CN113265218B - Elastic epoxy daub for tunnel segment caulking and preparation method thereof - Google Patents
Elastic epoxy daub for tunnel segment caulking and preparation method thereof Download PDFInfo
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- CN113265218B CN113265218B CN202110721362.XA CN202110721362A CN113265218B CN 113265218 B CN113265218 B CN 113265218B CN 202110721362 A CN202110721362 A CN 202110721362A CN 113265218 B CN113265218 B CN 113265218B
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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
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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
- C08G59/46—Amides together with other curing agents
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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
- C08G59/621—Phenols
- C08G59/623—Aminophenols
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Sealing Material Composition (AREA)
Abstract
The invention discloses elastic epoxy daub for caulking tunnel segments and a preparation method thereof. The elastic epoxy daub comprises the following components in parts by mass: 1-1.5 of component A and component B, wherein the component A is composed of epoxy resin, a diluent, a thixotropic agent and the like, and the component B is composed of a curing agent, a thixotropic agent and the like. The elastic epoxy daub provided by the invention has good toughness, and the elongation can reach more than 200%; the adhesive has good bonding effect on the concrete of the pipe piece and good impermeability, tests that the dry-state positive tensile bonding strength is more than 2.5MPa, the wet-state positive tensile bonding strength is more than 2.0MPa, and the adhesive is matched with the concrete and tests that the impermeability grade is more than P12; the elastic epoxy daub not only has excellent fatigue stress resistance, but also has excellent damp-heat aging resistance, and can be used in dynamic load environments of subway operation and underground humid environments for a long time. The elastic epoxy mastic provided by the invention is suitable for caulking and sealing tunnel segments.
Description
Technical Field
The invention relates to the field of tunnel segment construction, in particular to elastic epoxy cement for caulking tunnel segments and a preparation method thereof.
Background
During the shield construction, the water seepage of the tunnel can cause the leakage of underground engineering, and further bring many hazards, such as damage to a structural main body, corrosion to equipment, influence on appearance, harm to operation safety and the like. When the shield method is adopted, the waterproof design is extremely important, the waterproof design of the shield tunnel follows the principle of 'taking prevention as a main part, multiple sets of prevention and comprehensive treatment', and the waterproof of the joint of the duct piece is particularly important on the basis of the self-waterproof of the duct piece. The waterproof structure of the duct piece joint mainly comprises two waterproof structures, namely waterproof of an elastic sealing gasket between duct pieces and waterproof of a caulking joint between adjacent duct pieces inside a tunnel. Although the waterproof function of the pipe piece joint sealing gasket is the main waterproof line of the joint, the caulking waterproof function as the auxiliary waterproof function still plays an important role in the aspects of waterproof, water stopping and drainage.
In the waterproofing of duct pieces, the caulk is often sealed with an unshaped caulk sealing material. The sealant is not shaped, as the name suggests, the sealant is non-prefabricated and unshaped, most of the sealant is building sealant, and polysulfide rubber sealant, polyurethane sealant and water-swelling sealant are commonly found in the market. Based on construction experience and use effect, the applicant finds that the sealing materials provided by the prior art have respective advantages and disadvantages. For example, polysulfide rubber sealant is mostly a two-component sealant, the main agent is liquid polysulfide polymer, the curing agent is metal oxide, the main agent and the curing agent are uniformly mixed according to a specified proportion when in use, and a high-elasticity sealing body similar to rubber is formed after curing reaction, although the performance of the curing body is better, the liquid polysulfide polymer has large molecular weight, the material is very viscous, and the stirring is difficult and the construction is inconvenient during the embedding and filling operation; although the polyurethane sealant is simple to operate and convenient to construct, due to underground construction, the construction environment is often high in humidity, even has clear water and is difficult to remove, and the polyurethane sealant is very sensitive to moisture, so that the bonding effect of the polyurethane sealant on a concrete base surface can be directly influenced when the polyurethane sealant is used, and the long-term use of the material is influenced; although the water-swelling sealant is easy to operate and construct, the water-swelling sealant is easy to break through because the material has low strength and poor bonding effect on a base surface and cannot bear water pressure. In the light of the bonding capability, the common general knowledge in the industry firstly thinks of epoxy materials, but it must be understood that the tunnel segment is in a dynamic load environment for a long time, and the conventional epoxy adhesives have poor toughness and high brittleness, cannot be used for a long time and are not suitable for use.
Disclosure of Invention
In view of the defects in the prior art, the invention provides the elastic epoxy daub for caulking tunnel segments and the preparation method thereof, the elastic epoxy daub has excellent toughness, durability and long-term use, the bonding effect on the segments is good, the anti-permeability grade after the epoxy daub is combined with the segments is greater than P12, and the defects of the existing sealing material for caulking can be effectively overcome.
The invention provides elastic epoxy daub for caulking tunnel segments, which comprises a component A and a component B, wherein the mass ratio of the component A to the component B is 1: 1-1.5;
the component A comprises the following raw materials in parts by weight: 75 parts of bisphenol A epoxy resin, 10 parts of bisphenol F epoxy resin, 15-25 parts of diluent, 2-4 parts of silane coupling agent, 5-10 parts of thixotropic agent and 5-15 parts of filler;
the component B comprises the following raw materials in parts by weight: 100 parts of curing agent, 5-10 parts of thixotropic agent and 5-15 parts of filler;
the curing agent is A19 curing agent, and the A19 curing agent is a modified curing agent consisting of a first polymer and a second polymer and having low modulus and high flexibility; the first polymer is a polymer of formaldehyde, 1, 3-xylylenediamine, and phenol; the second polymer is a polymer of unsaturated aliphatic acid dimer, tall oil fatty acid and polyalkyl tetramine; the active hydrogen equivalent weight of the A19 curing agent is 120;
the filler is spherical active silicon micro powder of 3000 meshes in the department of Nippon.
In addition, the invention also provides a preparation method of the elastic epoxy daub for caulking tunnel segments, which comprises the following steps:
putting the raw materials in the component A into a double-planet stirrer according to the parts by weight, and uniformly dispersing and stirring to obtain the component A;
putting the raw materials in the component B into a double-planet stirrer according to parts by weight, and uniformly dispersing and stirring to obtain the component B;
and (2) mixing the component A and the component B according to the mass ratio of 1: 1-1.5, and uniformly mixing to obtain the elastic epoxy daub for caulking the tunnel segment.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention provides an elastic epoxy daub sealing material which is matched with a duct piece for use, and the dry-state positive tensile bonding strength is tested to be more than 2.5MPa, the wet-state positive tensile bonding strength is tested to be more than 2.0MPa, and the anti-permeability grade is tested to be more than P12. The sealing material has strong bonding capability and good impermeability. The sealing material of the invention adopts an epoxy resin curing agent system, and has obviously more excellent bonding effect compared with the commonly used sealing materials such as polysulfide rubber sealant, polyurethane sealant, water-swelling sealant and the like in the prior art. Furthermore, the epoxy resin curing system adopted by the invention is not as critical as polyurethane sealant, and still has strong adhesive force for the duct piece in the underground humid environment.
2. The elastic epoxy daub provided by the invention has the elongation of more than 200%, solves the technical problems that the conventional epoxy materials are poor in toughness, low in elongation and not suitable for a long-term vibration load environment, and enriches the types of caulking sealing materials.
As is known to all, epoxy materials have poor toughness and are easy to damage under a vibration load environment for a long time, and the common knowledge in the industry is not recommended to be used in a long-term dynamic load environment. The epoxy material has excellent bonding reliability, can improve the elongation rate on the premise of ensuring the bonding effect, is applied to a dynamic load environment, and is a technical problem which is difficult to solve in the industry. In order to solve the problems, the invention is developed by a large amount of formulas, particularly an A19 curing agent system is adopted, and an A19 curing agent is a modified amine curing agent with ultrahigh elongation and is matched with epoxy resin for use, so that the elongation at break is more than 200%. The elastic epoxy mastic provided by the invention can be effective for a long time in the technical field of tunnel segment installation, such as dynamic load environments of continuous operation of subways, high-speed rails and the like, and can not be cracked.
3. The elastic epoxy daub provided by the invention has excellent long-term use. The invention particularly selects the A19 curing agent and the Scobitaceae 3000-mesh spherical active silica powder, the A19 curing agent endows the material with excellent toughness, the Scobitaceae 3000-mesh spherical active silica powder is in a nanometer grade, and a small amount of the spherical active silica powder is added, so that the body strength of the material is enhanced on the premise of ensuring the deformability and the elongation of the material, and the aging resistance effect of the elastic epoxy daub is further improved. Considering the long-term dynamic load environment and the humid environment of the elastic epoxy daub, the long-term use performance evaluation is carried out on the elastic epoxy daub by referring to the current national standard GB 50728-The test shows that the strength of the elastic epoxy daub provided by the invention is hardly reduced in a 90d damp-heat aging resistance test; the material passes 2 x 10 6 The secondary fatigue load effect is that the test piece has no obvious change and is not damaged.
Test results show that the elastic epoxy daub provided by the invention has the humidity-heat-aging resistance and fatigue stress action resistance which meet the requirements of structural reinforcement, can be used for a long time in a dynamic load environment and a humid environment where the duct piece is located, and can be used for more than 30 years in an evaluation service life.
In conclusion, the elastic epoxy daub provided by the invention has good toughness and good bonding effect with the pipe piece, the impermeability grade is higher than P12 after combination, and the elastic epoxy daub has excellent fatigue stress resistance and damp-heat aging resistance and can be used in the environment for a long time. The elastic epoxy mastic provided by the invention is suitable for caulking sealing of subway segments.
Detailed Description
The present invention will be described in further detail with reference to examples. It is to be understood that the specific embodiments described herein are merely illustrative of the invention and are not to be construed as limiting the invention.
Example 1
An elastic epoxy daub for caulking tunnel segments consists of A, B bi-components;
the component A comprises the following raw materials in parts by weight: 75 parts of bisphenol A epoxy resin, 10 parts of bisphenol F epoxy resin, 20 parts of diluent, 4 parts of silane coupling agent, 5 parts of thixotropic agent and 10 parts of filler;
the component B comprises the following raw materials in parts by weight: 100 parts of curing agent, 5 parts of thixotropic agent and 10 parts of filler;
the curing agent is A19 curing agent, and the A19 curing agent is a modified curing agent which is composed of a first polymer and a second polymer and has low modulus and high flexibility; the first polymer is a polymer of formaldehyde, 1, 3-xylylenediamine and phenol; the second polymer is a polymer of unsaturated fatty acid dimer, tall oil fatty acid and polyalkyl tetramine; the active hydrogen equivalent of the A19 curing agent is 120;
the filler is spherical active silicon micropowder of 3000 meshes of the Sulbicaceae family;
the preparation method of the elastic epoxy daub comprises the following steps:
putting the raw materials in the component A into a double-planet stirrer according to the parts by weight, and uniformly dispersing and stirring to obtain a component A;
putting raw materials in the component B into a double-planet stirrer according to parts by weight, and uniformly dispersing and stirring to obtain a component B;
the component A and the component B are mixed according to the mass ratio of 1: 1 to obtain the elastic epoxy daub for caulking the tunnel segment.
Example 2
An elastic epoxy daub for caulking tunnel segments consists of A, B bi-components;
the component A comprises the following raw materials in parts by weight: 75 parts of bisphenol A epoxy resin, 10 parts of bisphenol F epoxy resin, 20 parts of diluent, 4 parts of silane coupling agent, 5 parts of thixotropic agent and 10 parts of filler;
the component B comprises the following raw materials in parts by weight: 100 parts of curing agent, 5 parts of thixotropic agent and 10 parts of filler;
the curing agent is A19 curing agent, and the A19 curing agent is a modified curing agent which is composed of a first polymer and a second polymer and has low modulus and high flexibility; the first polymer is a polymer of formaldehyde, 1, 3-xylylenediamine and phenol; the second polymer is a polymer of unsaturated aliphatic acid dimer, tall oil fatty acid and polyalkyl tetramine; the active hydrogen equivalent weight of the A19 curing agent is 120;
the filler is spherical active silicon micropowder of 3000 meshes of the Sulbicaceae family;
the preparation method of the elastic epoxy daub comprises the following steps:
putting the raw materials in the component A into a double-planet stirrer according to the parts by weight, and uniformly dispersing and stirring to obtain a component A;
putting the raw materials in the component B into a double-planet stirrer according to the parts by weight for uniformly dispersing and stirring to obtain the component B;
the component A and the component B are mixed according to the mass ratio of 1: 1.2, and obtaining the elastic epoxy daub for caulking the tunnel segment.
Example 3
An elastic epoxy daub for caulking tunnel segments consists of A, B bi-components;
the component A comprises the following raw materials in parts by weight: 75 parts of bisphenol A epoxy resin, 10 parts of bisphenol F epoxy resin, 20 parts of diluent, 4 parts of silane coupling agent, 5 parts of thixotropic agent and 10 parts of filler;
the component B comprises the following raw materials in parts by weight: 100 parts of curing agent, 5 parts of thixotropic agent and 10 parts of filler;
the curing agent is A19 curing agent, and the A19 curing agent is a modified curing agent which is composed of a first polymer and a second polymer and has low modulus and high flexibility; the first polymer is a polymer of formaldehyde, 1, 3-xylylenediamine and phenol; the second polymer is a polymer of unsaturated fatty acid dimer, tall oil fatty acid and polyalkyl tetramine; the active hydrogen equivalent weight of the A19 curing agent is 120;
the filler is spherical active silicon micropowder of 3000 meshes of the Sulbicaceae family;
the preparation method of the elastic epoxy daub comprises the following steps:
putting the raw materials in the component A into a double-planet stirrer according to the parts by weight, and uniformly dispersing and stirring to obtain a component A;
putting raw materials in the component B into a double-planet stirrer according to parts by weight, and uniformly dispersing and stirring to obtain a component B;
the component A and the component B are mixed according to the mass ratio of 1: 1.5, and obtaining the elastic epoxy daub for caulking the tunnel segment.
The elastic epoxy daub obtained in the above embodiment is tested for tensile properties according to GB/T528-; testing the elastic recovery rate of the material according to JCT 881 and 2017 building sealant for concrete joint; testing the bonding performance and long-term use of the engineering structure reinforcing material according to GB 50728-2011 'safety identification technical specification of the engineering structure reinforcing material'; the concrete and the elastic epoxy daub are bonded by using hydraulic concrete with the impermeability grade larger than P12 (the actual impermeability grade is P14), the impermeability of the bonded test piece is tested according to GB/T50082-2009 "ordinary concrete long-term performance and durability", and the detailed performance is shown in the following tables 1 and 2.
TABLE 1 Performance test Table for elastic epoxy mastic
Table 2 performance test table for bonding test piece of hydraulic concrete and elastic epoxy daub
In the description of the present specification, the description of the term "one embodiment" or the like means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the application. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (2)
1. The elastic epoxy daub for caulking tunnel segments is characterized by comprising a component A and a component B, wherein the mass ratio of the component A to the component B is 1: 1-1.5;
the component A comprises the following raw materials in parts by weight: 75 parts of bisphenol A epoxy resin, 10 parts of bisphenol F epoxy resin, 15-25 parts of diluent, 2-4 parts of silane coupling agent, 5-10 parts of thixotropic agent and 5-15 parts of filler;
the component B comprises the following raw materials in parts by weight: 100 parts of curing agent, 5-10 parts of thixotropic agent and 5-15 parts of filler;
the curing agent is A19 curing agent, and the A19 curing agent is a modified curing agent consisting of a first polymer and a second polymer and having low modulus and high flexibility; the first polymer is a polymer of formaldehyde, 1, 3-xylylenediamine and phenol; the second polymer is a polymer of unsaturated aliphatic acid dimer, tall oil fatty acid and polyalkyl tetramine; the active hydrogen equivalent weight of the A19 curing agent is 120;
the filler is spherical active silicon micro powder of 3000 meshes in the department of Nippon.
2. A preparation method of elastic epoxy daub for tunnel segment caulking is characterized by comprising the following steps:
putting the raw materials of the component A in the claim 1 into a double-planet stirrer according to the parts by weight, and uniformly dispersing and stirring to obtain the component A;
putting the raw materials of the component B in the claim 1 into a double-planet stirrer according to the parts by weight, and uniformly dispersing and stirring to obtain the component B;
and (2) mixing the component A and the component B according to the mass ratio of 1: 1-1.5, and mixing uniformly to obtain the elastic epoxy daub for caulking the tunnel segment.
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| CN109777333A (en) * | 2017-11-13 | 2019-05-21 | 北京天山新材料技术有限公司 | A kind of epoxy adhesive and preparation method thereof |
| CN112322239A (en) * | 2020-10-29 | 2021-02-05 | 中铁第一勘察设计院集团有限公司 | Special glue for splicing UHPC (ultra high performance polycarbonate) bridges |
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| US5319062A (en) * | 1991-07-31 | 1994-06-07 | Lion Corporation | Method for curing an epoxy resin with a polyamide derived from a polyamide and a substantially non-cyclic dimer acid |
| JP2011213983A (en) * | 2010-03-17 | 2011-10-27 | Dic Corp | Amine-based curing agent, epoxy resin composition, and cured product thereof |
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