below, but application mode of the invention is without being limited thereto.
Embodiment 1:
The present invention provides a kind of preparation methods of environment-friendly, high-intensity type ring oxygroup chemical grouting material, comprising the following steps:
1) the crosslinking diluent of 50~80 parts of epoxy resin and 20~50 parts is mixed to get A liquid；
2) 5~10 parts of curing agent and 1~5 part of promotor are mixed to get B liquid；
3) 1~10 part of initiator is separately formed C component；
4) A liquid and B liquid are mixed evenly when using, C component is then added, obtains environment-friendly, high-intensity type after mixing evenly
Epoxy group chemical grouting material.
Embodiment 2:
On the basis of embodiment 1, epoxy resin described in step 1 is bisphenol A type epoxy resin, the bisphenol A-type
Epoxy resin is one of E-35 type epoxy resin, E-44 type epoxy resin or E-51 type epoxy resin or at least two.
Crosslinking diluent described in step 1 is one kind of methyl methacrylate, butyl acrylate or hy-droxybutyl
Or at least two.
Curing agent described in step 2 is one of diethylenetriamine, triethylene tetramine or tetraethylenepentamine or at least two
Kind.
Promotor described in step 2 is N, one of N dimethyl aniline, ethyl imidazol(e) or methylimidazole.
Initiator described in step 3 is prepared by following steps: by peroxide and atent solvent according to mass ratio (50
~80): the proportion mixing of (20~50) is sufficiently dehydrated acquisition initiator after standing 24 hours.
The peroxide is one of organic peroxide or at least two；The peroxide is more preferably
One of benzoyl peroxide, cyclohexanone peroxide, dilauroyl peroxide, t-butylperbenzoate or at least two.It is described
Inertia solution be one or both of fragrant rouge；The inertia solution is more preferably dibutyl phthalate.
The present invention selects crosslinking diluent instead of furfural-acetone series reactive diluent and to sacrifice grouting material
Mechanical property is the glycidol ether diluent of cost, and component does not include the volatile materials such as formaldehyde, acetone, to human body and ring
Border is friendly, meets Green Development theory；And the viscosity of initial slurry is low, solidfied material excellent mechanical, grout coordinate ratio is simple, easily
In grasp, the slurries component source of goods is wide, and price is low, and storage and transportation is convenient.The constituent of this material both participates in curing reaction, extremely by liquid
Solid reaction process does not have mass loss, and volume stability is excellent, so the material is excellent to the substantial effect in filled space
In other similar products.
Embodiment 3:
It is a kind of environmental protection low viscosity high-strength epoxy base grouting material be prepared by following methods:
1) preparation of initiator (C component): by two fourth of 65 mass parts benzoyl peroxides and 50 mass parts phthalic acid
Ester uniformly mixes, and after standing 24 hours, sufficiently dehydration obtains initiator.
2) preparation of environmentally friendly low viscosity high-strength epoxy base grouting material:
A liquid: 75 mass parts E-51 type epoxy resins are uniformly mixed to obtain with 25 mass parts methyl methacrylates；
B liquid: 10 mass parts diethylenetriamines and 4 mass parts N, N dimethyl aniline are uniformly mixed and obtain；
A liquid, B liquid are uniformly mixed to obtain nontoxic low viscosity high-strength epoxy with 8 mass parts initiators (C component) when use
Base grouting material.
Embodiment 4:
It is a kind of environmental protection low viscosity high-strength epoxy base grouting material be prepared by following methods:
1) preparation of initiator (C component): by two fourth of 55 mass parts cyclohexanone peroxides and 45 mass parts phthalic acid
Ester uniformly mixes, and after standing 24 hours, sufficiently dehydration obtains initiator.
2) preparation of environmentally friendly low viscosity high-strength epoxy base grouting material:
A liquid: 65 mass parts E-51 type epoxy resins are uniformly mixed to obtain with 35 mass parts butyl acrylates；
B liquid: 9 mass parts triethylene tetramines are uniformly mixed to obtain with 2 mass parts methylimidazoles；
A liquid, B liquid are uniformly mixed to obtain nontoxic low viscosity high-strength epoxy with 4 mass parts initiators (C component) when use
Base grouting material.
Embodiment 5:
It is a kind of environmental protection low viscosity high-strength epoxy base grouting material be prepared by following methods:
1) preparation of initiator (C component): with 3 step of example (1).
2) preparation of environmentally friendly low viscosity high-strength epoxy base grouting material:
A liquid: 55 mass parts E-44 type epoxy resin are uniformly mixed to obtain with 45 mass parts methyl methacrylates；
B liquid: 8 mass parts diethylenetriamines and 3 mass parts N, N dimethyl aniline are uniformly mixed and obtain；
A liquid, B liquid are uniformly mixed to obtain nontoxic low viscosity high-strength epoxy with 6 mass parts initiators (C component) when use
Base grouting material.
Embodiment 6:
It is a kind of environmental protection low viscosity high-strength epoxy base grouting material be prepared by following methods:
1) preparation of initiator (C component): with 3 step of example (1).
2) preparation of environmentally friendly low viscosity high-strength epoxy base grouting material:
A liquid: 65 mass parts E-44 type epoxy resin are uniformly mixed to obtain with 35 mass parts methyl methacrylates；
B liquid: 9 mass parts triethylene tetramines are uniformly mixed to obtain with 2 mass parts methylimidazoles；
A liquid, B liquid are uniformly mixed to obtain nontoxic low viscosity high-strength epoxy with 4 mass parts initiators (C component) when use
Base grouting material.
Embodiment 7:
It is a kind of environmental protection low viscosity high-strength epoxy base grouting material be prepared by following methods:
1) preparation of initiator (C component): with 4 step of example (1).
2) preparation of environmentally friendly low viscosity high-strength epoxy base grouting material:
A liquid: 55 mass parts E-51 type epoxy resins are uniformly mixed to obtain with 45 mass parts methyl methacrylates；
B liquid: 8 mass parts diethylenetriamines and 1.5 mass parts N, N dimethyl aniline are uniformly mixed and obtain；
A liquid, B liquid are uniformly mixed to obtain nontoxic low viscosity high-strength epoxy with 3 mass parts initiators (C component) when use
Base grouting material.
Embodiment effect
Epoxy base grouting material prepared by example 3~7 carries out physics, mechanical index measurement, at the beginning of which includes: slurries
Beginning viscosity, working life, perfusion ability, cubical contraction, compression strength, adhesive strength.Wherein: initial viscosity refers to grouting material
The viscosity for using rotary viscosity design determining immediately after mixing, referring to GB/T2794-2013 standard test；Working life refers to filling
Pulp material viscosity reaches the 200mPas time experienced from initial viscosity, referring to GB/T7123.1-2002 standard test；It fills
Note ability and cubical contraction reference JG/T333-2011 standard test, compression strength reference GB/T2567-2008 standard test,
Adhesive strength is referring to JG/T1041-2007 standard test.
Epoxy base grouting material main performance index is as shown in table 1:
1 epoxy base grouting material main performance index of table
| Project | Index | Remarks |
| Slurry viscosity (mPaS) | ≤200 | 20℃±3℃ |
| Serum density (g/cm3) | 1.05±0.05 | 20℃±3℃ |
| Curing time (h) | 1~6 | 20 DEG C ± 3 DEG C (adjustable) |
| Compressive strength of solidified body (MPa) | ≥70 | |
| Solidified body tensile strength (MPa) | ≥20 | |
| Solidified body shearing strength (MPa) | ≥5.0 | It is Nian Jie with steel |
| Solidify bulk modulus (GPa) | 1.1~1.2 |
Measurement result is as listed in table 2:
Physics, the mechanical index of the environmentally friendly low viscosity high-strength epoxy base grouting material of table 2
Table 2 lists physics based on nontoxic low viscosity high-strength epoxy base grouting material example 3~7 of the invention, power
Learn index determining.Corresponding index measured value shows: nontoxic low viscosity high-strength epoxy base grouting material prepared by the present invention,
Initial viscosity in 30mPas hereinafter, and typically not greater than 20mPas, perfusion capacity index be far below 8min standard index
It is required that illustrating that ability is perfused with excellent in grouting material；The working life of grouting material between 145min to 330min, and
And can be changed by component and be adjusted, the grouting time demand under different operating conditions can be met；The volume contraction of grouting material
Rate is less than 0.8%, to ensure grouting material to by the filling effect of filling body；The compression strength highest of grouting material solidfied material
91MPa is reached, and has been not less than 80MPa, adhesive strength is up to 5.1MPa under drying condition, is bonded in Soaking environment strong
Degree is not less than 3.0MPa, it was demonstrated that the mechanical property of grouting material is better than the mechanical property of general concrete, to open concrete
It splits and plays effective reinforcing effect.
This material still keeps good curing reaction in wet environment, and thermal adaptability is preferable, Celsius -5
Degree workability of material into 55 degrees Celsius of environment temperature is unaffected, and can be changed by component ratio and realize solidification
Time adjustment.This material concrete castability remains ahead level in epoxy base grouting material, works normally viscosity number lower than similar
Product proves through engineering practice, and the crack less than 0.1mm can effectively pour into (regulation: greater than 0.3mm in Regulations
Crack needs to be in the milk).This material solidification intensity value is very high, and much larger than the value of concrete strength of general performance, elasticity modulus is
The 1/30 to 1/40 of modulus of elasticity of concrete can be approximately considered with certain elasticity for opposite concrete.
It is mixed that environmental protection low viscosity high-strength epoxy group chemical grouting material of the present invention can be applied to plate, beam or rod structure
The reinforcing of solidifying soil cracking seam and the anti-Seepage of the concrete crack of water conservancy project；Also it can be used as the contact between concrete and metal material
Grouting material.
Above-described embodiment is exemplary embodiment of the invention, but embodiments of the present invention are not by the limit of embodiment
System, other any made under the principles of the present invention change, modification, replacement, combination, simplification etc., is accordingly to be regarded as equivalent displacement
Mode is all included in the scope of protection of the present invention.
Claims (1)
1. a kind of preparation method of environmental protection low viscosity high-strength epoxy base grouting material, which comprises the following steps:
1) the crosslinking diluent of 50~80 parts of epoxy resin and 20 ~ 50 parts is mixed to get A liquid；
2) 5 ~ 10 parts of curing agent and 1 ~ 5 part of promotor are mixed to get B liquid；
3) 1~10 part of initiator is separately formed C component；
4) first A liquid and B liquid are mixed evenly when using, C component is then added, obtains environmentally friendly low viscosity after mixing evenly
High-strength epoxy base grouting material；
The epoxy resin is bisphenol A type epoxy resin；The bisphenol A type epoxy resin is E-35 type epoxy resin, E-
One of 44 type epoxy resin or E-51 type epoxy resin or at least two；
The crosslinking diluent is methyl methacrylate, one kind of butyl acrylate or hy-droxybutyl or at least two
Kind；
The curing agent is one of diethylenetriamine, triethylene tetramine or tetraethylenepentamine or at least two；
The promotor is N, one of accelerine, ethyl imidazol(e) or methylimidazole；
The initiator is prepared by following steps: by peroxide and atent solvent according to mass ratio (50~80): (20~
50) proportion mixing is sufficiently dehydrated acquisition initiator after standing 24 hours；
The peroxide is benzoyl peroxide, in cyclohexanone peroxide, dilauroyl peroxide, t-butylperbenzoate
One kind or at least two；The atent solvent is dibutyl phthalate；
The initial viscosity of the environmental protection low viscosity high-strength epoxy base grouting material is in 30 mPas or less.
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| CN107254030B (en) * | 2017-06-28 | 2019-02-01 | 绵阳惠利环氧工程有限公司 | A kind of acrylate ended aqueous epoxy curing agent and preparation method thereof having self-defoaming ability |
| CN110305447A (en) * | 2019-07-03 | 2019-10-08 | 南昌航空大学 | A kind of fast epoxy resin curing system with synergistic effect |
| CN113308209B (en) * | 2020-02-27 | 2022-07-08 | 中国水利水电科学研究院 | Mixed diluent, environment-friendly high-permeability epoxy grouting material prepared from mixed diluent and preparation method of environment-friendly high-permeability epoxy grouting material |
| CN112457054A (en) * | 2020-12-16 | 2021-03-09 | 南京友西科技股份有限公司 | Repair slurry and repair method for concrete surface fine cracks |
| CN113061323A (en) * | 2021-04-13 | 2021-07-02 | 广州大学 | Grouting material, preparation method and application |
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