Epoxy resin binder as well as preparation method and application thereof

Abstract

The invention provides an epoxy resin binder and a preparation method and application thereof, and relates to the technical field of steel bridge deck pavement, the epoxy resin binder comprises the following components: a main agent and a curing agent; the main agent comprises the following components: bisphenol A epoxy resin, a reactive diluent, a non-reactive diluent, a nano rubber toughening agent, a liquid rubber toughening agent and an optional first antioxidant; the curing agent comprises the following components: an amine curing agent, a phenol curing agent, a coupling agent and an optional second antioxidant. The epoxy resin adhesive is a high-temperature anti-shearing type epoxy resin adhesive, has good high-temperature stability when being used for steel bridge deck pavement, still keeps relatively high tensile strength and shear strength with a steel plate, a wearing layer and a protective layer at high temperature, and balances the relationship with indexes such as tensile strength, ductility and construction holding time; and the possibility of shear failure of the steel bridge deck pavement at high temperature can be reduced.

Description

Technical Field

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

[0002] The epoxy asphalt concrete paving system has the advantages of high strength, high modulus, good high temperature rutting resistance, toughening and strengthening the steel structure system, extending the service life of the steel bridge, and short maintenance cycle. In the past two decades, it has been widely used in the steel bridge deck paving of many key bridge projects in my country, such as Runyang Bridge, Huangpu Bridge, Humen Bridge, Zhongshan Bridge, etc. In the epoxy asphalt concrete paving system, the wear layer and the protective layer are made of hot-mixed epoxy asphalt concrete (EA), and the two are bonded by epoxy resin adhesive (also known as adhesive layer oil); at the same time, the epoxy resin adhesive can be used as a waterproof adhesive layer between the protective layer and the steel plate (or anti-corrosion layer). It can be seen from the application scene that the epoxy resin adhesive is required to have good interlayer bonding strength, high flexibility to adapt to the deformation of the steel bridge deck under load and ambient temperature, and good waterproof stability and chemical corrosion resistance. In 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 showed structural defects such as shifting and delamination due to the failure of epoxy resin adhesives.

[0003] Most of the existing technologies focus on the pull-out performance at room temperature and 60°C, but lack attention to the shear performance. The diseases such as push and delamination are more affected by the shearing effect of heavy-loaded vehicles on the road surface during acceleration and braking. Therefore, the importance of the anti-shear performance of epoxy resin adhesives at higher temperatures (such as 70°C) is more prominent. Patent CN113861907 discloses an epoxy adhesive layer oil, in which a high-temperature curing agent and a high-performance auxiliary agent are introduced into the curing agent component. The pull-out strength at 25°C and 60°C is relatively high, at 8.3MPa and 4.7MPa respectively, but the elongation is only 200%, and the flexibility is insufficient; the epoxy adhesive layer oil disclosed in patent CN113549418, the curing agent is compounded with a high-temperature curing agent, a rubber toughening agent and a phenolic curing agent, the elongation is 250-350%, but the tensile strength is only 2.5-3.3MPa, and it also lacks high-temperature shear strength performance. The epoxy adhesive disclosed in patent CN 110373143 uses polyamide and polyetheramine as curing agent, and has a high tensile strength of more than 10MPa, but a low elongation of 60-200%, insufficient flexibility, and lacks high-temperature drawing performance and high-temperature shearing performance. The hot-melt epoxy resin adhesive disclosed in patent CN115651585 uses at least one monoprimary amine or di-secondary amine as curing agent, and adds silicon powder, which has a high tensile strength (4.5-5.8MPa) and elongation (300%-450%), but also lacks high-temperature bonding performance.

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

[0005] One of the purposes of the present invention is to provide an epoxy resin adhesive to solve at least one of the technical problems existing in the prior art. The epoxy resin adhesive has balanced tensile strength, elongation and bonding strength, and has good high temperature stability. At a high temperature of 70°C, it still maintains high bonding pull-out strength and shear strength with steel plates, wear layers, and protective layers. At the same time, it has a long construction retention time, avoiding the problem of excessive viscosity growth during construction in the high temperature season in summer.

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

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

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

[0009] In a first aspect, the present invention provides an epoxy resin adhesive, the components of which include: 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 amide amine curing agent;

[0014] Preferably, the main agent comprises the following raw materials 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 by weight: 40-60 parts of fatty amine curing agent, 10-40 parts of amide amine curing agent, 20-30 parts of phenolic curing agent, 1-3 parts of coupling agent and 1-3 parts of second antioxidant.

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

[0017] Preferably, the bisphenol A type 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] Further, the liquid rubber toughening agent includes carboxyl-terminated liquid nitrile rubber CTBN;

[0022] Preferably, the nano rubber toughening agent comprises fully vulcanized carboxylated 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 carbon number of the alkyl group in 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 for preparing the epoxy resin adhesive 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 part of the bisphenol A type epoxy resin are mixed for the first time to obtain a paste-like nano rubber masterbatch, and then the nano rubber masterbatch, the active diluent and the remaining part of the bisphenol A type epoxy resin are mixed for the 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 amide amine curing agent, the phenolic curing agent, the coupling agent and the second antioxidant for the 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, and discharging the materials after removing bubbles;

[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 paving.

[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 agent component. After the liquid rubber toughening agent forms a prepolymer with the bisphenol A type epoxy resin, phase separation occurs in situ during the subsequent reaction with an amine curing agent to form a micrometer-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 type epoxy resin, A uniform nano-scale rubber phase is formed; the rigid shell of the nano-rubber toughening agent 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 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 a higher elongation and higher 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 an amine curing agent and a phenol curing agent in a composite curing agent component, has a low initial viscosity, has a stable viscosity growth rate after being mixed with a main agent, avoids rapid viscosity growth and gelation during summer construction, has a long construction retention time, and is 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 a main agent, thereby solving the problems of agglomeration and slow dissolution speed and uneven mixing of nano rubber particles when they are 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 case of any potential ambiguity, the definitions provided herein take precedence over any dictionary or external definitions. In this application, unless otherwise stated, the use of "or" means "and / or". In addition, the use of the term "including" and other forms is non-limiting.

[0053] The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work 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 amide amine curing agent;

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

[0059] Further, 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 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] Among them, the first antioxidant is 1-3 parts, for example, it can be 1 part, 2 parts, 3 parts, etc.;

[0066] Preferably, the curing agent comprises the following raw materials by weight: 40-60 parts of fatty amine curing agent, 10-40 parts of amide amine 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 type 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 carboxylated 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 resistant shear type flexible epoxy resin binder for steel bridge deck paving of the present invention uses carboxyl-terminated liquid nitrile rubber and fully vulcanized nano carboxyl nitrile rubber particles in the main agent component. After the carboxyl-terminated liquid nitrile rubber forms a prepolymer with bisphenol A epoxy resin, it undergoes phase separation in situ during the subsequent reaction with an amine curing agent to form a micrometer-level rubber phase region, which has a toughening effect on the epoxy resin binder and greatly improves the elongation and flexibility of the epoxy resin binder; after the fully vulcanized nano carboxyl nitrile rubber particles react with the bisphenol A epoxy resin, a uniform nanometer-level rubber phase is formed; the fully vulcanized rigid shell has a reinforcing effect on the epoxy resin binder and maintains the bonding strength at high temperature, especially the shear strength. The combination of the composite toughening agent forms a micrometer-nanometer-level multiple "sea-island" structure in the system, and has a "soft-hard" multifunctional phase region, so that the flexibility and high temperature bonding performance of the epoxy resin binder are effectively balanced, and at the same time, it has a higher elongation and a higher high temperature pull-out 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, the antioxidant 168 is a phosphite antioxidant.

[0085] In the present invention, a hindered phenol and phosphite compound antioxidant system is adopted to avoid the degradation of the main agent components during the kneading machine dispersion and subsequent mixing process.

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

[0087] Preferably, the carbon number of the alkyl group in 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 by 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, amide amine and phenolic curing agent are used in combination in the curing agent component, the initial viscosity is low, and after mixing with the main agent, the viscosity has a stable growth rate, which avoids the rapid growth of viscosity and gelation during summer construction, has a long construction retention time, and is 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, the antioxidant 168 is a phosphite antioxidant.

[0096] In the present invention, a hindered phenol and phosphite compound antioxidant system is adopted to avoid the degradation of the main agent components during the kneading machine dispersion and subsequent mixing process.

[0097] The second aspect of the present invention provides a method for preparing the epoxy resin adhesive, the method for preparing the epoxy resin adhesive 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 part of the bisphenol A type epoxy resin are mixed for the first time to obtain a paste-like nano rubber masterbatch, and then the nano rubber masterbatch, the active diluent and the remaining part of the bisphenol A type epoxy resin are mixed for the 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 amide amine curing agent, the phenolic curing agent, the coupling agent and the second antioxidant for the third time.

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

[0104] In the present invention, a kneader is used to pre-disperse the fully vulcanized nano carboxyl nitrile rubber to prepare a masterbatch, and then a secondary mixing is performed to prepare a main agent, which solves the problems of agglomeration and slow dissolution speed and uneven mixing of nano rubber particles when directly mixed. The kneader is further 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 discharging the materials after removing bubbles;

[0108] Preferably, the rotation speed during normal pressure stirring of the second mixing is 300-500 rpm, for example, it can be 300 rpm, 350 rpm, 400 rpm, 450 rpm, 500 rpm, etc., and the rotation speed during vacuum stirring is 100-200 rpm, for example, it can be 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 the 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 the second time for 20-40 minutes, for example, 20 minutes, 25 minutes, 30 minutes, 35 minutes, 40 minutes, etc., and discharging after removing bubbles;

[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 paving.

[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. It still maintains high tensile strength and shear strength with steel plates, wear layers, and protective layers at high temperatures, 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 are prepared according to existing methods or directly purchased from the market.

[0115] In the following embodiments:

[0116] The bisphenol A epoxy resin is 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 was purchased from Solvay Company, with a brand name A14, A16, A18, A20.

[0120] The amide amine 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 twelve to fourteen 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 toughener VP-501, 18 parts of liquid rubber toughener CTBN, 2 parts of antioxidant 1076, 1 part of antioxidant 168, 1 part of inactive diluent mesitylene, and 15 parts of active diluent carbon twelve to fourteen 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] Embodiment 7-12 provides a method for preparing an epoxy resin adhesive, comprising the following steps:

[0147] Preparation of main agent components:

[0148] 1) Add the nano rubber toughener, liquid rubber toughener, antioxidant, inactive diluent and 10 parts of bisphenol A epoxy resin in the amount of Examples 1-6 into a Σ paddle kneader in sequence, stir at a speed of 150 rpm for 20 min into a paste, and evenly disperse the nano rubber particles in the epoxy resin matrix to form a masterbatch.

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

[0150] Prepare the curing agent component:

[0151] The reaction kettle was preheated to 70-80° C., and the fatty amine curing agent, amide amine curing agent, phenolic curing agent, coupling agent and antioxidant in Examples 1-6 were added at one time. After stirring at a high speed (400 rpm) in vacuum for 60 min, the temperature was lowered to 30-40° C., and the mixture was stirred at a low speed (150 rpm) in vacuum for 30 min to remove bubbles and discharge the mixture to obtain a curing agent component.

[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 Embodiment 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) at normal pressure for 100 min, and then stirring was performed 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 min, the temperature was lowered to 30-40° C., and stirring at low speed (100 rpm) in vacuum was continued for 40 min;

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

[0158] Embodiment 14

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

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

[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 includes the following raw materials in parts by weight:

[0165] When preparing the main agent component, no nano rubber toughening agent VP-501 was added, the amount of liquid rubber toughening agent CTBN was 15 parts, and the other components were the same as in Example 1.

[0166] Comparative Example 2

[0167] This comparative example provides an epoxy resin adhesive, which includes 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 other components were the same as in Example 1.

[0169] Comparative Example 3

[0170] This comparative example provides an epoxy resin adhesive, which includes 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 includes 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, which differs from Example 7 in 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] It can be seen from the data in Table 2 that in terms of mechanical strength, the higher the content of nano rubber toughening agent in the main agent and amide amine 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 a steel plate of >2.5MPa at a high temperature of 70°C, a pull-out strength of a composite part of >2.0MPa, and an oblique shear strength of a 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%. It also has a relatively long 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 aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned 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 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; The components of the curing agent include: an amine curing agent, a phenolic curing agent, a coupling agent and an optional second antioxidant.

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; Preferably, the amine curing agent includes at least one of a fatty amine curing agent and an amide amine curing agent; Preferably, the main agent comprises the following raw materials 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; Preferably, the curing agent comprises the following raw materials by weight: 40-60 parts of fatty amine curing agent, 10-40 parts of amide amine curing agent, 20-30 parts of phenolic curing agent, 1-3 parts of coupling agent and 1-3 parts of second antioxidant.

3. The epoxy resin adhesive according to claim 1, characterized in that: The bisphenol A type epoxy resin includes a bisphenol A glycidyl ether epoxy resin containing two epoxy groups; Preferably, the bisphenol A type epoxy resin includes at least one of E51, E44, E39, E20 and E12; Preferably, the reactive diluent includes a hydrophobic long-chain alkyl glycidyl ether in the molecule; 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; Preferably, the inactive diluent includes at least one of xylene and mesitylene.

4. The epoxy resin adhesive according to claim 1, characterized in that: The liquid rubber toughening agent includes carboxyl-terminated liquid nitrile rubber (CTBN); Preferably, the nano rubber toughening agent comprises fully vulcanized carboxylated nitrile rubber nanoparticles; Preferably, the acrylonitrile content of the fully vulcanized carboxylated nitrile rubber nanoparticles is 22-30%; Preferably, the average particle size of the fully vulcanized carboxylated nitrile rubber nanoparticles is 80-100 nm; Preferably, the first antioxidant includes antioxidant 168 , and at least one of antioxidant 1010 , antioxidant 1076 , antioxidant 1135 , and antioxidant 245 .

5. The epoxy resin adhesive according to claim 2, characterized in that: The fatty amine curing agent includes a long-chain alkyl primary amine; Preferably, the carbon number of the alkyl group in the long-chain alkyl primary amine is 12-18; 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.; Preferably, the phenolic curing agent includes at least one of 2,4,6-tris(dimethylaminomethyl)phenol, nonylphenol and resorcinol; Preferably, the coupling agent comprises aminosilane; Preferably, the coupling agent includes at least one of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, and 3-aminoethylaminopropyltrimethoxysilane; Preferably, the second antioxidant includes antioxidant 168 and at least one of antioxidant 1010 , antioxidant 1076 , antioxidant 1135 , and antioxidant 245 .

6. The method for preparing the epoxy resin adhesive according to any one of claims 1 to 5, characterized in that: 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 part of the bisphenol A type epoxy resin are mixed for the first time to obtain a paste-like nano rubber masterbatch, and then the nano rubber masterbatch, the active diluent and the remaining part of the bisphenol A type epoxy resin are mixed for the 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 amide amine curing agent, the phenolic curing agent, the coupling agent and the second antioxidant for the third time.

7. The method for preparing the epoxy resin adhesive according to claim 6, characterized in that: The first mixing comprises: stirring the mixed raw materials at room temperature for 15-25 minutes; Preferably, the stirring speed of the first mixing is 100-200 rpm.

8. The method for preparing the epoxy resin adhesive according to claim 6, characterized in that: 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, and discharging the materials after removing bubbles; 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; Preferably, the temperature of the second mixing is 100-110°C.

9. The method for preparing the epoxy resin adhesive according to claim 6, characterized in that: The third mixing includes: vacuum stirring the mixed raw materials for 50-70 minutes, cooling to 30-40°C, vacuum stirring for 20-40 minutes, removing bubbles and then discharging; 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; Preferably, the preheating temperature of the third mixing is 70-80°C.

10. Use of the epoxy resin adhesive according to any one of claims 1 to 5 in steel bridge deck paving.

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