Epoxy resin waterproof adhesive layer and preparation method thereof

Abstract

The invention relates to an epoxy resin waterproof adhesive layer and a preparation method thereof. An epoxy resin monomer and an amine curing agent are used as film forming matters, a dearomatization solvent is used as a dispersing agent, and the dearomatization solvent is at least one of SK410 and SK410B or a mixture of the SK410 and the SK410B or a mixture of at least one of the SK410 and the SK410B and acetone; the moisture absorption rate is adjusted by adjusting the solid content of the waterproof glue solution; the waterproof adhesive layer is low in raw material cost, simple in preparation process, capable of adjusting curing conditions according to specific production conditions, high in maneuverability, capable of effectively reducing the moisture absorption rate after acting on a base material, capable of achieving the moisture absorption rate inhibiting effect of 60%, suitable for surface waterproof operation treatment of composite material products in various fields such as aircrafts and the like, and capable of achieving the waterproof effect after acting on the surface of a heat-proof composite material. The environment storage stability is improved.

Description

TECHNICAL FIELD

[0001] The present application relates to a waterproof adhesive layer, in particular to an epoxy resin waterproof adhesive layer and a preparation method thereof, and belongs to the technical field of composite materials and processes. BACKGROUND

[0002] Fiber-reinforced phenolic resin-based composite materials have been widely used due to their good heat insulation performance, high strength and modulus mechanical properties, corrosion resistance and other advantages. The main forming manufacturing processes of fiber-reinforced phenolic resin-based materials include laying forming, winding forming and mold pressing, and at present, all fiber-reinforced phenolic resin-based composite products have the need for surface waterproof treatment. A suitable waterproof adhesive layer can be used to fill the small gaps on the surface of the product, increase its moisture resistance, corrosion resistance, aging resistance and corrosion resistance, prolong the storage period, and inhibit the shrinkage deformation caused by internal stress of the product.

[0003] Epoxy resin can form a three-dimensional network structure after the monomer and the curing agent are reacted, and has the advantages of high bonding strength, excellent chemical stability, low shrinkage, strong waterproofness, no environmental pollution and the like. It has strong bonding ability for various polar materials represented by composite materials and has been widely used in the waterproof field. At present, the epoxy resin waterproof system has mature cases in the fields of building, bridge and road. It is used for waterproof ground, bridge concrete anti-seepage, etc. The common commercial epoxy resin has a large viscosity, and before its application, a proper amount of diluent needs to be added to adjust the viscosity of the epoxy resin to a suitable value, and then it can be used for surface waterproof treatment of resin-based composite materials. The commonly used solvent system is a furfural-acetone dilution system or a modified aldehyde-acetone dilution system, and the aldehyde and ketone involved in the system have high toxicity and strong irritation.

[0004] In recent years, researchers have made corresponding harmless attempts, and the common directions are as follows: preparation of high solid content epoxy resin, water-based modification of epoxy resin and solvent replacement. Among them, the high solid content epoxy resin waterproof glue system has high solid content, and the viscosity is above 300 mPa·s, which has high requirements for waterproof construction process, and the thickness uniformity needs to be controlled by mechanical equipment or to increase the polishing post-processing process, and usually needs to use heating equipment to shorten the curing time to prevent the glue from flowing again under the action of gravity, which is suitable for preparing millimeter thick glue film, and is not suitable for surface waterproof treatment of fabric reinforced resin matrix composite products with relatively rough surface; the hydrophilic modification of the epoxy resin matrix has high investment cost, and the waterproof performance of the cured product of the hydrophilic modified epoxy resin is not as good as that of the traditional epoxy resin; the amount of surfactant is not less than 10% of the amount of resin, and finally remains on the surface of the heat-proof product, which has unknown influence on the heat-proof function; and the water-soluble waterproof glue system needs to be dispersed by high-speed mechanical stirring device during preparation process, and needs to be heated above 80 DEG C for 4-5 hours in an oven during curing process, which causes additional occupation of equipment resources. Therefore, the key to developing the waterproof glue layer system for the surface of the heat-proof functional composite material is to find a suitable fast-drying solvent to prepare a waterproof glue system with low viscosity, fast curing speed and mild curing conditions. SUMMARY

[0005] The technical problem solved by the present application is to provide an epoxy resin waterproof glue layer and a preparation method thereof. The epoxy resin waterproof glue layer uses a de-aromatic solvent as a dispersant, and through optimization of components and proportions, the moisture absorption rate of the waterproof glue layer after acting on the base material can be effectively reduced, the preparation process is simple, and the waterproof glue layer can be cured at room temperature. The waterproof glue layer can be used on the surface of an aircraft heat-proof composite material to improve the environmental storage stability, and has potential wide application prospects in the civil field.

[0006] The technical scheme adopted by the present application is as follows:

[0007] A preparation method of an epoxy resin waterproof glue layer, comprising the following steps:

[0008] stirring and mixing bisphenol A type epoxy resin monomer, amine curing agent and de-aromatic solvent to form a waterproof glue solution;

[0009] coating the waterproof glue solution on the surface of the base material, and curing at room temperature or under heating conditions to obtain a waterproof glue layer;

[0010] The de-aromatic solvent is at least one of SK410 and SK410B or a mixture of the two, or a mixture of at least one of SK410 and SK410B and acetone;

[0011] The amine curing agent required is: (amine equivalent / epoxy equivalent) ±5, based on 100 parts by mass of the bisphenol A type epoxy resin monomer;

[0012] The de-aromatic solvent required is: 150-400 parts by mass, based on 100 parts by mass of the bisphenol A type epoxy resin monomer.

[0013] In the method for preparing the epoxy resin waterproof adhesive layer described above, the curing time at room temperature is ≥24 h.

[0014] In the method for preparing the epoxy resin waterproof adhesive layer described above, the curing under heating conditions comprises: curing at 60-100 ℃ for 1-3 h.

[0015] In the method for preparing the epoxy resin waterproof adhesive layer described above, the coating method for applying the waterproof adhesive liquid to the surface of the substrate comprises: using rubbing, scraping, brushing or spraying.

[0016] In the method for preparing the epoxy resin waterproof adhesive layer described above, the bisphenol A type epoxy resin monomer is one or a combination of WSR618, E51 or E44.

[0017] In the method for preparing the epoxy resin waterproof adhesive layer described above, the epoxy equivalent of the bisphenol A type epoxy resin monomer is ≤270 g / mol.

[0018] In the method for preparing the epoxy resin waterproof adhesive layer described above, the amine curing agent is one or a combination of tetraethylenepentamine, dihexyltriamine or m-xylylenediamine.

[0019] In the method for preparing the epoxy resin waterproof adhesive layer described above, the single forming thickness of the waterproof adhesive layer prepared is less than 10 microns.

[0020] An epoxy resin waterproof adhesive layer is prepared by using the method described above.

[0021] Compared with the prior art, the present application at least has the following beneficial effects:

[0022] (1), the present application provides an epoxy resin waterproof adhesive layer and a preparation method thereof, the waterproof adhesive layer uses epoxy resin monomer and amine curing agent as film-forming material, and uses special de-aromatic solvent as dispersant, the de-aromatic solvent is at least one of SK410 and SK410B or a mixture of the two, or a mixture of at least one of SK410 and SK410B and acetone; by adjusting the solid content of the waterproof adhesive liquid, the moisture absorption rate is adjusted; room temperature curing or heating curing process can be selected according to actual needs, the moisture absorption rate of the resin-based composite material substrate after the surface preparation waterproof adhesive layer can be reduced by more than 20%, and at the same time, it will not have negative effects on its basic functions.

[0023] (2) The raw materials for the waterproof adhesive layer prepared in the embodiment of the present invention are low in cost and easy to obtain, and the preparation is simple and fast. The curing conditions can be adjusted according to the specific production conditions, and the flexibility is strong. It is suitable for surface waterproofing of composite materials products in various fields.

[0024] (3) The epoxy resin waterproof adhesive layer in the embodiment of the present invention, which uses a dearomatized hydrocarbon solvent of a special component as a dispersant, has a simple preparation process and can be cured at room temperature. After acting on the substrate, it can effectively reduce the moisture absorption rate, and the moisture absorption rate inhibition effect can reach 60%. It can be used on the surface of aircraft heat-resistant composite materials to improve its environmental storage stability. At the same time, it has potential for broad application prospects in the civilian field. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 This is a flow chart of the method for preparing the epoxy resin waterproof adhesive layer of the present invention;

[0026] Figure 2 This is a photograph of the curing process of the waterproof adhesive layer on the surface of the high-silica / phenolic substrate in Example 3 of the present invention;

[0027] Figure 3 This is the surface energy spectrum of the waterproof adhesive layer in Example 3 of the present invention. DETAILED DESCRIPTION

[0028] The present invention will be described in further detail below with reference to the accompanying drawings and specific embodiments:

[0029] The invention provides an epoxy resin waterproof adhesive layer using a dearomatized hydrocarbon solvent as a dispersant, wherein the film-forming material is a bisphenol A epoxy resin monomer and an amine curing agent, and the process diluent is a dearomatized hydrocarbon solvent.

[0030] like Figure 1 As shown, the method for preparing an epoxy resin waterproof adhesive layer using a dearomatized hydrocarbon solvent as a dispersant of the present invention comprises the following steps:

[0031] 1. Stir and mix bisphenol A epoxy resin monomer, amine curing agent and dearomatized solvent to form a waterproof glue;

[0032] In the embodiment of the present invention,

[0033] The epoxy equivalent of the bisphenol A epoxy resin monomer is ≤270 g / mol, and the specific bisphenol A epoxy resin monomer is one or a combination of WSR618, E51 or E44.

[0034] The amine curing agent is one or a combination of tetraethylenepentamine, dihexyltriamine or meta-xylenediamine.

[0035] The de-aromatic solvent is at least one of SK410, SK410B or a mixture of the two, or a mixture of at least one of SK410, SK410B and acetone. The SK410 and SK410B are commercially available cleaning agents from Huaxing New Materials Co., Ltd.

[0036] The amine curing agent is used in an amount of (amine equivalent / epoxy equivalent) ± 5 parts by mass per 100 parts by mass of the bisphenol A type epoxy resin monomer.

[0037] The de-aromatic solvent is used in an amount of 150-400 parts by mass per 100 parts by mass of the bisphenol A type epoxy resin monomer.

[0038] 2. A waterproof adhesive layer is prepared on the surface of the substrate by manual rubbing / coating or automatic brushing / spraying.

[0039] 3. The waterproof adhesive layer is obtained by curing at room temperature for ≥24 h or by heating at 60-100 °C for 1-3 h.

[0040] The single-molding thickness of the prepared epoxy resin waterproof adhesive layer is less than 10 microns.

[0041] The moisture absorption inhibition of the prepared epoxy resin waterproof adhesive layer can reach 60%.

[0042] Example 1

[0043] First, an epoxy resin waterproof adhesive solution with a de-aromatic solvent as a dispersant is prepared with the following raw material ratio: 20 g of bisphenol A type epoxy resin monomer, 3 g of tetraethylenepentamine, and 50 g of SK410B, which are fully stirred and mixed uniformly.

[0044] Then, the surface is treated by manual rubbing process until the required thickness range of the waterproof adhesive layer is met.

[0045] Finally, the coating is cured at room temperature for ≥24 h.

[0046] The water absorption rate of the high-silica / phenolic substrate treated by this method is 0.17%, while the water absorption rate of the high-silica / phenolic substrate without the waterproof adhesive layer is 0.30%. The moisture absorption inhibition rate of the adhesive layer to the substrate in this example is 43%.

[0047] Example 2

[0048] First, an epoxy resin waterproof adhesive solution with a de-aromatic solvent as a dispersant is prepared with the following raw material ratio: 20 g of bisphenol A type epoxy resin monomer, 3 g of tetraethylenepentamine, and 60 g of SK410B, which are fully stirred and mixed uniformly.

[0049] Then, the surface is treated by manual rubbing process until the required thickness range of the waterproof adhesive layer is met.

[0050] Finally, the coating is cured at room temperature for > 24 h.

[0051] The water absorption of the high-silica / phenolic substrate treated by this method is 0.12%, and the moisture absorption inhibition rate reaches 60%.

[0052] Example 3

[0053] First, the epoxy resin waterproof glue solution with a de-aromatic solvent as a dispersant, the raw material ratio is: bisphenol A type epoxy resin monomer 20 g, tetraethylene pentamine 3 g, SK410 70 g, fully stirred and mixed uniformly.

[0054] Then, the surface treatment is carried out by artificial rubbing coating process until the required thickness range of the waterproof glue layer is met.

[0055] Finally, the coating is cured at room temperature for > 24 h.

[0056] The water absorption of the high-silica / phenolic substrate treated by this method is 0.15%, and the moisture absorption inhibition rate reaches 50%.

[0057] As shown in Figure 2 the curing process photos of the waterproof glue layer on the surface of the high-silica / phenolic substrate at 0 h, 12 h, 24 h, and 36 h in this embodiment.

[0058] As shown in Figure 3 the surface energy spectrum of the waterproof glue layer in this embodiment.

[0059] Example 4

[0060] First, the epoxy resin waterproof glue solution with a de-aromatic solvent as a dispersant, the raw material ratio is: bisphenol A type epoxy resin monomer 20 g, tetraethylene pentamine 3 g, SK410B 45 g, SK410 15 g, fully stirred and mixed uniformly.

[0061] Then, the surface treatment is carried out by automatic spraying process until the required thickness range of the waterproof glue layer is met.

[0062] Finally, the coating is heated and cured in an oven at 60°C for 2.5 h.

[0063] The water absorption of the high-silica / phenolic substrate treated by this method is 0.14%, and the moisture absorption inhibition rate reaches 53%.

[0064] Example 5

[0065] First, the epoxy resin waterproof glue solution with a de-aromatic solvent as a dispersant, the raw material ratio is: epoxy resin E51 monomer 20 g, m-xylylenediamine 3.5 g, SK410B 30 g, SK410 40 g, acetone 10 g, fully stirred and mixed uniformly.

[0066] Then, the surface treatment is carried out by artificial rubbing coating process until the required thickness range of waterproof adhesive layer is met.

[0067] Finally, the coating is cured at room temperature for ≥24h.

[0068] The water absorption rate of the high-silica / phenolic substrate treated by the method is 0.18%, and the moisture absorption inhibition rate reaches 40%.

[0069] Example 6

[0070] First, the epoxy waterproof adhesive solution with a de-aromatic solvent as a dispersant has the following raw material ratio: 20g of epoxy resin E44 monomer, 4g of dihexyl triamine, 30g of SK410, and 12g of acetone, which are fully stirred and mixed uniformly.

[0071] Then, the surface treatment is carried out by artificial rubbing coating process until the required thickness range of waterproof adhesive layer is met.

[0072] Finally, the coating is cured at room temperature for ≥24h.

[0073] The water absorption rate of the high-silica / phenolic substrate treated by the method is 0.15%, and the moisture absorption inhibition rate reaches 50%.

[0074] Comparative Example 1

[0075] First, the epoxy waterproof adhesive solution with a de-aromatic solvent as a dispersant has the following raw material ratio: 20g of bisphenol A type epoxy resin monomer, 3g of tetraethylene pentamine, and 50g of acetone, which are fully stirred and mixed uniformly.

[0076] Then, the surface treatment is carried out by artificial rubbing coating process until the required thickness range of waterproof adhesive layer is met.

[0077] Finally, the coating is cured at room temperature for ≥24h.

[0078] The water absorption rate of the high-silica / phenolic substrate treated by the method is 0.24%, and the moisture absorption inhibition rate reaches 20%.

[0079] In this example, only acetone is used as a solvent, which significantly reduces the moisture absorption inhibition rate.

[0080] The above description is only the best specific embodiment of the present application, but the protection scope of the present application is not limited to this. Any changes or replacements that can be easily thought of by those skilled in the art within the technical range disclosed by the present application should be covered in the protection scope of the present application.

[0081] The contents not described in detail in the specification of the present application are the known technology of the skilled in the art.

Claims

1. A method for preparing an epoxy resin waterproof adhesive layer, characterized in that: The steps include: Stir and mix bisphenol A epoxy resin monomer, amine curing agent and dearomatized solvent to form waterproof glue; The waterproof adhesive is applied to the surface of the substrate and cured at room temperature or under heating conditions to obtain a waterproof adhesive layer; The dearomatized solvent is at least one of SK410 and SK410B or a mixture of the two, or a mixture of at least one of SK410 and SK410B and acetone; Based on 100 parts by mass of bisphenol A epoxy resin monomer, the mass parts of the required amine curing agent are: (amine equivalent / epoxy equivalent) ± 5; Based on 100 parts by mass of the bisphenol A epoxy resin monomer, the required parts by mass of the dearomatized solvent is 150-400.

2. The method for preparing the epoxy resin waterproof adhesive layer according to claim 1, wherein: The curing time of curing at room temperature is ≥24h.

3. The method for preparing the epoxy resin waterproof adhesive layer according to claim 1, wherein: The curing under the heating condition includes curing at 60-100° C. for 1-3 hours.

4. The method for preparing the epoxy resin waterproof adhesive layer according to claim 1, wherein: The waterproof adhesive solution may be applied to the surface of the substrate by wiping, scraping, brushing or spraying.

5. The method for preparing the epoxy resin waterproof adhesive layer according to claim 1, wherein: The bisphenol A epoxy resin monomer is one or a combination of WSR618, E51 or E44.

6. The method for preparing the epoxy resin waterproof adhesive layer according to claim 5, characterized in that: The epoxy equivalent of the bisphenol A epoxy resin monomer is ≤270 g / mol.

7. The method for preparing the epoxy resin waterproof adhesive layer according to claim 1, characterized in that: The amine curing agent is one or a combination of tetraethylenepentamine, dihexyltriamine or meta-xylenediamine.

8. The method for preparing the epoxy resin waterproof adhesive layer according to claim 1, characterized in that: The single molding thickness of the prepared waterproof adhesive layer is less than 10 microns.

9. An epoxy resin waterproof adhesive layer, characterized in that: The method according to any one of claims 1 to 8 is used for preparation.

Images