An epoxy two-component adhesive, its preparation method and application

Abstract

The present invention belongs to the technical field of adhesives, and discloses an epoxy two-component adhesive, a preparation method and an application thereof. The adhesive comprises component A and component B; Component A comprises the following components: epoxy resin, environmentally friendly reactive diluent, functional filler, modified calcium carbonate, first other filler, thixotropic agent; Component B comprises the following components: self-made modified amine curing agent, accelerator, modified calcium carbonate, second other filler. The adhesive of the present invention is used as a rock slab adhesive, solves the problems of poor water resistance and yellowing resistance of the rock slab adhesive, and improves the environmental friendliness of the rock slab adhesive.

Description

Technical Field

[0001] The present invention belongs to the technical field of adhesives, and more specifically, relates to an epoxy two-component adhesive, a preparation method and an application thereof. Background Art

[0002] In recent years, "sintered stone" has frequently appeared in people's vision. The English name of sintered stone is "SINTERED STONE", which is translated as "sintered dense stone". It is made of natural stone materials and inorganic clay through a special process, formed by vacuum extrusion molding and fired in an automatic closed computer-controlled roller hearth kiln at 1300°. It has the characteristics of high strength, low water absorption, lightness, large size, good decorative effect, etc., and has become a new material to replace some traditional decorative materials such as stone, glass, wallpaper, aluminum plate, ceramic plate, etc. Compared with traditional ceramic tiles, sintered stone has outstanding ductility, and large-size paving can effectively reduce the generation of gaps. Therefore, it is widely used in the home furnishing field such as background walls, kitchen and bathroom cabinets, coffee tables and dining tables, wash basins, etc., and even in the curtain walls of public spaces and interior home decoration paving. Thus, sintered stone glue, as an auxiliary bonding material for sintered stone, has emerged as the times require.

[0003] At present, most of the commercially available sintered stone glues are of unsaturated polyester resin, acrylic system and even polyurethane system, which have obvious strong pungent odors, seriously affecting the health of construction workers and the construction environment. At the same time, the cured products of unsaturated polyester resin and acrylic system sintered stone glues have poor strength and low adhesion, and the processed finished products are easy to loosen and fall off. Although the polyurethane system sintered stone glue has high initial bonding strength, its aging resistance, especially its water resistance, is poor, and quality problems are likely to occur when used in a humid environment, resulting in the falling of sintered stone and the yellowing and blackening of the glued parts.

[0004] At present, benzene methanol and glycidyl ether solvents are generally used as diluents in the epoxy two-component adhesives on the market. As a non-reactive diluent, benzene methanol does not participate in the cross-linking reaction and will eventually slowly migrate to the surface of the adhesive to emit, reducing the bonding strength; although glycidyl ether diluents have polymerization activity, they are highly toxic and have obvious odors, which is not conducive to the health of construction workers and environmental protection requirements.

[0005] Therefore, there is an urgent need to propose a new epoxy two-component adhesive, a preparation method and an application thereof Summary of the Invention

[0006] The object of the present invention is to overcome the deficiencies of the prior art and propose an epoxy two-component adhesive, a preparation method and an application thereof. The adhesive of the present invention is used as sintered stone glue, which solves the problems of poor water resistance and yellowing resistance of sintered stone glue and improves the environmental protection of sintered stone glue.

[0007] To achieve the above object, in the first aspect of the present invention, an epoxy two-component adhesive is provided, which includes component A and component B;

[0008] The component A includes the following components:

[0009] Epoxy resin;

[0010] Environmentally friendly active diluent;

[0011] Functional filler;

[0012] Modified calcium carbonate;

[0013] First other filler;

[0014] Thixotropic agent;

[0015] The component B includes the following components:

[0016] Self-made modified amine curing agent;

[0017] Accelerator;

[0018] Modified calcium carbonate;

[0019] Second other filler.

[0020] According to the present invention, preferably,

[0021] The component A includes the following components by weight:

[0022] 30 - 45 parts of epoxy resin;

[0023] 1 - 10 parts of environmentally friendly active diluent;

[0024] 1 - 5 parts of functional filler;

[0025] 30 - 50 parts of modified calcium carbonate;

[0026] 10 - 30 parts of first other filler;

[0027] 1 - 5 parts of thixotropic agent;

[0028] The component B includes the following components by weight:

[0029] 25 - 35 parts of self-made modified amine curing agent;

[0030] 5 - 10 parts of accelerator;

[0031] 45 - 60 parts of modified calcium carbonate;

[0032] 10 - 30 parts of second other filler.

[0033] According to the present invention, preferably,

[0034] The component A includes the following components by weight:

[0035] 35 - 40 parts of epoxy resin;

[0036] 5 - 10 parts of environmentally friendly reactive diluent;

[0037] 3 - 5 parts of functional filler;

[0038] 40 - 50 parts of modified calcium carbonate;

[0039] 10 - 30 parts of the first other filler;

[0040] 3 - 5 parts of thixotropic agent;

[0041] The component B includes the following components in parts by weight:

[0042] 25 - 30 parts of self - made modified amine curing agent;

[0043] 5 - 10 parts of accelerator;

[0044] 45 - 55 parts of modified calcium carbonate;

[0045] 10 - 30 parts of the second other filler.

[0046] According to the present invention, preferably, the epoxy resin is bisphenol A epoxy resin and / or bisphenol F epoxy resin.

[0047] According to the present invention, preferably, the environmentally friendly reactive diluent is propylene carbonate and / or ethylene carbonate.

[0048] According to the present invention, preferably, the functional filler is calcium carbonate whisker with a particle size of 375 - 500 mesh.

[0049] According to the present invention, preferably, the thixotropic agent is nano - calcium carbonate.

[0050] According to the present invention, preferably, the first other filler is at least one of heavy calcium, barium sulfate and silica powder.

[0051] According to the present invention, preferably, the self - made modified amine curing agent is prepared by ring - opening addition reaction of terminal amino polyether, isophorone diamine, 1,3 - cyclohexanedimethylamine and hydrogenated epoxy resin under the conditions of reactive diluent, dispersant and accelerator.

[0052] According to the present invention, preferably, the accelerator is aminoethyl piperazine and / or epoxy phosphate.

[0053] According to the present invention, preferably, the second other filler is at least one of heavy calcium, barium sulfate and silica powder.

[0054] According to the present invention, preferably, the preparation method of the self - made modified amine curing agent includes the following steps:

[0055] (1) Mix the terminal amino polyether, isophorone diamine, partially hydrogenated epoxy resin, and 1,3-cyclohexanedimethanamine evenly by stirring to obtain a first product;

[0056] (2) Mix the first product, the remaining partially hydrogenated epoxy resin, active diluent, dispersant, and accelerator evenly by stirring to obtain the self-made modified amine curing agent.

[0057] According to the present invention, preferably, the weight parts of the raw materials for preparing the self-made modified amine curing agent are as follows: 10-20 parts of terminal amino polyether, 5-15 parts of isophorone diamine, 10-20 parts of 1,3-cyclohexanedimethanamine, 15-25 parts of hydrogenated epoxy resin, 25-30 parts of active diluent, 1-5 parts of dispersant, and 1-10 parts of accelerator.

[0058] According to the present invention, preferably, the type of the active diluent is at least one of AGE, benzyl glycidyl ether, and 1,4-butanediol diglycidyl ether.

[0059] According to the present invention, preferably, the dispersant is ammonium polycarboxylate and / or a polymer type block copolymer containing a pigment affinity group.

[0060] According to the present invention, preferably, the accelerator is p-toluenesulfonic acid and / or salicylic acid.

[0061] According to the present invention, preferably,

[0062] The dosage ratio of the hydrogenated epoxy resin to isophorone diamine in step (1) is 1:(0.8-1.2);

[0063] The dosage ratio of the hydrogenated epoxy resin to 1,3-cyclohexanedimethanamine in step (2) is 1:(1-3).

[0064] According to the present invention, preferably, the temperature of the mixing and stirring is 40-90 °C, and the time is 1-4 h.

[0065] In the present invention, as a preferred embodiment, the preparation method of the self-made modified amine curing agent includes the following steps: Mix the terminal amino polyether and isophorone diamine, add the partially hydrogenated epoxy resin in a dropwise manner, stir and control the temperature at 50-70 °C, add 1,3-cyclohexanedimethanamine under continuous stirring, and mix evenly to obtain a first product; Mix the first product, the remaining partially hydrogenated epoxy resin, active diluent, dispersant, and accelerator, mix and stir evenly and raise the reaction temperature to 70-80 °C, stir for 1-3 hours, and discharge under vacuum to obtain the self-made modified amine curing agent.

[0066] According to the present invention, preferably, the dosage ratio of component A to component B is 1:(0.8-1.2).

[0067] The second aspect of the present invention provides a preparation method of the epoxy two - component adhesive, and the preparation method includes the following steps:

[0068] S1: Stir and disperse the epoxy resin, environmentally friendly active diluent, thixotropic agent, functional filler, modified calcium, and other fillers evenly to obtain the component A;

[0069] S2: Stir and disperse the self - made modified amine curing agent, accelerator, modified calcium, and other fillers evenly to obtain the component B.

[0070] The third aspect of the present invention provides an application of the epoxy two - component adhesive in laying rock slabs and / or installing integrated basins.

[0071] The beneficial effects of the technical solution of the present invention are as follows:

[0072] (1) The epoxy two - component adhesive prepared by the present invention has low odor, low VOC, high environmental protection compared with commercially available rock slab adhesive products, and has good water resistance and yellowing resistance, high bonding strength, and can effectively solve problems such as obvious volume shrinkage and poor bonding of existing rock slab adhesive products, and thus problems such as rock slab falling off.

[0073] (2) The present invention abandons the selection of traditional epoxy diluents, adopts a solvent - free system, and selects the new generation of environmentally friendly "semi - active" diluent propylene carbonate with high boiling point, which is non - toxic, colorless, odorless, has strong dilution ability, can replace traditional glycidyl ether - type diluents such as 501, 692, 748, etc., and the C = O bond it contains can undergo ring - opening cross - linking reaction with - NH2, increasing the cross - linking density. The formed polyether carbonate polyol can precipitate to form a dispersed phase during the resin curing process, showing good strengthening and toughening effects, making the cured product rigid - flexible; at the same time, this substance also has polarity, can better wet inorganic fillers, and disperse them into the adhesive system, thereby improving the wetting and ductility of the adhesive on the surface of the rock slab.

[0074] (3) The curing agent used in the component B of the present invention is a self - made cycloaliphatic amine curing agent without benzyl alcohol system, which minimizes the VOC of the product, improves the environmental protection performance of the product, and reduces the harm to the human body.

[0075] (4) The present invention uses two accelerators without color - changing groups, aminoethyl piperazine and epoxy phosphate, in combination with the curing agent in the component B, which not only makes the product have good yellowing resistance, but also has a low reaction curing shrinkage rate, better adhesion and reaction activity, effectively improving the water resistance and bonding strength of the adhesive layer.

[0076] Other features and advantages of the present invention will be described in detail in the following specific implementation section. Specific implementation mode

[0077] The preferred embodiments of the present invention will be described in more detail below. Although the preferred embodiments of the present invention are described below, it should be understood that the present invention can be implemented in various forms and should not be limited by the embodiments set forth herein. On the contrary, these embodiments are provided to make the present invention more thorough and complete, and to fully convey the scope of the present invention to those skilled in the art.

[0078] In the following examples:

[0079] The preparation method of the self-made modified amine curing agent includes the following steps: Mix the terminal amino polyether and isophorone diamine, and add part of the hydrogenated epoxy resin dropwise (the dosage ratio of the hydrogenated epoxy resin to isophorone diamine is 1:1), stir and control the temperature at 65 °C, and add 1,3-cyclohexanedimethanamine under continuous stirring, mix evenly to obtain the first product; Mix the first product, the remaining part of the hydrogenated epoxy resin (the dosage ratio of the hydrogenated epoxy resin to 1,3-cyclohexanedimethanamine is 1:1), AGE, ammonium polycarboxylate and p-toluenesulfonic acid, mix and stir evenly and raise the reaction temperature to 75 °C, stir for 2 hours, evacuate and discharge to obtain the self-made modified amine curing agent.

[0080] The weight parts of the raw materials for preparing the self-made modified amine curing agent are: 15 parts of terminal amino polyether, 10 parts of isophorone diamine, 15 parts of 1,3-cyclohexanedimethanamine, 25 parts of hydrogenated epoxy resin, 27 parts of AGE, 3 parts of ammonium polycarboxylate and 5 parts of toluenesulfonic acid.

[0081] Examples 1-4 respectively provide an epoxy two-component adhesive, and the adhesive formulation is shown in Table 1.

[0082] Table 1

[0083]

[0084] Test Example

[0085] This test example tests the epoxy two-component adhesives prepared in Examples 1-4.

[0086] The test methods include:

[0087] The method for evaluating the odor level refers to: HGT 4065-2008 / Method for Evaluating the Odor of Adhesives;

[0088] The method for determining the total volatile organic compounds refers to: GB 18583-2008, bulk adhesives;

[0089] The yellowing property refers to: GB / T 39294-2020;

[0090] The bonding strength test and freeze-thaw cycle test under different conditions refer to: JC 887-2001.

[0091] The test results are shown in Table 2. As can be seen from Table 2, compared with the comparative example, the epoxy two-component adhesives prepared in Examples 1-4 have obvious advantages such as low odor, low VOC, and high environmental protection, and at the same time, the bonding strength, water resistance, and yellowing resistance of the products are better. The comparative example is a commercially available rock slab adhesive product.

[0092] Table 2

[0093]

[0094] As can be seen from Table 2, in terms of product use and cost performance, Example 1 can already meet the application requirements. However, since bisphenol F epoxy resin is not added to Component A, there may be a risk of crystallization when used at low temperatures. The best Example 4 added 5 parts of bisphenol F epoxy resin on the basis of Example 1, which not only reduced the overall viscosity of the resin, but also reduced the risk of crystallization of the product when used at low temperatures, and the overall performance was also improved. The best Example 4 showed good performance in the immersion and freeze-thaw cycle tests, with a low performance loss rate, which was sufficient to meet the use requirements in a humid environment.

[0095] The embodiments of the present invention have been described above. The above description is exemplary and not exhaustive, and is not limited to the disclosed embodiments. Many modifications and changes are obvious to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.

Claims

1. Application of epoxy two-component adhesive in laying of rock slabs and / or installation of integrated basins, characterized in that, The epoxy two-component adhesive comprises Component A and Component B; Component A comprises the following components: Epoxy resin; Environmentally friendly active diluent; the environmentally friendly active diluent is propylene carbonate and / or ethylene carbonate; Functional filler; The functional filler is calcium carbonate whiskers with a particle size of 375 - 500 mesh; Modified calcium carbonate; First other filler; Thixotropic agent; Component B comprises the following components: Self-made modified amine curing agent; The self-made modified amine curing agent is prepared by ring-opening addition reaction of terminal amino polyether, isophorone diamine, 1,3-cyclohexanediamine and hydrogenated epoxy resin under the conditions of active diluent, dispersant and first accelerator; Second accelerator; Modified calcium carbonate; Second other filler; The second accelerator is aminoethyl piperazine and / or epoxy phosphate.

2. According to the application described in claim 1, wherein, Component A comprises the following components by weight: 30 - 45 parts of epoxy resin; 1 - 10 parts of environmentally friendly active diluent; 1 - 5 parts of functional filler; 30 - 50 parts of modified calcium carbonate; 10 - 30 parts of first other filler; 1 - 5 parts of thixotropic agent; Component B comprises the following components by weight: 25 - 35 parts of self-made modified amine curing agent; 5 - 10 parts of second accelerator; 45 - 60 parts of modified calcium carbonate; 10 - 30 parts of second other filler.

3. According to the application described in claim 2, wherein, Component A comprises the following components by weight: 35 - 40 parts of epoxy resin; 5 - 10 parts of environmentally friendly active diluent; 3 - 5 parts of functional filler; 40 - 50 parts of modified calcium carbonate; 10 - 30 parts of first other filler; 3 - 5 parts of thixotropic agent; Component B comprises the following components by weight: 25 - 30 parts of self-made modified amine curing agent; 5 - 10 parts of second accelerator; 45 - 55 parts of modified calcium carbonate; 10 - 30 parts of second other filler.

4. According to the application described in claim 1, wherein, The epoxy resin is bisphenol A epoxy resin and / or bisphenol F epoxy resin; The thixotropic agent is nano calcium carbonate; The first other filler is at least one of heavy calcium, barium sulfate and silica powder.

5. According to the application described in claim 1, wherein, The second other filler is at least one of heavy calcium, barium sulfate and silica powder.

6. The application according to claim 5, wherein The preparation method of the self-made modified amine curing agent comprises the following steps: (1) Mix the terminal amino polyether, isophorone diamine, partial hydrogenated epoxy resin and 1,3-cyclohexanediamine and stir evenly to obtain a first product; (2) Mix the first product, the remaining part of hydrogenated epoxy resin, active diluent, dispersant and first accelerator and stir evenly to obtain the self-made modified amine curing agent.

7. According to the application described in claim 6, wherein, The weight parts of the raw materials for preparing the self-made modified amine curing agent are: 10 - 20 parts of terminal amino polyether, 5 - 15 parts of isophorone diamine, 10 - 20 parts of 1,3-cyclohexanediamine, 15 - 25 parts of hydrogenated epoxy resin, 25 - 30 parts of active diluent, 1 - 5 parts of dispersant and 1 - 10 parts of first accelerator; The type of the active diluent is at least one of AGE, benzyl glycidyl ether and 1,4-butanediol diglycidyl ether; The dispersant is an ammonium polycarboxylate salt and / or a polymer block copolymer containing a pigment affinity group; The first accelerator is p-toluenesulfonic acid and / or salicylic acid; The dosage ratio of the hydrogenated epoxy resin to isophorone diamine in step (1) is 1:(0.8 - 1.2); The dosage ratio of the hydrogenated epoxy resin to 1,3-cyclohexanedimethanamine in step (2) is 1:(1 - 3); The temperature of the mixing and stirring is 40 - 90 °C, and the time is 1 - 4 h.

8. The application according to claim 1, wherein The dosage ratio of the A component to the B component is 1:(0.8 - 1.2).

9. The application according to any one of claims 1-8, wherein The preparation method of the epoxy two-component adhesive comprises the following steps: S1: Stir and disperse the epoxy resin, the environmentally friendly active diluent, the thixotropic agent, the functional filler, the modified calcium and other fillers uniformly to obtain the A component; S2: Stir and disperse the self-made modified amine curing agent, the second accelerator, the modified calcium and other fillers uniformly to obtain the B component.

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