Epoxy resin adhesive and its preparation method and application

Abstract

The present invention provides an epoxy resin adhesive, its preparation method, and its application, relating to the technical field of steel bridge deck pavement. The epoxy resin adhesive comprises a main agent and a curing agent. The main agent comprises a bisphenol A epoxy resin, a reactive diluent, an inactive diluent, a nano-rubber toughening agent, a liquid rubber toughening agent, and an optional first antioxidant. The curing agent comprises an amine curing agent, a phenolic curing agent, a coupling agent, and an optional second antioxidant. The epoxy resin adhesive is a high-temperature, shear-resistant epoxy resin adhesive. It exhibits excellent high-temperature stability when used in steel bridge deck pavement. At high temperatures, it maintains high tensile strength and shear strength with steel plates, wear layers, and protective layers. It also maintains a balanced relationship with tensile strength, elongation, and construction retention time, reducing the likelihood of shear failure of steel bridge deck pavement at high temperatures.

Description

Technical Field

[0001] The present invention relates to the technical field of steel bridge deck pavement, and in particular to an epoxy resin adhesive and a preparation method and application thereof. Background Art

[0002] Epoxy asphalt concrete paving systems offer high strength, high modulus, and excellent high-temperature rutting resistance. They can toughen and reinforce steel structures, extend the service life of steel bridges, and shorten maintenance cycles. Over the past two decades, they have been widely used in steel bridge deck pavements on many key bridge projects in my country, such as the Runyang Bridge, Huangpu Bridge, Humen Bridge, and Zhongshan Bridge. In epoxy asphalt concrete paving systems, the wearing course and protective course are made of hot-mix epoxy asphalt concrete (EA), bonded together with an epoxy resin adhesive (also known as tack coat). The epoxy resin adhesive also serves as a waterproof bonding layer between the protective course and the steel plate (or anti-corrosion layer). The application scenarios indicate that epoxy resin adhesives are required to exhibit good interlayer bonding strength, high flexibility to accommodate deformation of the steel bridge deck under load and ambient temperature, and good waterproof stability and resistance to chemical corrosion. During actual application, it was found that, especially in southern my country, the actual maximum service temperature of steel bridge deck pavement exceeded 70°C. Some steel bridge decks with heavy vehicle loads prematurely developed structural defects such as slippage and delamination due to the failure of epoxy resin adhesives.

[0003] Existing technologies mostly focus on pull-out performance at room temperature and 60°C, but lack attention to shear performance. Defects such as slippage and delamination are more affected by the shearing effects of heavy-duty vehicle acceleration and braking on the road surface. Therefore, the importance of epoxy resin adhesives' shear resistance at higher temperatures (such as 70°C) becomes even more prominent. Patent CN113861907 discloses an epoxy tack coat oil that incorporates a high-temperature curing agent and a high-performance additive into its curing agent component. Its pull-out strength at 25°C and 60°C is high, at 8.3 MPa and 4.7 MPa, respectively, but its elongation is only 200%, indicating insufficient flexibility. Patent CN113549418 discloses an epoxy tack coat oil that incorporates a high-temperature curing agent, a rubber toughening agent, and a phenolic curing agent. Its elongation is 250-350%, but its tensile strength is only 2.5-3.3 MPa, and it also lacks high-temperature shear strength. The epoxy adhesive disclosed in patent CN 110373143 uses polyamide and polyetheramine as curing agents. While it exhibits high tensile strength exceeding 10 MPa, it also exhibits low elongation, ranging from 60% to 200%, insufficient flexibility, and poor high-temperature pullout and shear properties. Patent CN 115651585 discloses a hot-melt epoxy resin adhesive, which uses at least one primary or secondary monoamine and contains silica powder as a curing agent. While it exhibits high tensile strength (4.5-5.8 MPa) and elongation (300%-450%), it also lacks high-temperature bonding properties.

[0004] In view of this, the present invention is proposed. Summary of the Invention

[0005] One of the objectives of the present invention is to provide an epoxy resin adhesive that addresses at least one of the technical problems existing in the prior art. The epoxy resin adhesive exhibits balanced tensile strength, elongation, and bonding strength, and exhibits excellent high-temperature stability. Even at temperatures of 70°C, the adhesive maintains high pull-out and shear strengths with steel plates, wear layers, and protective layers. Furthermore, the adhesive has a long application life, avoiding the problem of rapid viscosity growth during application during hot summer months.

[0006] A second object of the present invention is to provide a method for preparing an epoxy resin adhesive.

[0007] A third object of the present invention is to provide an application of an epoxy resin adhesive in steel bridge deck pavement, wherein the epoxy resin adhesive has a bonding strength with the steel plate at 70°C of ≥1.5MPa, a shear strength with epoxy asphalt concrete at 70°C of ≥0.8MPa, and an elongation at break at 23°C of ≥300%.

[0008] In order to achieve the above-mentioned purpose of the present invention, the following technical solutions are adopted:

[0009] In a first aspect, the present invention provides an epoxy resin adhesive, the components of the epoxy resin adhesive comprising: a main agent and a curing agent;

[0010] The components of the main agent include: bisphenol A type epoxy resin, active diluent, inactive diluent, nano rubber toughening agent, liquid rubber toughening agent and optional first antioxidant;

[0011] The components of the curing agent include: an amine curing agent, a phenolic curing agent, a coupling agent and an optional second antioxidant.

[0012] Furthermore, the weight ratio of the main agent to the curing agent is 1.0:1.0-1.5;

[0013] Preferably, the amine curing agent includes at least one of a fatty amine curing agent and an amidoamine curing agent;

[0014] Preferably, the main agent comprises the following raw materials in parts by weight: 100 parts of bisphenol A epoxy resin, 5-15 parts of active diluent, 1-3 parts of inactive diluent, 5-8 parts of nano rubber toughening agent, 10-20 parts of liquid rubber toughening agent and 1-3 parts of first antioxidant;

[0015] Preferably, the curing agent comprises the following raw materials in parts by weight: 40-60 parts of aliphatic amine curing agent, 10-40 parts of amidoamine curing agent, 20-30 parts of phenolic curing agent, 1-3 parts of coupling agent and 1-3 parts of second antioxidant.

[0016] Furthermore, the bisphenol A epoxy resin includes a bisphenol A glycidyl ether epoxy resin containing two epoxy groups;

[0017] Preferably, the bisphenol A epoxy resin includes at least one of E51, E44, E39, E20 and E12;

[0018] Preferably, the reactive diluent includes a hydrophobic long-chain alkyl glycidyl ether in the molecule;

[0019] Preferably, the reactive diluent comprises at least one of butyl glycidyl ether, benzyl glycidyl ether, octyl glycidyl ether, carbon twelve to fourteen glycidyl ether, decyl glycidyl ether, phenyl glycidyl ether and o-cresyl glycidyl ether;

[0020] Preferably, the inactive diluent comprises at least one of xylene and mesitylene;

[0021] Furthermore, the liquid rubber toughening agent includes carboxyl-terminated liquid nitrile rubber CTBN;

[0022] Preferably, the nano rubber toughening agent comprises fully vulcanized carboxyl nitrile rubber nanoparticles;

[0023] Preferably, the acrylonitrile content of the fully vulcanized carboxylated nitrile rubber nanoparticles is 22-30%;

[0024] Preferably, the average particle size of the fully vulcanized carboxylated nitrile rubber nanoparticles is 80-100 nm;

[0025] Preferably, the first antioxidant includes antioxidant 168 and at least one of antioxidant 1010 , antioxidant 1076 , antioxidant 1135 , and antioxidant 245 .

[0026] Further, the fatty amine curing agent includes a long-chain alkyl primary amine;

[0027] Preferably, the number of carbon atoms in the alkyl group of the long-chain alkyl primary amine is 12-18;

[0028] Preferably, the amine value of the amidoamine curing agent is 400-500 mg KOH / g, and the glass transition temperature of the amidoamine curing agent is 60-70° C.;

[0029] Preferably, the phenolic curing agent includes at least one of 2,4,6-tris(dimethylaminomethyl)phenol, nonylphenol and resorcinol;

[0030] Preferably, the coupling agent is aminosilane;

[0031] Preferably, the coupling agent includes at least one of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, and 3-aminoethylaminopropyltrimethoxysilane;

[0032] Preferably, the second antioxidant includes antioxidant 168 and at least one of antioxidant 1010 , antioxidant 1076 , antioxidant 1135 , and antioxidant 245 .

[0033] In a second aspect, the present invention provides a method for preparing the epoxy resin adhesive, the method comprising the following steps:

[0034] Mixing the main agent and the curing agent in the formula to obtain the epoxy resin adhesive;

[0035] Wherein, the main agent is prepared by the following method:

[0036] The nano rubber toughening agent, the liquid rubber toughening agent, the first antioxidant, the inactive diluent and a portion of the bisphenol A type epoxy resin are mixed for the first time to obtain a pasty nano rubber masterbatch, and then the nano rubber masterbatch, the active diluent and the remaining portion of the bisphenol A type epoxy resin are mixed for a second time to obtain the main agent;

[0037] The curing agent is prepared by the following method:

[0038] The curing agent is obtained by mixing the formulated amount of the fatty amine curing agent, the amidoamine curing agent, the phenolic curing agent, the coupling agent and the second antioxidant for a third time.

[0039] Furthermore, the first mixing includes: stirring the mixed raw materials at room temperature for 15-25 minutes;

[0040] Preferably, the stirring speed of the first mixing is 100-200 rpm.

[0041] Furthermore, the second mixing includes: stirring the mixed raw materials at normal pressure for 100-150 minutes, then stirring them under vacuum for 5-15 minutes, removing bubbles and then discharging the materials;

[0042] Preferably, the rotation speed of the second mixing during normal pressure stirring is 300-500 rpm, and the rotation speed during vacuum stirring is 100-200 rpm;

[0043] Preferably, the temperature of the second mixing is 100-110°C.

[0044] Furthermore, the third mixing includes: performing a first vacuum stirring on the mixed raw materials for 50-70 minutes, then cooling to 30-40° C., and then performing a second vacuum stirring for 20-40 minutes, removing bubbles, and then discharging the materials;

[0045] Preferably, the rotation speed of the first vacuum stirring of the third mixing is 300-500 rpm, and the rotation speed of the second vacuum stirring is 100-200 rpm;

[0046] Preferably, the preheating temperature of the third mixing is 70-80°C.

[0047] In a third aspect, the present invention provides a use of the epoxy resin adhesive in steel bridge deck pavement.

[0048] Compared with the prior art, the present invention has the following beneficial effects:

[0049] The epoxy resin adhesive provided by the present invention is a high-temperature resistant shear-type flexible epoxy resin adhesive. The epoxy resin adhesive of the present invention uses a liquid rubber toughening agent and a nano rubber toughening agent in the main component. After the liquid rubber toughening agent forms a prepolymer with the bisphenol A epoxy resin, phase separation occurs in situ during the subsequent reaction with an amine curing agent to form a micron-level rubber phase region, which has a toughening effect on the epoxy resin adhesive and greatly improves the elongation and flexibility of the epoxy resin adhesive; after the nano rubber toughening agent reacts with the bisphenol A epoxy resin, A uniform nano-level rubber phase is formed; the rigid shell of the nano-rubber toughening agent strengthens the epoxy resin adhesive, maintaining the bonding strength at high temperatures, especially the shear strength. The combination of the composite toughening agent forms a multiple "sea-island" structure at the micron-nano level in the system, with a "soft-hard" multifunctional phase region, which effectively balances the flexibility and high-temperature bonding performance of the epoxy resin adhesive. At the same time, it has high elongation and high high-temperature tensile strength and shear strength, which can effectively avoid the displacement and delamination of steel bridge decks in high-temperature areas.

[0050] The epoxy resin adhesive of the present invention uses a composite of an amine curing agent and a phenolic curing agent in the curing agent component, has a low initial viscosity, and has a stable viscosity growth rate after mixing with the main agent, thereby avoiding rapid viscosity growth and gelation during summer construction, having a long construction retention time, and being easy to construct.

[0051] The preparation method of the epoxy resin adhesive of the present invention pre-disperses the nano rubber toughening agent to prepare a masterbatch, and then performs secondary mixing to prepare the main agent, thereby solving the problems of agglomeration, slow dissolution rate and uneven mixing of nano rubber particles when directly mixed. DETAILED DESCRIPTION

[0052] Unless otherwise defined herein, scientific and technical terms used in conjunction with the present invention shall have the meanings commonly understood by those of ordinary skill in the art. The meaning and scope of the terms should be clear; however, in the event of any potential ambiguity, the definitions provided herein take precedence over any dictionary or external definitions. In this application, the use of "or" means "and / or" unless otherwise stated. In addition, the use of the term "including" and other forms is non-limiting.

[0053] The following will clearly and completely describe the technical solutions of the present invention in conjunction with the embodiments. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0054] The first aspect of the present invention provides an epoxy resin adhesive, the components of the epoxy resin adhesive include: a main agent and a curing agent;

[0055] The components of the main agent include: bisphenol A type epoxy resin, active diluent, inactive diluent, nano rubber toughening agent, liquid rubber toughening agent and optional first antioxidant;

[0056] The components of the curing agent include: an amine curing agent, a phenolic curing agent, a coupling agent and an optional second antioxidant.

[0057] Preferably, the amine curing agent includes at least one of a fatty amine curing agent and an amidoamine curing agent;

[0058] The epoxy resin adhesive of the present invention uses a composite of an amine curing agent and a phenolic curing agent in the curing agent component, has a low initial viscosity, and has a stable viscosity growth rate after mixing with the main agent, thereby avoiding rapid viscosity growth and gelation during summer construction, having a long construction retention time, and being easy to construct.

[0059] Furthermore, the weight ratio of the main agent to the curing agent is 1.0:1.0-1.5, for example, it can be 1.0:1.0, 1.0:1.1, 1.0:1.2, 1.0:1.3, 1.0:1.4, 1.0:1.5, etc.;

[0060] Preferably, the main agent comprises the following raw materials in parts by weight: 100 parts of bisphenol A epoxy resin, 5-15 parts of active diluent, 1-3 parts of inactive diluent, 5-8 parts of nano rubber toughening agent, 10-20 parts of liquid rubber toughening agent and 1-3 parts of first antioxidant;

[0061] Among them, the active diluent is 5-15 parts, for example, it can be 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, etc.;

[0062] Among them, the inactive diluent is 1-3 parts, for example, it can be 1 part, 2 parts, 3 parts, etc.;

[0063] Among them, the nano rubber toughening agent is 5-8 parts, for example, it can be 5 parts, 6 parts, 7 parts, 8 parts, etc.;

[0064] Among them, the liquid rubber toughening agent is 10-20 parts, for example, it can be 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, etc.;

[0065] Wherein, the first antioxidant is 1-3 parts, for example, 1 part, 2 parts, 3 parts, etc.;

[0066] Preferably, the curing agent comprises the following raw materials in parts by weight: 40-60 parts of aliphatic amine curing agent, 10-40 parts of amidoamine curing agent, 20-30 parts of phenolic curing agent, 1-3 parts of coupling agent and 1-3 parts of second antioxidant.

[0067] Among them, the fatty amine curing agent is 40-60 parts, for example, it can be 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, etc.;

[0068] Among them, the amidoamine curing agent is 10-40 parts, for example, it can be 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, etc.;

[0069] Wherein, the phenol curing agent is 20-30 parts, for example, it can be 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, etc.;

[0070] Wherein, the coupling agent is 1-3 parts, for example, it can be 1 part, 2 parts, 3 parts, etc.;

[0071] The second antioxidant is 1-3 parts, for example, 1 part, 2 parts, 3 parts, etc.

[0072] Furthermore, the bisphenol A epoxy resin is a bisphenol A glycidyl ether epoxy resin containing two epoxy groups;

[0073] Preferably, the bisphenol A epoxy resin includes at least one of E51, E44, E39, E20 and E12;

[0074] Preferably, the active diluent is a long-chain alkyl glycidyl ether with hydrophobicity in the molecule;

[0075] Preferably, the reactive diluent comprises at least one of butyl glycidyl ether, benzyl glycidyl ether, octyl glycidyl ether, carbon twelve to fourteen glycidyl ether, decyl glycidyl ether, phenyl glycidyl ether and o-cresyl glycidyl ether;

[0076] Preferably, the inactive diluent comprises at least one of xylene and mesitylene;

[0077] Furthermore, the liquid rubber toughening agent is carboxyl-terminated liquid nitrile rubber CTBN;

[0078] Preferably, the nano rubber toughening agent is fully vulcanized carboxyl nitrile rubber nanoparticles;

[0079] Preferably, the acrylonitrile content of the fully vulcanized carboxylated nitrile rubber nanoparticles is 22-30%;

[0080] Preferably, the average particle size of the fully vulcanized carboxylated nitrile rubber nanoparticles is 80-100 nm;

[0081] In the present invention, a carboxyl-terminated nitrile rubber toughening agent is used, and a higher acrylonitrile content increases the polarity of the rubber, thereby improving the compatibility of the rubber with the epoxy resin matrix before curing.

[0082] The high-temperature shear-resistant flexible epoxy resin adhesive for steel bridge deck paving of the present invention uses a composite of carboxyl-terminated liquid nitrile rubber and fully vulcanized nano-carboxyl-nitrile rubber particles in the main component. After the carboxyl-terminated liquid nitrile rubber forms a prepolymer with bisphenol A epoxy resin, it undergoes in-situ phase separation during the subsequent reaction with an amine curing agent, forming a micron-level rubber phase region, which has a toughening effect on the epoxy resin adhesive and greatly improves the elongation and flexibility of the epoxy resin adhesive; after the fully vulcanized nano-carboxyl-nitrile rubber particles react with the bisphenol A epoxy resin, they form a uniform nano-level rubber phase; and the fully vulcanized rigid shell strengthens the epoxy resin adhesive and maintains the bonding strength at high temperatures, especially the shear strength. The combination of the composite toughening agent forms a micron-nanometer-level multiple "sea-island" structure in the system, with a "soft-hard" multifunctional phase region, so that the flexibility and high-temperature bonding performance of the epoxy resin adhesive are effectively balanced, while having high elongation and high high-temperature tensile strength and shear strength. It can effectively avoid the displacement and delamination of steel bridge decks in high temperature areas.

[0083] Preferably, the first antioxidant includes antioxidant 168 and at least one of antioxidant 1010 , antioxidant 1076 , antioxidant 1135 , and antioxidant 245 .

[0084] Among them, antioxidant 168 is a phosphite antioxidant.

[0085] In the present invention, hindered phenol and phosphite composite antioxidant system is adopted to avoid degradation of main agent components during the kneader dispersion and subsequent mixing processes.

[0086] Furthermore, the fatty amine curing agent is a long-chain alkyl primary amine;

[0087] Preferably, the number of carbon atoms in the alkyl group of the long-chain alkyl primary amine is 12-18;

[0088] Preferably, the amine value of the amidoamine curing agent is 400-500 mg KOH / g, and the glass transition temperature of the amidoamine curing agent is 60-70° C.;

[0089] Preferably, the glass transition temperature is measured using DSC;

[0090] Preferably, the phenolic curing agent includes at least one of 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30), nonylphenol (NP) and resorcinol (R-80);

[0091] In the present invention, flexible long-chain fatty amine, amidoamine and phenolic curing agent are compositely used in the curing agent component, the initial viscosity is low, and after mixing with the main agent, the viscosity growth rate is stable, thereby avoiding the rapid increase of viscosity and gelation during summer construction, having a long construction retention time, and being easy to construct.

[0092] Preferably, the coupling agent is aminosilane;

[0093] Preferably, the coupling agent includes at least one of 3-aminopropyltrimethoxysilane (KH-540), 3-aminopropyltriethoxysilane (KH-550), N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane (CG-602), and 3-aminoethylaminopropyltrimethoxysilane (KH-792);

[0094] Preferably, the second antioxidant includes antioxidant 168 and at least one of antioxidant 1010 , antioxidant 1076 , antioxidant 1135 , and antioxidant 245 .

[0095] Among them, antioxidant 168 is a phosphite antioxidant.

[0096] In the present invention, hindered phenol and phosphite composite antioxidant system is adopted to avoid degradation of main agent components during the kneader dispersion and subsequent mixing processes.

[0097] A second aspect of the present invention provides a method for preparing the epoxy resin adhesive, the method comprising the following steps:

[0098] Mixing the main agent and the curing agent in the formula to obtain the epoxy resin adhesive;

[0099] Wherein, the main agent is prepared by the following method:

[0100] The nano rubber toughening agent, the liquid rubber toughening agent, the first antioxidant, the inactive diluent and a portion of the bisphenol A type epoxy resin are mixed for the first time to obtain a pasty nano rubber masterbatch, and then the nano rubber masterbatch, the active diluent and the remaining portion of the bisphenol A type epoxy resin are mixed for a second time to obtain the main agent;

[0101] The curing agent is prepared by the following method:

[0102] The curing agent is obtained by mixing the formulated amount of the fatty amine curing agent, the amidoamine curing agent, the phenolic curing agent, the coupling agent and the second antioxidant for a third time.

[0103] Furthermore, the epoxy resin binder is prepared using a kneader;

[0104] In the present invention, a kneader is used to pre-disperse the fully vulcanized nano-carboxylated nitrile rubber to prepare a masterbatch, and then a secondary mixing is performed to prepare the main agent, thereby solving the problems of agglomeration and slow dissolution of the nano-rubber particles and uneven mixing when directly mixed. The kneader is more preferably a Σ paddle kneader.

[0105] Preferably, the first mixing comprises: stirring the mixed raw materials at room temperature for 15-25 minutes, for example, 15 minutes, 16 minutes, 17 minutes, 18 minutes, 19 minutes, 20 minutes, 21 minutes, 22 minutes, 23 minutes, 24 minutes, 25 minutes, etc.;

[0106] Preferably, the stirring speed of the first mixing is 100-200 rpm, for example, 100 rpm, 150 rpm, 200 rpm, etc.

[0107] Further, the second mixing includes: stirring the mixed raw materials at normal pressure for 100-150min, for example, 100min, 110min, 120min, 130min, 140min, 150min, etc., and then vacuum stirring for 5-15min, for example, 5min, 6min, 7min, 8min, 9min, 10min, 11min, 12min, 13min, 14min, 15min, etc., and removing bubbles before discharging;

[0108] Preferably, the rotation speed during normal pressure stirring of the second mixing is 300-500 rpm, for example, 300 rpm, 350 rpm, 400 rpm, 450 rpm, 500 rpm, etc., and the rotation speed during vacuum stirring is 100-200 rpm, for example, 100 rpm, 150 rpm, 200 rpm, etc.

[0109] Preferably, the temperature of the second mixing is 100-110°C, for example, it can be 100°C, 101°C, 102°C, 103°C, 104°C, 105°C, 106°C, 107°C, 108°C, 109°C, 110°C, etc.

[0110] Further, the third mixing includes: vacuum stirring the mixed raw materials for a first time for 50-70 minutes, for example, 50 minutes, 55 minutes, 60 minutes, 65 minutes, 70 minutes, etc., then cooling to 30-40°C, for example, 30°C, 31°C, 32°C, 33°C, 34°C, 35°C, 36°C, 37°C, 38°C, 39°C, 40°C, etc., and then vacuum stirring for a second time for 20-40 minutes, for example, 20 minutes, 25 minutes, 30 minutes, 35 minutes, 40 minutes, etc., and removing bubbles before discharging;

[0111] Preferably, the rotation speed of the first vacuum stirring of the third mixing is 300-500 rpm, for example, 300 rpm, 350 rpm, 400 rpm, 450 rpm, 500 rpm, etc., and the rotation speed of the second vacuum stirring is 100-200 rpm, for example, 100 rpm, 150 rpm, 200 rpm, etc. Preferably, the preheating temperature of the third mixing is 70-80°C, for example, 70°C, 71°C, 72°C, 73°C, 74°C, 75°C, 76°C, 77°C, 78°C, 79°C, 80°C, etc.

[0112] A third aspect of the present invention provides a use of the epoxy resin adhesive in steel bridge deck pavement.

[0113] This epoxy resin adhesive is a high-temperature shear-resistant epoxy resin adhesive. It has good high-temperature stability when used for steel bridge deck pavement. At high temperatures, it still maintains high tensile strength and shear strength with steel plates, wear layers, and protective layers, and balances the relationship with indicators such as tensile strength, elongation, and construction retention time. It can reduce the possibility of shear failure of steel bridge deck pavement at high temperatures.

[0114] The present invention is further described below by way of examples. Unless otherwise specified, the materials in the examples were prepared according to existing methods or directly purchased from the market.

[0115] In the following embodiments:

[0116] The bisphenol A epoxy resin was purchased from Sinopec Yueyang Baling Petrochemical Co., Ltd. or Nan Ya Plastics Industry Co., Ltd.

[0117] The liquid rubber toughening agent CTBN was purchased from CVC Company in the United States.

[0118] The fully vulcanized nano-carboxyl nitrile rubber was purchased from Sinopec Beijing Chemical Research Institute Co., Ltd. with the brand name VP-501.

[0119] The long-chain alkyl primary amine curing agent is purchased from Solvay Company, brand A14, A16, A18, A20.

[0120] The amidoamine curing agent is purchased from Evonik Company with the brand name ANCAMIDE 502, 506.

[0121] Example 1

[0122] This embodiment provides an epoxy resin adhesive, which includes the following raw materials in parts by weight:

[0123] The main agent components include: 100 parts of bisphenol A epoxy resin E44, 5 parts of nano rubber toughening agent VP-501, 10 parts of liquid rubber toughening agent CTBN, 2 parts of antioxidant 1010, 1 part of antioxidant 168, 1.5 parts of inactive diluent xylene, and 10 parts of active diluent phenyl glycidyl ether;

[0124] The curing agent components include: 50 parts of fatty amine curing agent tetradecyl primary amine 35 parts of amidoamine curing agent ANCAMIDE 502, 20 parts of phenolic curing agent resorcinol, 1.5 parts of coupling agent KH540, 2 parts of antioxidant 1010 and 1 part of antioxidant 168.

[0125] Example 2

[0126] This embodiment provides an epoxy resin adhesive, which includes the following raw materials in parts by weight:

[0127] The main agent components include: 100 parts of bisphenol A epoxy resin E44, 6.5 parts of nano rubber toughener VP-501, 15 parts of liquid rubber toughener CTBN, 2 parts of antioxidant 1135, 1 part of antioxidant 168, 1.5 parts of inactive diluent xylene, and 12 parts of active diluent decyl glycidyl ether.

[0128] The curing agent components include: 54 parts of fatty amine curing agent hexadecyl primary amine 31 parts of amidoamine curing agent ANCAMIDE 502, 15 parts of phenolic curing agent 2,4,6-tris(dimethylaminomethyl)phenol, 2 parts of coupling agent KH550, 2 parts of antioxidant 1135 and 1 part of antioxidant 168.

[0129] Example 3

[0130] This embodiment provides an epoxy resin adhesive, which includes the following raw materials in parts by weight:

[0131] The main agent components include: 100 parts of bisphenol A epoxy resin E44, 8 parts of nano rubber toughening agent VP-501, 18 parts of liquid rubber toughening agent CTBN, 2 parts of antioxidant 1076, 1 part of antioxidant 168, 1 part of inactive diluent mesitylene, and 15 parts of active diluent carbon 12-14 glycidyl ether.

[0132] The curing agent components include: 57 parts of fatty amine curing agent octadecyl primary amine 28 parts of amidoamine curing agent ANCAMIDE 502, 17 parts of phenolic curing agent nonylphenol, 1.8 parts of coupling agent KH792, 2 parts of antioxidant 1076 and 1 part of antioxidant 168.

[0133] Example 4

[0134] This embodiment provides an epoxy resin adhesive, which includes the following raw materials in parts by weight:

[0135] The main agent components include: 100 parts of bisphenol A epoxy resin E51, 6.5 parts of nano rubber toughener VP-501, 15 parts of liquid rubber toughener CTBN, 2 parts of antioxidant 1135, 1 part of antioxidant 168, 1.5 parts of inactive diluent xylene, and 12 parts of active diluent decyl glycidyl ether.

[0136] The curing agent components include: 54 parts of fatty amine curing agent hexadecyl primary amine 31 parts of amidoamine curing agent ANCAMIDE 506, 15 parts of phenolic curing agent 2,4,6-tris(dimethylaminomethyl)phenol, 2 parts of coupling agent KH550, 2 parts of antioxidant 1135 and 1 part of antioxidant 168.

[0137] Example 5

[0138] This embodiment provides an epoxy resin adhesive, which includes the following raw materials in parts by weight:

[0139] The main agent components include: 100 parts of bisphenol A epoxy resin E51, 8 parts of nano rubber toughening agent VP-501, 18 parts of liquid rubber toughening agent CTBN, 2 parts of antioxidant 1076, 1 part of antioxidant 168, 1 part of inactive diluent mesitylene, and 15 parts of active diluent carbon 12-14 glycidyl ether.

[0140] The curing agent components include: 57 parts of fatty amine curing agent octadecyl primary amine 28 parts of amidoamine curing agent ANCAMIDE 506 and 17 parts of phenolic curing agent nonylphenol, 1.8 parts of coupling agent KH792, 2 parts of antioxidant 1076 and 1 part of antioxidant 168.

[0141] Example 6

[0142] This embodiment provides an epoxy resin adhesive, which includes the following raw materials in parts by weight:

[0143] The main agent components include: 100 parts of bisphenol A epoxy resin E44, 5 parts of nano rubber toughening agent VP-501, 20 parts of liquid rubber toughening agent CTBN, 2 parts of antioxidant 1010, 1 part of antioxidant 168, 3 parts of inactive diluent xylene, and 5 parts of active diluent phenyl glycidyl ether.

[0144] The curing agent components include: 47 parts of fatty amine curing agent tetradecyl primary amine 15 parts of amidoamine curing agent ANCAMIDE 502, 23 parts of phenolic curing agent resorcinol, 3 parts of KH540, 2 parts of antioxidant 1010 and 1 part of antioxidant 168.

[0145] Examples 7-12

[0146] Examples 7-12 provide a method for preparing an epoxy resin adhesive, comprising the following steps:

[0147] Preparation of main agent components:

[0148] 1) In a Σ paddle kneader, the nano rubber toughening agent, liquid rubber toughening agent, antioxidant, inactive diluent, and 10 parts of bisphenol A epoxy resin in the amounts of Examples 1-6 were added in sequence and stirred at 150 rpm for 20 min to form a paste, so that the nano rubber particles were evenly dispersed in the epoxy resin matrix to form a masterbatch.

[0149] 2) The remaining 90 parts of bisphenol A epoxy resin from Examples 1-6, the formulated amount of reactive diluent, and the nano-rubber masterbatch prepared in step 1) were added to a reaction kettle in sequence, and the mixture was stirred at high speed (400 rpm) at normal pressure for 120 min at 100-110° C., and then stirred at low speed (150 rpm) under vacuum for 10 min to remove bubbles and obtain the main agent component.

[0150] Prepare the curing agent component:

[0151] The reactor was preheated to 70-80° C., and the fatty amine curing agent, amidoamine curing agent, phenolic curing agent, coupling agent and antioxidant in Examples 1-6 were added at one time. After stirring at high speed (400 rpm) in vacuum for 60 min, the temperature was lowered to 30-40° C., and stirring at low speed (150 rpm) in vacuum for 30 min was continued. After removing bubbles and discharging the material, the curing agent component was obtained.

[0152] The main agent and curing agent prepared above were mixed respectively to obtain the epoxy resin adhesives of Examples 7-12.

[0153] Example 13

[0154] This embodiment provides a method for preparing an epoxy resin adhesive, which differs from Example 7 in that:

[0155] In step 1) of preparing the main agent, stirring was performed at a speed of 100 rpm for 25 min. In step 2) of preparing the main agent component, stirring was performed at a high speed (500 rpm) under normal pressure for 100 min, and then at a low speed (100 rpm) under vacuum for 15 min.

[0156] In the step of preparing the curing agent, after stirring at high speed (500 rpm) in vacuum for 50 minutes, the temperature was lowered to 30-40°C, and stirring was continued at low speed (100 rpm) in vacuum for 40 minutes;

[0157] The remaining steps are consistent with Example 7.

[0158] Example 14

[0159] This embodiment provides a method for preparing an epoxy resin adhesive, which differs from Example 7 in that:

[0160] In step 1) of preparing the main agent, the mixture was stirred at a speed of 200 rpm for 15 minutes. In step 2) of preparing the main agent component, the mixture was stirred at a high speed (300 rpm) under normal pressure for 150 minutes, and then at a low speed (200 rpm) under vacuum for 5 minutes.

[0161] In the step of preparing the curing agent, after stirring at high speed (300 rpm) in vacuum for 70 min, the temperature was lowered to 30-40°C, and stirring was continued at low speed (200 rpm) in vacuum for 20 min;

[0162] The remaining steps are consistent with Example 7.

[0163] Comparative Example 1

[0164] This comparative example provides an epoxy resin adhesive, which comprises the following raw materials in parts by weight:

[0165] When preparing the main component, the nano rubber toughening agent VP-501 was not added, the amount of liquid rubber toughening agent CTBN was 15 parts, and the remaining components were the same as in Example 1.

[0166] Comparative Example 2

[0167] This comparative example provides an epoxy resin adhesive, which comprises the following raw materials in parts by weight:

[0168] When preparing the main component, no liquid rubber toughening agent CTBN was added, the amount of nano rubber toughening agent VP-501 was 15 parts, and the remaining components were the same as in Example 1.

[0169] Comparative Example 3

[0170] This comparative example provides an epoxy resin adhesive, which comprises the following raw materials in parts by weight:

[0171] When preparing the curing agent component, do not add amide amine curing agent ANCAMIDE, tetradecyl primary amine The dosage is 85 parts, and the other components are the same as in Example 1.

[0172] Comparative Example 4

[0173] This comparative example provides an epoxy resin adhesive, which comprises the following raw materials in parts by weight:

[0174] When preparing the curing agent component, no octadecyl primary amine is added

[0175] The amount of amidoamine curing agent ANCAMIDE 502 used is 85 parts, and the other components are the same as in Example 1.

[0176] Comparative Examples 5-8

[0177] This comparative example provides a method for preparing an epoxy resin adhesive. The difference from Example 7 is that the epoxy resin adhesive is prepared using the raw materials in the formula amounts of Comparative Examples 1-4 in sequence, and the remaining steps are consistent with Example 7.

[0178] The constituent raw materials of the epoxy resin adhesives of the above examples and comparative examples are shown in Table 1. The epoxy resin adhesives prepared in Examples 7-14 and Comparative Examples 5-8 were tested, and the test results are shown in Table 2.

[0179] Table 1:

[0180]

[0181]

[0182]

[0183] Table 2:

[0184]

[0185]

[0186] As can be seen from the data in Table 2, in terms of mechanical strength, the higher the content of nano-rubber toughening agent in the main agent and amidoamine in the curing agent, the higher the tensile strength and bonding strength of the cured product; in terms of flexibility, the higher the content of liquid rubber toughening agent in the main agent and fatty amine in the curing agent, the higher the elongation at break of the cured product; in terms of construction performance, the higher the content of phenolic curing agent in the curing agent, the shorter the construction residence time of the system.

[0187] In the present embodiments 1-6, the cured product obtained by compounding the nano-rubber toughening agent and the liquid rubber toughening agent in the main agent and compounding the fatty amine and the amide amine in the curing agent has a pull-out strength with the steel plate of >2.5MPa at a high temperature of 70°C, a pull-out strength of the composite part of >2.0MPa, and an oblique shear strength of the composite part of >3.5MPa. It has good high-temperature resistance at 70°C, high toughness, tensile strength of >8MPa, and elongation at break of >300%. At the same time, it has a longer construction retention time of >130min at 23°C and >50min at 40°C.

[0188] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the above embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. An epoxy resin adhesive, characterized in that The components of the epoxy resin adhesive include: a main agent and a curing agent; The main agent comprises the following raw materials in parts by weight: 100 parts of bisphenol A epoxy resin, 5-15 parts of active diluent, 1-3 parts of inactive diluent, 5-8 parts of nano rubber toughening agent, 10-20 parts of liquid rubber toughening agent and 1-3 parts of first antioxidant; The curing agent comprises the following raw materials in parts by weight: 40-60 parts of aliphatic amine curing agent, 10-40 parts of amidoamine curing agent, 20-30 parts of phenolic curing agent, 1-3 parts of coupling agent and 1-3 parts of second antioxidant; The liquid rubber toughening agent includes carboxyl-terminated liquid nitrile rubber (CTBN); The nano rubber toughening agent comprises fully vulcanized carboxyl nitrile rubber nano particles.

2. The epoxy resin adhesive according to claim 1, characterized in that The weight ratio of the main agent to the curing agent is 1.0:1.0-1.

5.

3. The epoxy resin adhesive according to claim 1, characterized in that The bisphenol A type epoxy resin includes bisphenol A glycidyl ether epoxy resin containing two epoxy groups.

4. The epoxy resin adhesive according to claim 1, characterized in that The bisphenol A epoxy resin includes at least one of E51, E44, E39, E20 and E12.

5. The epoxy resin adhesive according to claim 1, wherein The active diluent includes a long-chain alkyl glycidyl ether with hydrophobicity in the molecule.

6. The epoxy resin adhesive according to claim 1, characterized in that The active diluent includes at least one of butyl glycidyl ether, benzyl glycidyl ether, octyl glycidyl ether, carbon 12-14 glycidyl ether, decyl glycidyl ether, phenyl glycidyl ether and o-cresyl glycidyl ether.

7. The epoxy resin adhesive according to claim 1, characterized in that The non-reactive diluent includes at least one of xylene and mesitylene.

8. The epoxy resin adhesive according to claim 1, characterized in that The acrylonitrile content of the fully vulcanized carboxyl nitrile rubber nanoparticles is 22-30%.

9. The epoxy resin adhesive according to claim 1, characterized in that The average particle size of the fully vulcanized carboxyl nitrile rubber nanoparticles is 80-100 nm.

10. The epoxy resin adhesive according to claim 1, wherein The first antioxidant includes antioxidant 168 and at least one of antioxidant 1010 , antioxidant 1076 , antioxidant 1135 , and antioxidant 245 .

11. The epoxy resin adhesive according to claim 1, characterized in that The fatty amine curing agent includes a long-chain alkyl primary amine.

12. The epoxy resin adhesive according to claim 11, characterized in that The number of carbon atoms of the alkyl group in the long-chain alkyl primary amine is 12-18.

13. The epoxy resin adhesive according to claim 1, characterized in that The amine value of the amidoamine curing agent is 400-500 mg KOH / g, and the glass transition temperature of the amidoamine curing agent is 60-70°C.

14. The epoxy resin adhesive according to claim 1, wherein The phenolic curing agent includes at least one of 2,4,6-tris(dimethylaminomethyl)phenol, nonylphenol and resorcinol.

15. The epoxy resin adhesive according to claim 1, characterized in that The coupling agent includes aminosilane.

16. The epoxy resin adhesive according to claim 1, characterized in that The coupling agent includes at least one of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, and 3-aminoethylaminopropyltrimethoxysilane.

17. The epoxy resin adhesive according to claim 1, characterized in that The second antioxidant includes antioxidant 168 and at least one of antioxidant 1010 , antioxidant 1076 , antioxidant 1135 , and antioxidant 245 .

18. The method for preparing the epoxy resin adhesive according to any one of claims 1 to 17, wherein: The preparation method of the epoxy resin adhesive comprises the following steps: Mixing the main agent and the curing agent in the formula to obtain the epoxy resin adhesive; Wherein, the main agent is prepared by the following method: The nano rubber toughening agent, the liquid rubber toughening agent, the first antioxidant, the inactive diluent and a portion of the bisphenol A type epoxy resin are mixed for the first time to obtain a pasty nano rubber masterbatch, and then the nano rubber masterbatch, the active diluent and the remaining portion of the bisphenol A type epoxy resin are mixed for a second time to obtain the main agent; The curing agent is prepared by the following method: The curing agent is obtained by mixing the formulated amount of the fatty amine curing agent, the amidoamine curing agent, the phenolic curing agent, the coupling agent and the second antioxidant for a third time.

19. The method for preparing the epoxy resin adhesive according to claim 18, wherein: The first mixing comprises: stirring the mixed raw materials at room temperature for 15-25 minutes.

20. The method for preparing the epoxy resin adhesive according to claim 18, wherein: The stirring speed of the first mixing is 100-200 rpm.

21. The method for preparing the epoxy resin adhesive according to claim 18, wherein: The second mixing comprises: stirring the mixed raw materials at normal pressure for 100-150 minutes, then stirring them under vacuum for 5-15 minutes, removing bubbles and then discharging the materials.

22. The method for preparing the epoxy resin adhesive according to claim 18, wherein: The rotation speed of the second mixing during normal pressure stirring is 300-500 rpm, and the rotation speed during vacuum stirring is 100-200 rpm.

23. The method for preparing the epoxy resin adhesive according to claim 18, wherein: The temperature of the second mixing is 100-110°C.

24. The method for preparing the epoxy resin adhesive according to claim 18, wherein: The third mixing comprises: performing a first vacuum stirring on the mixed raw materials for 50-70 minutes, then cooling to 30-40° C., and then performing a second vacuum stirring for 20-40 minutes, removing bubbles, and then discharging the materials.

25. The method for preparing the epoxy resin adhesive according to claim 18, wherein: The rotation speed of the first vacuum stirring of the third mixing is 300-500 rpm, and the rotation speed of the second vacuum stirring is 100-200 rpm.

26. The method for preparing the epoxy resin adhesive according to claim 18, wherein: The preheating temperature of the third mixing is 70-80°C.

27. Use of the epoxy resin adhesive according to any one of claims 1 to 17 in steel bridge deck pavement.

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