CN113444457B - High-modulus high-toughness epoxy structural adhesive and preparation method and application thereof - Google Patents

High-modulus high-toughness epoxy structural adhesive and preparation method and application thereof Download PDF

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CN113444457B
CN113444457B CN202011077085.5A CN202011077085A CN113444457B CN 113444457 B CN113444457 B CN 113444457B CN 202011077085 A CN202011077085 A CN 202011077085A CN 113444457 B CN113444457 B CN 113444457B
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epoxy
poss
epoxy resin
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amino
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CN113444457A (en
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李波
孙德文
马英杰
候平平
刘畅
尹浩
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Sobute New Materials Co Ltd
Bote New Materials Taizhou Jiangyan Co Ltd
Nanjing Bote New Materials Co Ltd
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Sobute New Materials Co Ltd
Bote New Materials Taizhou Jiangyan Co Ltd
Nanjing Bote New Materials Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J1/00—Adhesives based on inorganic constituents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

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Abstract

The invention discloses a high-modulus high-toughness epoxy structural adhesive and a preparation method and application thereof. The epoxy structural adhesive is A, B two-component adhesive, and the component A comprises epoxy resin, an epoxy diluent, epoxy grafted POSS, a wetting dispersant, a defoaming agent, a thixotropic agent and fine aggregate; the component B comprises a curing agent and a curing accelerator; the epoxy grafted POSS is prepared by grafting and modifying amino POSS by using a bifunctional epoxy diluent. According to the invention, the epoxy grafted POSS is introduced into the system, so that the problems of large brittleness and insufficient fracture toughness of the traditional epoxy resin are solved, the fracture toughness and the fracture elongation of the material are improved, the mechanical strength and the elastic modulus of the material are maintained or slightly improved, and the problems that the fracture toughness and the fracture elongation of the material are increased and the mechanical strength and the modulus of the material are reduced in the conventional epoxy-based material toughening method and means are solved.

Description

High-modulus high-toughness epoxy structural adhesive and preparation method and application thereof
Technical Field
The invention belongs to the technical field of building structure adhesives, and particularly relates to a high-modulus high-toughness epoxy structure adhesive as well as a preparation method and application thereof.
Background
Epoxy resins are widely used in various fields in national economy due to their excellent physical and mechanical properties, and among them, they are very commonly used in the construction field. The prefabricated part splicing glue is usually an epoxy resin-based material, and the main technical points of the epoxy resin material are high modulus, high strength, high bonding, fatigue resistance and creep resistance, but the epoxy resin material has significant disadvantages such as high brittleness and insufficient toughness. For the glue for splicing the prefabricated parts, the glue needs to have high modulus to resist material deformation and creep deformation caused under a heavy load condition, and also needs to have good impact toughness to resist instantaneous impact load and avoid material cracking failure caused by local stress concentration effect.
A great deal of modification means such as toughening of second-phase core-shell structure particles, toughening modification of molecular-level interpenetrating networks and the like exist at present for solving the problem of insufficient toughness of epoxy resin, but the modification means can increase the flexibility of epoxy materials and obviously reduce the strength and elastic modulus of the materials, so that the high modulus and the high toughness of the materials cannot be obtained simultaneously. In the current splicing design of prefabricated parts, in consideration of the safety of buildings, the glue for splicing the prefabricated parts has high bonding property and high modulus and also needs to have higher elongation at break (high fracture toughness) so as to improve the fatigue resistance and the earthquake resistance of buildings.
Chinese patent 201611173603.7 discloses a toughened and heat-resistant modified epoxy resin and a preparation method thereof, the invention bonds amino silicone oil in an epoxy resin system by taking Polysilsesquioxane (POSS) as a bridge, although the elongation at break of the epoxy-based material is increased to a certain extent, the chain flexibility is higher than that of a common carbon chain in the system due to the fact that the main chain of the amino silicone oil is polydimethylsiloxane, the chain has higher molecular weight, longer chain segment and strong network deformability, and although the elongation at break of the modified material is obviously increased, the elastic modulus of the material is greatly reduced, and the mechanical strength is insufficient.
Chinese patent 201410827360.9 discloses a two-component toughened impact-resistant epoxy structural adhesive and a preparation method thereof, the impact resistance and damping performance of the epoxy structural adhesive are improved by modifying polysulfide rubber, but the elastic modulus and partial mechanical properties of the material are reduced while the impact resistance is improved due to the addition of a polysulfide rubber flexible chain segment. Therefore, the prior art is difficult to improve the fracture toughness and the elongation at break of the splicing glue of the prefabricated part and keep higher elastic modulus of the material.
Disclosure of Invention
The invention provides a high-modulus high-toughness epoxy structural adhesive and a preparation method and application thereof, aiming at the problem that in the prior art, the fracture toughness and the elongation at break of prefabricated part splicing adhesive, bar-embedded anchoring adhesive or steel-bonded adhesive and the like are improved, and meanwhile, the problem that the higher elastic modulus of a material is difficult to maintain, namely the problem that the high modulus and the high toughness are difficult to obtain.
In order to achieve the purpose, the invention adopts the following technical scheme:
the high-modulus high-toughness epoxy structural adhesive is A, B two-component adhesive, and is prepared from the following components in parts by weight: the mass ratio of B is 5-35: 1;
the component A comprises the following components in parts by weight:
Figure BDA0002717803310000021
the component B comprises the following components in parts by weight:
15-45 parts of a curing agent,
0-3 parts of a curing accelerator.
The epoxy value of the epoxy resin in the component A is 0.44-0.55 mol/100 g;
preferably, the epoxy resin is selected from any one of bisphenol A epoxy resin and bisphenol F epoxy resin or a mixture of two of the bisphenol A epoxy resin and the bisphenol F epoxy resin in any proportion;
more preferably, the epoxy value of the bisphenol A epoxy resin is 0.51-0.55 mol/100g, the specific epoxy value of the bisphenol F epoxy resin is 0.44-0.55 mol/100g, and the epoxy resin is more preferably selected from one or more of bisphenol A epoxy resin E51 (epoxy value of 0.51mol/100g), bisphenol A epoxy resin E55 (epoxy value of 0.55mol/100g), bisphenol F epoxy resin F44 (epoxy value of 0.44mol/100g), bisphenol F epoxy resin F51 (epoxy value of 0.51mol/100g), and bisphenol F epoxy resin F55 (epoxy value of 0.55mol/100 g).
The epoxy diluent is selected from any one or a mixture of more than one of butyl glycidyl ether, benzyl glycidyl ether, dodecyl glycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether and cardanol glycidyl ether; the epoxy diluent mainly plays a role in diluting and viscosity reduction;
the epoxy grafted POSS is prepared by grafting and modifying amino POSS by using a bifunctional epoxy diluent; the mass ratio of the bifunctional epoxy diluent to the amino POSS is 100: 5-25;
the amino POSS structure is selected from one or a mixture of two of an amino polysilsesquioxane T6 structure and an amino polysilsesquioxane T8 structure;
the structure of the amino polysilsesquioxane T6, namely the structural formula of the T6 amino POSS is shown as the following formula (I):
Figure BDA0002717803310000031
the structure of the amino polysilsesquioxane T8, namely the structural formula of the T8 amino POSS is shown as the following formula (II):
Figure BDA0002717803310000032
r in the structures of T6 amino POSS and T8 amino POSS is gamma-CH2CH2CH2NH2I.e., gamma-aminopropyl;
the difunctional epoxy diluent is selected from any one or more than one mixture of C2-C6 alkyl glycol diglycidyl ether;
the specific preparation method of the epoxy grafted POSS comprises the following steps: dissolving amino POSS powder in toluene, wherein the dosage of the toluene solvent is 2-3 times of the total mass of the amino POSS and the bifunctional epoxy diluent, and heating to 60 +/-5 ℃; after the amino POSS is completely dissolved, adding the metered bifunctional epoxy diluent into a toluene solution of the amino POSS at one time, heating to 80 +/-5 ℃, stirring for reacting for 3-8 h, grafting the bifunctional epoxy diluent to an amino POSS end group in an open-loop manner to form epoxy grafted POSS, and removing the toluene solvent in vacuum at 100 +/-5 ℃ to obtain viscous epoxy grafted POSS;
the structure of the epoxy grafted POSS is shown as the formula (III) or (IV):
Figure BDA0002717803310000041
wherein R is1The groups are as follows:
Figure BDA0002717803310000042
wherein R is2Is C2-C6 alkyl;
the defoaming agent is a modified polysiloxane organic silicon defoaming agent for oily system epoxy resin, and has the function of eliminating bubbles in the system; preferably, the defoaming agent is a moderate chemical 6800 oily system organic silicon defoaming agent or a BYK061 modified organic silicon defoaming agent;
the wetting dispersant is an amphipathic copolymer (oil and water) containing carboxylic acid groups in an oily system, and is mainly used for wetting and dispersing filler in the system; preferably, the wetting and dispersing agent is a courtesy chemical 9250 or 983 wetting and dispersing agent;
the thixotropic agent is commercially available hydrophilic gas phase method nano silicon dioxide, and the specific surface area is 100-400 m2The concentration/g is mainly used for adjusting the thixotropic effect of the system and the construction state of the product; the preferred thixotropic agent is the gas phase method nano silicon dioxide of Wingda degussa A150, A200, A300 or A380;
the fine aggregate is any one or more of quartz powder, talcum powder, barium sulfate and calcium carbonate which are 200-800 meshes; preferably, the fine aggregate is one or a mixture of more than one quartz powder with 200-800 meshes;
the curing agent is aliphatic, aromatic and alicyclic polyamine curing agent or modified polyamine curing agent thereof; preferably, the polyamine curing agent is selected from any one or more than one of diethylenetriamine, triethylene tetramine, tetraethylene pentamine, isophorone diamine (IPDA), 1, 3-cyclohexane dimethylamine (1,3-BAC), and commercially available Nanjing forestry chemical research institute 401 curing agent;
the curing accelerator is a tertiary amine accelerator; preferably, the tertiary amine accelerator is 2,4, 6-tris (dimethylamino) phenol (DMP30) or 1, 8-diazabicycloundec-7-ene (DBU).
The invention relates to a preparation method of a high-modulus high-toughness epoxy structural adhesive, which specifically comprises the following steps:
(1) pre-reacting a bifunctional epoxy reactive diluent and amino POSS in a toluene solution at 80 +/-5 ℃ for 3-8 h, and removing the toluene solvent in vacuum at 100 +/-5 ℃ to obtain viscous epoxy grafted POSS;
(2) mixing epoxy resin, epoxy diluent, epoxy grafted POSS, wetting dispersant, defoaming agent and thixotropic agent in proportion, and dispersing at a high speed by using a high-speed dispersion machine, wherein the dispersion speed is 800-2000 r/min, the dispersion temperature is controlled at 20-40 ℃, and the dispersion time is 30-60 min to obtain a resin premix;
(3) adding fine aggregate into the resin premix prepared in the step (2) according to a set amount, heating the materials to 40-60 ℃, continuously and uniformly dispersing and stirring at a high speed, controlling the dispersion speed to be 800-1500 r/min, and dispersing for 20-40 min to obtain a component A;
(4) mixing a curing agent and a curing accelerator in proportion to obtain a component B;
(5) when in use, the A, B components are mixed and stirred evenly according to the proportion.
The invention adopts bifunctional epoxy active diluent to graft and modify amino POSS to obtain epoxy grafted POSS, and then the epoxy grafted POSS is used for modifying epoxy prefabricated part splicing glue.
The epoxy structural adhesive disclosed by the invention is not only applied to splicing adhesives of concrete prefabricated parts, but also can be applied to the field of building adhesives such as bar-planting anchoring adhesives and steel bonding adhesives.
Has the advantages that:
compared with the prior art, the invention has the following advantages and effects:
(1) according to the epoxy structural adhesive and the preparation method thereof, the problems of large brittleness and insufficient fracture toughness of the traditional epoxy resin are solved by introducing the epoxy grafted POSS into the system, the fracture toughness and the fracture elongation of the material are improved, and simultaneously the mechanical strength and the elastic modulus of the material are kept or slightly improved, so that the problems that the mechanical strength and the modulus of the material are reduced while the fracture toughness and the fracture elongation of the material are increased in the conventional epoxy base material toughening method and means, namely the high modulus and the high toughness (high deformability) cannot be obtained simultaneously are solved.
(2) According to the invention, the bifunctional epoxy diluent grafted and modified amino POSS is introduced into the epoxy resin matrix for epoxy resin modification, compared with the traditional POSS modified epoxy resin, POSS is usually directly doped in the epoxy matrix, and the bifunctional epoxy diluent grafted and modified amino POSS can improve the dispersibility of the amino POSS in the resin matrix and the matrix compatibility, so that the toughening and reinforcing effects of POSS are more obvious, and the obvious modification effect can be obtained by adding a small amount of POSS.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
The performance test of the epoxy structural adhesive is carried out according to relevant regulations in GB/T2567-2008 resin casting body performance test method and FIP international post-tensioned prestressing Association. Preparing the structural adhesive, forming the sample to be 23 +/-2 ℃, drying the sample at the curing temperature of 40 ℃ for 16h, drying the sample at the curing temperature of 60 ℃ for 4h, cooling the sample to 23 +/-2 ℃, and detecting the sample after the sample is kept for 24 h.
The preparation method of the high-modulus high-toughness epoxy structural adhesive comprises the following steps:
(1) dissolving amino POSS in a toluene solvent, adding a metered bifunctional epoxy reactive diluent, carrying out pre-reaction at 80 +/-5 ℃ for 3-8 h, and removing the toluene solvent at 100 +/-5 ℃ in vacuum to obtain epoxy grafted POSS for later use;
(2) mixing epoxy resin, epoxy diluent, epoxy grafted POSS, wetting dispersant, defoaming agent and thixotropic agent in proportion, and dispersing at a high speed by using a high-speed dispersion machine, wherein the dispersion speed is 800-2000 r/min, the dispersion temperature is controlled at 20-40 ℃, and the dispersion time is 30-60 min to obtain a resin premix;
(3) adding fine aggregate into the resin premix according to a proportion, heating the materials to 40-60 ℃, continuously and uniformly stirring by using a high-speed dispersion machine, controlling the dispersion rotation speed to be 800-1500 r/min, and dispersing for 20-40 min to obtain a component A;
(4) mixing a curing agent and a curing accelerator in proportion to obtain a component B;
(5) a, B components are mixed and stirred evenly according to a proportion to obtain the epoxy structural adhesive;
the method is characterized in that the step (5) is carried out before use, and the tensile strength, the elongation at break, the compressive strength, the instantaneous compression elastic modulus and the impact strength of the composite material are measured when the composite material is molded and cured for 7 days.
All parts in examples and comparative examples are parts by mass.
In the following examples:
bisphenol A type and bisphenol F type epoxy resins are products of resin factories in south Asia, and specifically comprise the following components: bisphenol A epoxy resin E51 (epoxy value 0.51mol/100g), bisphenol A epoxy resin E55 (epoxy value 0.55mol/100g), bisphenol F epoxy resin F44 (epoxy value 0.44mol/100g), bisphenol F epoxy resin F51 (epoxy value 0.51mol/100g), bisphenol F epoxy resin F55 (epoxy value 0.55mol/100 g);
the bifunctional epoxy diluent is a product of Shanghai chemical engineering science and technology limited company, and specifically comprises the following components: HY669 has chemical structure of ethylene glycol diglycidyl ether, epoxy value of 0.70-0.80 mol/100g, and industrial grade; HY622 has a chemical structure of butanediol diglycidyl ether, an epoxy value of 0.74-0.83 mol/100g, and is of industrial grade; HY632 has a chemical structure of hexanediol diglycidyl ether, an epoxy value of 0.65-0.70 mol/100g, and industrial grade;
the epoxy diluent is Anhui New technology limited, and specifically comprises butyl glycidyl ether (epoxy value is 0.59-0.63 mol/100g), benzyl glycidyl ether (epoxy value is 0.54-0.58 mol/100g), dodecyl glycidyl ether (epoxy value is 0.34-0.38 mol/100g), cardanol glycidyl ether (epoxy value is 0.24-0.28 mol/100g), polyethylene glycol diglycidyl ether (epoxy value is 0.3-0.35 mol/100g), and polypropylene glycol diglycidyl ether (epoxy value is 0.29-0.35 mol/100 g);
the amino POSS is a self-made T6 or T8 structure, the preparation method refers to literature hydrolysis method, and the top group is-CH2CH2CH2-NH2；
The defoaming agent is an organic silicon defoaming agent, a product of moderate chemistry, ltd, and the brand number of 6800;
the wetting and dispersing agent is a product of moderate chemistry, Inc., and is the brand number 9250;
the thixotropic agent is a product of Yingchuangdegsai Co., Ltd, and is of a brand number A200;
the epoxy grafted POSS was prepared as follows:
the first synthesis example:
dissolving 25g of amino POSS T8 in 360g of toluene, heating to 60 +/-5 ℃, adding 100g of ethylene glycol diglycidyl ether, heating to 80 +/-5 ℃ to react for 3 hours, heating to 100 +/-5 ℃, and removing the toluene solvent in vacuum to obtain the epoxy grafted POSS 1.
Synthesis example two:
dissolving 20g of amino POSS T8 in 300g of toluene, heating to 60 +/-5 ℃, adding 100g of butanediol diglycidyl ether, heating to 80 +/-5 ℃, reacting for 4 hours, heating to 100 +/-5 ℃, and removing the toluene solvent in vacuum to obtain the epoxy grafted POSS 2.
Synthesis example three:
dissolving 15g of amino POSS T8 in 280g of toluene, heating to 60 +/-5 ℃, adding 100g of hexanediol diglycidyl ether, heating to 80 +/-5 ℃, reacting for 8 hours, heating to 100 +/-5 ℃, and removing the toluene solvent in vacuum to obtain the epoxy grafted POSS 3.
Synthesis example four:
dissolving 10g of amino POSST8 in 220g of toluene, heating to 60 +/-5 ℃, adding 100g of hexanediol diglycidyl ether, heating to 80 +/-5 ℃, reacting for 8 hours, heating to 100 +/-5 ℃, and removing the toluene solvent in vacuum to obtain the epoxy grafted POSS 4.
Synthesis example five:
10g of amino POSST6 and 10g of amino PossT8 are dissolved in 300g of toluene, heated to 60 +/-5 ℃, added with 100g of butanediol diglycidyl ether, heated to 80 +/-5 ℃ for reaction for 4 hours, heated to 100 +/-5 ℃, and subjected to vacuum removal of toluene solvent to obtain the epoxy grafted POSS 5.
Synthesis example six:
dissolving 20g of amino POSST6 in 300g of toluene, heating to 60 +/-5 ℃, adding 100g of butanediol diglycidyl ether, heating to 80 +/-5 ℃, reacting for 4 hours, heating to 100 +/-5 ℃, and removing the toluene solvent in vacuum to obtain the epoxy grafted POSS 6.
The preparation example of the epoxy prefabricated part splicing adhesive is as follows:
example 1
The epoxy structural adhesive consists of a component A and a component B, wherein:
the component A comprises the following components in parts by weight:
Figure BDA0002717803310000091
the component B comprises the following components in parts by weight:
42 parts of a curing agent, namely,
1 part of a curing accelerator;
the epoxy resin is bisphenol F epoxy resin F51, the epoxy grafted POSS is epoxy grafted POSS4, the wetting dispersant is 9250, the defoaming agent is 6800, the thixotropic agent is Degussa A200 gas phase method nano silicon dioxide, the fine aggregate is 400-mesh quartz powder, the curing agent is 401, and the curing accelerator is 2,4, 6-tri (dimethylamino) phenol. The A, B components are respectively obtained by preparing the materials according to 2-5 steps in the preparation method, and the materials are measured according to the mass ratio of A: and B is 6:1, and the mixture is uniformly mixed and stirred and then molded to prepare a sample.
Example 2
The epoxy structural adhesive consists of a component A and a component B, wherein:
the component A comprises the following components in parts by weight:
Figure BDA0002717803310000092
the component B comprises the following components in parts by weight:
42 parts of a curing agent, namely,
2 parts of a curing accelerator;
the epoxy resin is bisphenol A epoxy resin E51, the epoxy diluent is butyl glycidyl ether, the epoxy grafted POSS is epoxy grafted POSS3, the wetting dispersant is 9250, the defoaming agent is 6800, the thixotropic agent is Degussa A200 gas phase method nano silicon dioxide, the fine aggregate is 400-mesh quartz powder, the curing agent is 401, and the curing accelerator is 2,4, 6-tri (dimethylamino) phenol. The A, B components are prepared from the materials according to the steps of 2-5 in the preparation method, and the mass ratio of A: and B is 8:1, and the mixture is uniformly mixed and stirred and then molded to prepare a sample.
Example 3
The epoxy structural adhesive consists of a component A and a component B, wherein:
the component A comprises the following components in parts by weight:
Figure BDA0002717803310000101
the component B comprises the following components in parts by weight:
42 parts of a curing agent, namely,
3 parts of an accelerant;
the epoxy resin is bisphenol A epoxy resin E51, the epoxy diluent is butyl glycidyl ether, the epoxy grafted POSS is epoxy grafted POSS2, the wetting dispersant is 9250, the defoaming agent is 6800, the thixotropic agent is Degussa A200 gas phase method nano silicon dioxide, the fine aggregate is 400-mesh quartz powder, the curing agent is 401, and the curing accelerator is 2,4, 6-tri (dimethylamino) phenol. The A, B components are prepared from the materials according to the steps of 2-5 in the preparation method, and the mass ratio of A: and B is 10:1, and the mixture is uniformly mixed and stirred and then molded to prepare a sample.
Example 4
The epoxy structural adhesive consists of a component A and a component B, wherein:
the component A comprises the following components in parts by weight:
Figure BDA0002717803310000102
Figure BDA0002717803310000111
the component B comprises the following components in parts by weight:
42 parts of a curing agent, namely,
2 parts of a curing accelerator;
the epoxy resin is bisphenol A epoxy resin E51, the epoxy diluent is butyl glycidyl ether, the epoxy grafted POSS is epoxy grafted POSS1, the wetting dispersant is 9250, the defoaming agent is 6800, the thixotropic agent is Degussa A200 gas phase method nano silicon dioxide, the fine aggregate is 400-mesh quartz powder, the curing agent is 401, and the curing accelerator is 1, 8-diazabicycloundece-7-ene. The A, B components are prepared from the materials according to the steps of 2-5 in the preparation method, and the mass ratio of A: and B is 9:1, and the mixture is uniformly mixed and stirred and then is molded to prepare a sample.
Example 5
The epoxy structural adhesive consists of a component A and a component B, wherein:
the component A comprises the following components in parts by weight:
Figure BDA0002717803310000112
the component B comprises the following components in parts by weight:
17 parts of a curing agent;
the epoxy resin is bisphenol A epoxy resin E55, the epoxy diluent is benzyl glycidyl ether, the epoxy grafted POSS is epoxy grafted POSS1, the wetting dispersant is 9250, the defoaming agent is 6800, the thixotropic agent is Degussa A200 gas phase method nano silicon dioxide, the fine aggregate is 200-mesh quartz powder, and the curing agent is triethylene tetramine. The A, B components are prepared from the materials according to the steps of 2-5 in the preparation method, and the mass ratio of A: and B, mixing and stirring uniformly 22:1, and molding to prepare a sample.
Example 6
The epoxy structural adhesive consists of a component A and a component B, wherein:
the component A comprises the following components in parts by weight:
Figure BDA0002717803310000121
the component B comprises the following components in parts by weight:
30 parts of a curing agent;
the epoxy resin is bisphenol F epoxy resin F55, the epoxy diluent is dodecyl glycidyl ether, the epoxy grafted POSS is epoxy grafted POSS1, the wetting dispersant is 9250, the defoaming agent is 6800, the thixotropic agent is Degussa A200 gas phase method nano silicon dioxide, the fine aggregate is 200 meshes of quartz powder, and the curing agent is isophorone diamine. The A, B components are prepared from the materials according to the steps of 2-5 in the preparation method, and the mass ratio of A: b is 13:1, and the mixture is evenly mixed and stirred and then is molded to prepare a sample
Example 7
The epoxy structural adhesive consists of a component A and a component B, wherein:
the component A comprises the following components in parts by weight:
Figure BDA0002717803310000122
the component B comprises the following components in parts by weight:
25 parts of a curing agent;
the epoxy resin is bisphenol F epoxy resin F51, the epoxy diluent is butanediol diglycidyl ether, the epoxy grafted POSS is epoxy grafted POSS1, the wetting dispersant is 9250, the defoaming agent is 6800, the thixotropic agent is Degussa A200 gas phase method nano silicon dioxide, the fine aggregate is 200-mesh quartz powder, and the curing agent is 1, 3-cyclohexyldimethylamine (1, 3-BAC). The A, B components are prepared from the materials according to the steps of 2-5 in the preparation method, and the mass ratio of A: and B is 15:1, and the mixture is uniformly mixed and stirred and then is molded to prepare a sample.
Example 8
The epoxy structural adhesive consists of a component A and a component B, wherein:
the component A comprises the following components in parts by weight:
Figure BDA0002717803310000131
the component B comprises the following components in parts by weight:
31 parts of a curing agent;
the epoxy resin is bisphenol F epoxy resin F51, the epoxy diluent is 10 parts of butanediol diglycidyl ether, 5 parts of benzyl glycidyl ether, the epoxy grafted POSS is epoxy grafted POSS1, the wetting dispersant is 9250, the defoaming agent is 6800, the thixotropic agent is Degussa A200 gas phase method nano silicon dioxide, the fine aggregate is 100 parts of 200-mesh quartz powder, 100 parts of 400-mesh quartz powder and 38 parts of 800-mesh quartz powder, the curing agent is 3 parts of tetraethylenepentamine, 20 parts of 401 curing agent and 8 parts of 1, 3-cyclohexyldimethylamine (1, 3-BAC). The A, B components are prepared from the materials according to the steps of 2-5 in the preparation method, and the mass ratio of A: and B is 12:1, and the mixture is uniformly mixed and stirred and then molded to prepare a sample.
Example 9
The epoxy structural adhesive consists of a component A and a component B, wherein:
the component A comprises the following components in parts by weight:
Figure BDA0002717803310000132
Figure BDA0002717803310000141
the component B comprises the following components in parts by weight:
42 parts of a curing agent, namely,
2 parts of a curing accelerator;
the epoxy resin is bisphenol A epoxy resin E51, the epoxy diluent is polypropylene glycol diglycidyl ether, the epoxy grafted POSS is epoxy grafted POSS1, the wetting dispersant is 9250, the defoaming agent is 6800, the thixotropic agent is Degussa A200 fumed silica, the fine aggregate is 400-mesh talcum powder, the curing agent is 401 curing agent, and the curing accelerator is 1, 8-diazabicycloundece-7-ene. The A, B components are prepared from the materials according to the steps of 2-5 in the preparation method, and the mass ratio of A: and B is 9:1, and the mixture is uniformly mixed and stirred and then is molded to prepare a sample.
Example 10
The epoxy structural adhesive consists of a component A and a component B, wherein:
the component A comprises the following components in parts by weight:
Figure BDA0002717803310000142
the component B comprises the following components in parts by weight:
42 parts of a curing agent, namely,
2 parts of a curing accelerator;
the epoxy resin is bisphenol A epoxy resin E51, the epoxy diluent is cardanol glycidyl ether, the epoxy grafted POSS is epoxy grafted POSS1, the wetting dispersant is 9250, the defoaming agent is 6800, the thixotropic agent is Degussa A200 gas phase method nano silicon dioxide, the fine aggregate is 800-mesh barium sulfate, the curing agent is 401 curing agent, and the curing accelerator is 1, 8-diazabicycloundece-7-ene. The A, B components are prepared from the materials according to the steps of 2-5 in the preparation method, and the mass ratio of A: and B is 9:1, and the mixture is uniformly mixed and stirred and then is molded to prepare a sample.
Example 11
The epoxy structural adhesive consists of a component A and a component B, wherein:
the component A comprises the following components in parts by weight:
Figure BDA0002717803310000151
the component B comprises the following components in parts by weight:
42 parts of a curing agent, namely,
2 parts of a curing accelerator;
the epoxy resin is bisphenol A epoxy resin E51, the epoxy diluent is polyethylene glycol diglycidyl ether, the epoxy grafted POSS is epoxy grafted POSS1, the wetting dispersant is 9250, the defoaming agent is 6800, the thixotropic agent is Degussa A200 fumed silica, the fine aggregate is 150 parts of 800-mesh barium sulfate, 88 parts of 600-mesh calcium carbonate, the curing agent is 401 curing agent, and the curing accelerator is 1, 8-diazabicycloundecan-7-ene. The A, B components are prepared from the materials according to the steps of 2-5 in the preparation method, and the mass ratio of A: and B is 9:1, and the mixture is uniformly mixed and stirred and then is molded to prepare a sample.
Example 12
The epoxy structural adhesive consists of a component A and a component B, wherein:
the component A comprises the following components in parts by weight:
Figure BDA0002717803310000152
the component B comprises the following components in parts by weight:
42 parts of a curing agent, namely,
2 parts of a curing accelerator;
the epoxy resin is bisphenol A epoxy resin E51, the epoxy diluent is polyethylene glycol diglycidyl ether, the epoxy grafted POSS is epoxy grafted POSS1, the wetting dispersant is 9250, the defoaming agent is 6800, the thixotropic agent is Degussa A200 gas phase method nano-silica, the fine aggregate is 600 mesh calcium carbonate, the curing agent is 42 parts of 401 curing agent, and the curing accelerator is 1, 8-diazabicycloundec-7-ene. The A, B components are prepared from the materials according to the steps of 2-5 in the preparation method, and the mass ratio of A: and B is 9:1, and the mixture is uniformly mixed and stirred and then is molded to prepare a sample.
Example 13
The epoxy structural adhesive consists of a component A and a component B, wherein:
the component A comprises the following components in parts by weight:
Figure BDA0002717803310000161
the component B comprises the following components in parts by weight:
42 parts of a curing agent, namely,
2 parts of a curing accelerator;
the epoxy resin is bisphenol A epoxy resin E51, the epoxy diluent is butyl glycidyl ether, the epoxy grafted POSS is epoxy grafted POSS5, the wetting dispersant is 9250, the defoaming agent is 6800, the thixotropic agent is Degussa A200 gas phase method nano silicon dioxide, the fine aggregate is 400-mesh quartz powder, the curing agent is 401, and the curing accelerator is 1, 8-diazabicycloundece-7-ene. The A, B components are prepared from the materials according to the steps of 2-5 in the preparation method, and the mass ratio of A: and B is 9:1, and the mixture is uniformly mixed and stirred and then is molded to prepare a sample.
Example 14
The epoxy structural adhesive consists of a component A and a component B, wherein:
the component A comprises the following components in parts by weight:
Figure BDA0002717803310000171
the component B comprises the following components in parts by weight:
42 parts of a curing agent, namely,
2 parts of a curing accelerator;
the epoxy resin is bisphenol A epoxy resin E51, the epoxy diluent is butyl glycidyl ether, the epoxy grafted POSS is epoxy grafted POSS6, the wetting dispersant is 9250, the defoaming agent is 6800, the thixotropic agent is Degussa A200 gas phase method nano silicon dioxide, the fine aggregate is 400-mesh quartz powder, the curing agent is 401, and the curing accelerator is 1, 8-diazabicycloundece-7-ene. The A, B components are prepared from the materials according to the steps of 2-5 in the preparation method, and the mass ratio of A: and B is 9:1, and the mixture is uniformly mixed and stirred and then is molded to prepare a sample.
Comparative example 1
The epoxy structural adhesive consists of a component A and a component B, wherein:
the component A comprises the following components in parts by weight:
Figure BDA0002717803310000172
the component B comprises the following components in parts by weight:
42 parts of a curing agent, namely,
3 parts of a curing accelerator;
wherein the epoxy resin is bisphenol A epoxy resin E51, the epoxy diluent is butyl glycidyl ether, the wetting dispersant is 9250, the defoamer is 6800, the thixotropic agent is Degussa A200 gas phase method nano silicon dioxide, the fine aggregate is 400 meshes of quartz powder, the curing agent is 401, and the curing accelerator is 2,4, 6-tri (dimethylamino) phenol. The A, B components are prepared from the materials according to the steps of 2-5 in the preparation method, and the mass ratio of A: and B is 10:1, and the mixture is uniformly mixed and stirred and then molded to prepare a sample.
Comparative example 2
The epoxy structural adhesive consists of a component A and a component B, wherein:
the component A comprises the following components in parts by weight:
Figure BDA0002717803310000181
the component B comprises the following components in parts by weight:
17 parts of a curing agent;
wherein the epoxy resin is bisphenol A epoxy resin E55, the epoxy diluent is benzyl glycidyl ether, the wetting dispersant is 9250, the defoamer is 6800, the thixotropic agent is Degussa A200 gas phase method nano silicon dioxide, the fine aggregate is 200 meshes of quartz powder, and the curing agent is triethylene tetramine. The A, B components are prepared from the materials according to the steps of 2-5 in the preparation method, and the mass ratio of A: and B, mixing and stirring uniformly 22:1, and molding to prepare a sample.
Comparative example 3
The epoxy structural adhesive consists of a component A and a component B, wherein:
the component A comprises the following components in parts by weight:
Figure BDA0002717803310000182
the component B comprises the following components in parts by weight:
30 parts of a curing agent;
wherein the epoxy resin is bisphenol F epoxy resin F55, the epoxy diluent is dodecyl glycidyl ether, the wetting dispersant is 9250, the defoamer is 6800, the thixotropic agent is Degussa A200 gas phase method nano silicon dioxide, the fine aggregate is 200 meshes of quartz powder, and the curing agent is isophorone diamine. The A, B components are prepared from the materials according to the steps of 2-5 in the preparation method, and the mass ratio of A: and B is 13:1, and the mixture is uniformly mixed and stirred and then molded to prepare a sample.
Comparative example 4 (see patent CN 201611173603.7A toughened, heat-resistant modified epoxy resin and preparation method thereof, example 4)
Taking 4g of gamma-glycidyl ether oxypropyl POSS and 4g of ethylene oxide POSS, adding 30g of amino silicone oil with the molecular weight of 8000, stirring at 70 ℃ for reaction for 3 hours to obtain uniform viscous solution, and naturally cooling to room temperature; then, 62.5g of epoxy resin E51,0.5g of catalyst aluminum chloride and 5g of curing agent diethylenetriamine are added into the viscous solution, and the required epoxy resin is obtained after reaction for 1 hour at 80 ℃.
Comparative example 5 (refer to patent CN 201611173603.7A toughened and heat-resistant modified epoxy resin and the preparation method thereof, example 4 is the preparation, 400-mesh quartz powder is combined to prepare the epoxy prefabricated part splicing glue)
Taking 4g of gamma-glycidyl ether oxypropyl POSS and 4g of ethylene oxide POSS, adding 30g of amino silicone oil with the molecular weight of 8000, stirring at 70 ℃ for reaction for 3 hours to obtain uniform viscous solution, and naturally cooling to room temperature; then, 62.5g of epoxy resin E51 is added into the viscous solution, after mixing and stirring evenly, 200g of 400-mesh quartz powder is added, high-speed dispersion and stirring are carried out for 20min at 1000r/min, 0.5g of catalyst aluminum chloride and 5g of curing agent diethylenetriamine are added, and curing is carried out for 1h at 80 ℃ to obtain the required epoxy resin sample.
Comparative example 6
The epoxy structural adhesive consists of a component A and a component B, wherein:
the component A comprises the following components in parts by weight:
Figure BDA0002717803310000191
the component B comprises the following components in parts by weight:
42 parts of a curing agent, namely,
2 parts of a curing accelerator;
the epoxy resin is bisphenol A epoxy resin E51, the epoxy diluent is butyl glycidyl ether, the amino POSS is T6, the wetting dispersant is 9250, the defoaming agent is 6800, the thixotropic agent is Degussa A200 gas phase method nano silicon dioxide, the fine aggregate is 400-mesh quartz powder, the curing agent is 401, and the curing accelerator is 1, 8-diazabicycloundecen-7-ene. The A, B components are prepared from the materials according to the steps of 2-5 in the preparation method, and the mass ratio of A: and B is 9:1, and the mixture is uniformly mixed and stirred and then is molded to prepare a sample.
Comparative example 7
The epoxy structural adhesive consists of a component A and a component B, wherein:
the component A comprises the following components in parts by weight:
Figure BDA0002717803310000201
the component B comprises the following components in parts by weight:
42 parts of a curing agent, namely,
2 parts of a curing accelerator;
the epoxy resin is bisphenol A epoxy resin E51, the epoxy diluent is butyl glycidyl ether, the amino POSS is T8, the wetting dispersant is 9250, the defoaming agent is 6800, the thixotropic agent is Degussa A200 gas phase method nano silicon dioxide, the fine aggregate is 400-mesh quartz powder, the curing agent is 401, and the curing accelerator is 1, 8-diazabicycloundecen-7-ene. The A, B components are prepared from the materials according to the steps of 2-5 in the preparation method, and the mass ratio of A: and B is 9:1, and the mixture is uniformly mixed and stirred and then is molded to prepare a sample.
The products obtained in the above examples and comparative examples were subjected to performance tests, and the test results are shown in table 1.
TABLE 1 Main mechanical Properties data of the various examples and comparative examples
Figure BDA0002717803310000202
Figure BDA0002717803310000211
The data in table 1 show that the high-modulus high-toughness epoxy structural adhesive obtained by the invention has high elongation at break and high impact strength, and simultaneously maintains a high compressive elastic modulus, compared with a sample without epoxy grafted POSS (comparative examples 1-3), the material of the invention has high tensile strength, elongation at break and impact strength, and simultaneously maintains a high compressive elastic modulus, which indicates that the epoxy structural adhesive obtained by the invention has good tensile strength and elongation at break, and simultaneously has an excellent compressive elastic modulus. As can be seen from comparative example 4, the amino silicone oil modified epoxy POSS improves the elongation at break of the epoxy resin, but the compressive elastic modulus is obviously lower, only 1830MPa, which is far from meeting the requirement that the compressive elastic modulus of the prefabricated part splicing adhesive in FIP International prestress tension Association is not less than 8000MPa, on the basis of comparative example 4, a certain amount of 400-mesh quartz powder (comparative example 5) is added into the system, and test data shows that the tensile strength, the elongation at break and the impact strength of a sample after the quartz powder is added are greatly reduced, the compressive elastic modulus is still lower although a certain degree is increased, and the requirement that the compressive elastic modulus of the prefabricated part splicing adhesive in FIP International prestress tension Association is not more than 8000MPa cannot be met. As can be seen from comparative examples 6 and 7, the epoxy resin system simply doped with amino POSS has lower mechanical properties than those of example 4, and has weaker improvement effect on the resin system.

Claims (12)

1. The high-modulus high-toughness epoxy structural adhesive is characterized by being A, B two-component adhesive, and comprising the following components in parts by weight: the mass ratio of B is 5-35: 1;
the component A comprises the following components in parts by weight:
Figure FDA0003468555890000011
the component B comprises the following components in parts by weight:
15-45 parts of a curing agent,
0-3 parts of a curing accelerator;
the epoxy value of the epoxy resin in the component A is 0.44-0.55 mol/100 g;
the epoxy diluent is selected from more than one of butyl glycidyl ether, benzyl glycidyl ether, dodecyl glycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether and cardanol glycidyl ether;
the epoxy grafted POSS is prepared by grafting and modifying amino POSS by using a bifunctional epoxy diluent, wherein the mass ratio of the bifunctional epoxy diluent to the amino POSS is 100: 5-25; the amino POSS structure is selected from one or a mixture of two of an amino polysilsesquioxane T6 structure and an amino polysilsesquioxane T8 structure; the difunctional epoxy diluent is a mixture of more than one of C2-C6 alkyl glycol diglycidyl ether;
the defoaming agent is a modified polysiloxane organic silicon defoaming agent for the oily epoxy resin;
the wetting dispersant is an amphipathic copolymer containing carboxylic acid groups in an oily system, and the copolymer is hydrophilic and lipophilic;
the thixotropic agent is commercially available hydrophilic gas phase method nano silicon dioxide, and the specific surface area is 100-400 m2/g；
The fine aggregate is selected from more than one of 200-800 meshes of quartz powder, talcum powder, barium sulfate and calcium carbonate;
the curing agent is aliphatic, aromatic and alicyclic polyamine curing agent or modified polyamine curing agent thereof;
the curing accelerator is a tertiary amine accelerator.
2. The high modulus high toughness epoxy structural adhesive according to claim 1, wherein said epoxy resin is selected from any one of bisphenol a epoxy resin and bisphenol F epoxy resin or a mixture of two of them in any ratio.
3. The high modulus high toughness epoxy structural adhesive according to claim 2, wherein said epoxy value of said bisphenol A epoxy resin is 0.51-0.55 mol/100g, and said epoxy value of said bisphenol F epoxy resin is 0.44-0.55 mol/100 g.
4. The high modulus high toughness epoxy structural adhesive according to claim 2 or 3, wherein said epoxy resin is selected from more than one of bisphenol A epoxy resin E51, bisphenol A epoxy resin E55, bisphenol F epoxy resin F44, bisphenol F epoxy resin F51, bisphenol F epoxy resin F55.
5. The high modulus high toughness epoxy structural adhesive according to claim 1, wherein said amino polysilsesquioxane T6 structure, T6 amino POSS, has the following formula (i):
Figure FDA0003468555890000021
the structure of the amino polysilsesquioxane T8, namely the structural formula of the T8 amino POSS is shown as the following formula (II):
Figure FDA0003468555890000022
r in the structures of T6 amino POSS and T8 amino POSS is gamma-CH2CH2CH2NH2。
6. The high modulus high toughness epoxy structural adhesive according to claim 5, wherein said epoxy grafted POSS is prepared by the following specific method: dissolving amino POSS powder in toluene, wherein the dosage of the toluene solvent is 2-3 times of the total mass of the amino POSS and the bifunctional epoxy diluent, and heating to 60 +/-5 ℃; and after the amino POSS is completely dissolved, adding the metered bifunctional epoxy diluent into a toluene solution of the amino POSS at one time, heating to 80 +/-5 ℃, stirring for reacting for 3-8 h, grafting the bifunctional epoxy diluent to the end group of the amino POSS in an open-loop manner to form epoxy grafted POSS, and removing the toluene solvent in the epoxy grafted POSS at 100 +/-5 ℃ in vacuum to obtain the viscous epoxy grafted POSS.
7. The high modulus high toughness epoxy structural adhesive according to claim 6, wherein said epoxy grafted POSS has a structure represented by formula (III) or (IV):
Figure FDA0003468555890000031
wherein R is1The groups are as follows:
Figure FDA0003468555890000032
wherein R is2Is C2-C6 alkyl.
8. The high modulus high toughness epoxy structural adhesive according to claim 1, wherein said defoamer is a humble 6800 oily system silicone defoamer or a BYK061 modified silicone defoamer;
the wetting dispersant is a moderate chemical 9250 or 983 wetting dispersant;
the thixotropic agent is fumed nano silicon dioxide of Yingchuangdegussa A150, A200, A300 or A380.
9. The high modulus high toughness epoxy structural adhesive according to claim 1, wherein the fine aggregate is one or a mixture of more than one of 200-800 mesh quartz powder.
10. The high modulus high toughness epoxy structural adhesive according to claim 1, wherein said polyamine curing agent is selected from any one or more of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, isophorone diamine, 1, 3-cyclohexyldimethylamine, commercially available Nanjing forestry chemical research institute 401 curing agent;
the tertiary amine accelerator is 2,4, 6-tri (dimethylamino) phenol or 1, 8-diazabicycloundec-7-ene.
11. The method for preparing an epoxy structural adhesive according to any one of claims 1 to 10, comprising the following steps:
(1) pre-reacting a bifunctional epoxy reactive diluent and amino POSS in a toluene solution at 80 +/-5 ℃ for 3-8 h, and removing the toluene solvent in vacuum at 100 +/-5 ℃ to obtain viscous epoxy grafted POSS;
(2) mixing epoxy resin, epoxy diluent, epoxy grafted POSS, wetting dispersant, defoaming agent and thixotropic agent in proportion, and dispersing at a high speed by using a high-speed dispersion machine, wherein the dispersion speed is 800-2000 r/min, the dispersion temperature is controlled at 20-40 ℃, and the dispersion time is 30-60 min to obtain a resin premix;
(3) adding fine aggregate into the resin premix prepared in the step (2) according to a set amount, heating the materials to 40-60 ℃, continuously and uniformly dispersing and stirring at a high speed, controlling the dispersion speed to be 800-1500 r/min, and dispersing for 20-40 min to obtain a component A;
(4) mixing a curing agent and a curing accelerator in proportion to obtain a component B;
(5) when in use, the A, B components are mixed and stirred evenly according to the proportion.
12. The application method of the epoxy structural adhesive as claimed in any one of claims 1 to 10, wherein the epoxy structural adhesive is applied to a concrete prefabricated part splicing adhesive, a steel bar planting anchoring adhesive or a steel bonding adhesive.
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