Anti-corrosion primer for cementing titanium alloy and composite material and preparation method of anti-corrosion primer

Abstract

The invention discloses an anti-corrosion primer for cementing a titanium alloy and a composite material and a preparation method of the anti-corrosion primer, and relates to the field of anti-corrosion primer for cementing the titanium alloy and the composite material, and the anti-corrosion primer comprises epoxy resin, an amine curing agent, thermoplastic resin, a corrosion inhibitor and a mixed solvent. The preparation method comprises the following steps: weighing epoxy resin and a corrosion inhibitor for later use, roughly mixing, and uniformly dispersing to prepare a dispersion of the corrosion inhibitor and the epoxy resin; the preparation method comprises the following steps: dissolving thermoplastic resin in a mixed solvent in a stirring state at normal temperature, adding a dispersion of a corrosion inhibitor and epoxy resin and epoxy resin after the thermoplastic resin is completely dissolved, and dissolving and stirring uniformly for later use; and uniformly dispersing and dissolving the amine curing agent in another solvent, and stirring and uniformly dispersing the amine curing agent and the mixed liquid after the amine curing agent is completely dissolved. The anti-corrosion primer can greatly improve the corrosion resistance and durability of the titanium alloy, and is used for binding and bonding the composite material blade and the titanium alloy of power equipment.

Description

Technical Field

[0001] The present invention relates to the field of anti-corrosion primer for bonding titanium alloy and composite material, and specifically relates to a method for preparing an anti-corrosion primer for bonding titanium alloy and composite material by using epoxy resin, thermoplastic resin, aromatic amine curing agent, corrosion inhibitor and mixed solvent. Background Art

[0002] Titanium alloy is widely used in the aerospace field due to its excellent properties such as low density and high strength. Titanium alloy is quite stable chemically in general environments and has good corrosion resistance, especially excellent corrosion resistance under alkaline and neutral conditions. However, its corrosion resistance decreases significantly under acidic conditions. As the main component material of the blades of power equipment, the working environment of titanium alloy is relatively complex. In order to extend the service life and safety of the blades, it is imperative to invent an anti-corrosion primer for bonding titanium alloy and composite material, which can meet the manufacturing requirements for bonding the composite material blades of power equipment and the titanium alloy edging. However, the existing anti-corrosion primers, due to different compositions, especially the corrosion inhibitors, are not suitable for the anti-corrosion primer in the bonding process of titanium alloy and composite material, and cannot improve the anti-corrosion durability of titanium alloy. Summary of the Invention

[0003] The purpose of the present invention is to solve the above technical problems and provide an anti-corrosion base glue for bonding titanium alloy and composite material and its preparation method.

[0004] An anti-corrosion base glue for bonding titanium alloy and composite material of the present invention is composed of 70 - 100 parts by weight of epoxy resin, 25 - 35 parts by weight of amine curing agent, 60 - 80 parts by weight of thermoplastic resin, 4 - 9 parts by weight of corrosion inhibitor and 1100 - 1500 parts by weight of mixed solvent.

[0005] Further, the anti-corrosion base glue is composed of 85 - 95 parts by weight of epoxy resin, 28 - 32 parts by weight of amine curing agent, 65 - 75 parts by weight of thermoplastic resin, 5 - 8 parts by weight of corrosion inhibitor and 1300 - 1400 parts by weight of mixed solvent.

[0006] Further, the epoxy resin is composed of bisphenol A epoxy resin, brominated epoxy resin and 3,3',5,5'-tetramethylbiphenyl diglycidyl ether in a weight ratio of (1 - 3):(0.3 - 0.5):0.8.

[0007] Further, the epoxy resin is composed of bisphenol A epoxy resin, brominated epoxy resin and 3,3',5,5'-tetramethylbiphenyl diglycidyl ether in a weight ratio of (1 - 3):(0.3 - 0.5):0.8; and the bisphenol A epoxy resin is bisphenol A epoxy resin of E-51, E-20 or E-44 model.

[0008] Further, the amine curing agent is composed of 4,4'-diaminodiphenyl sulfone, 4,4'-oxydianiline, and 1,6-diaminohexane in a weight ratio of (1-3):(1-2):1.

[0009] Further, the thermoplastic resin is one or more of polyether ketone ketone, polyphenylene sulfide, and heteroarylene biphenyl copolymerized polyarylether sulfone.

[0010] Further, the corrosion inhibitor is formed by mixing tetramethylammonium chloride and tetramethylammonium nitrate in a mass ratio of 1-3:1.

[0011] Further, the mixed solvent is prepared from chloroform and cyclohexanone.

[0012] A method for an anti-corrosion primer for bonding titanium alloy and composite material according to the present invention is as follows:

[0013] S1. Weigh 70-100 parts of epoxy resin, 25-35 parts of amine curing agent, 60-80 parts of thermoplastic resin, 4-9 parts of corrosion inhibitor, and 1100-1500 parts of mixed solvent by weight respectively;

[0014] S2. Take equal amounts of the epoxy resin and the corrosion inhibitor weighed in step S1 for standby. First, roughly mix the two, and then uniformly disperse the two through a three-roll mill to obtain a dispersion of the corrosion inhibitor and the epoxy resin.

[0015] S3. Dissolve the thermoplastic resin in the mixed solvent under stirring at room temperature. After complete dissolution, add the dispersion of the corrosion inhibitor and the epoxy resin and the epoxy resin prepared in step B2, dissolve and stir, and set aside after uniformity.

[0016] S4. Uniformly disperse and dissolve the amine curing agent in the solvent. After complete dissolution, stir and disperse it uniformly with the mixed liquid prepared in step S3 to prepare a slow-release primer.

[0017] Further, the solvent is prepared from chloroform and cyclohexanone.

[0018] The present invention has the following beneficial effects:

[0019] The present invention selects two relatively unique corrosion inhibitors: tetramethylammonium chloride and a kind of adsorption-type corrosion inhibitor, tetramethylammonium chloride. Its molecular structural formula contains N heteroatoms and polar groups. Its structure is similar to that of common surfactants and has amphiphilic properties. It can be oriented on the metal surface to form a hydrophobic film, thereby isolating the corrosive medium and playing a very strong protective role on the titanium alloy. In addition, tetramethylammonium chloride contains Cl⁻, which has high activity. Cl⁻ will combine with titanium to form a dense oxide layer, which will hinder the erosion of air and water on the titanium alloy and achieve the purpose of anti-corrosion. Ammonium nitrate is a corrosion inhibitor with oxidation characteristics, which can form a dense passivation film on the surface of the titanium alloy, thereby playing a role in inhibiting metal corrosion. The above two corrosion inhibitors form a protective layer on the surface of the titanium alloy through various interactions, preventing the titanium alloy from being corroded by air, water, etc., and improving the anti-corrosion performance and durability of the titanium alloy.

[0020] The anti-corrosion primer glue of the present invention can greatly improve the corrosion resistance and durability of the titanium alloy and is used for the adhesive manufacturing of the composite material blade of the power equipment and the titanium alloy edging. Specific embodiments

[0021] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer and more understandable, the spirit of the content disclosed by the present invention will be described in detail below. After any person skilled in the art in the technical field concerned understands the embodiments of the content of the present invention, they can make changes and modifications based on the technology taught by the content of the present invention, which do not deviate from the spirit and scope of the content of the present invention.

[0022] The illustrative embodiments of the present invention and their descriptions are used to explain the present invention, but do not limit the present invention.

[0023] Example 1

[0024] A method for an anti-corrosion base glue for bonding titanium alloy and composite material in this embodiment is characterized in that the preparation method is as follows:

[0025] S1. Weigh 70 parts by weight of epoxy resin, 25 parts by weight of amine curing agent, 60 parts by weight of thermoplastic resin, 4 parts by weight of corrosion inhibitor, and 1100 parts of mixed solvent respectively;

[0026] S2. Take the epoxy resin and corrosion inhibitor weighed in step S1 and set them aside. First, mix them roughly, and then disperse them evenly through a three-roll mill to obtain a dispersion of the corrosion inhibitor and epoxy resin;

[0027] S3. Dissolve the thermoplastic resin in chloroform under stirring at room temperature. After complete dissolution, add the dispersion of the corrosion inhibitor and epoxy resin and the epoxy resin prepared in step S2, dissolve and stir, and set aside after being uniform;

[0028] S4. Uniformly disperse and dissolve the amine curing agent in another solvent. After complete dissolution, stir and disperse it evenly with the mixed liquid prepared in step S3 to prepare the slow-release primer.

[0029] Example 2

[0030] A method for preparing an anti-corrosion primer for bonding titanium alloy and composite material in this example is characterized in that the preparation method is as follows:

[0031] S1. Weigh 85 parts of epoxy resin, 28 parts of amine curing agent, 72 parts of thermoplastic resin, 8 parts of corrosion inhibitor and 1400 parts of mixed solvent respectively by weight;

[0032] S2. Take the epoxy resin and corrosion inhibitor weighed in step S1 for standby. First, roughly mix the two, and then uniformly disperse the two through a three-roll mill to obtain a dispersion of the corrosion inhibitor and epoxy resin;

[0033] S3. Dissolve the thermoplastic resin in chloroform under stirring at room temperature. After complete dissolution, add the dispersion of the corrosion inhibitor and epoxy resin and epoxy resin prepared in step S2, dissolve and stir, and set aside after uniformity;

[0034] S4. Uniformly disperse and dissolve the amine curing agent in another solvent. After complete dissolution, stir and disperse it evenly with the mixed liquid prepared in step S3 to prepare the slow-release primer.

[0035] Example 3

[0036] The difference between the anti-corrosion primer for bonding titanium alloy and composite material in this example and Example 2 is that the primer in this example is composed of the following raw materials by weight:

[0037] 85 - 95 parts of epoxy resin, 28 - 32 parts of amine curing agent, 65 - 75 parts of thermoplastic resin, 5 - 8 parts of corrosion inhibitor, 1300 - 1400 parts of mixed solvent.

[0038] Example 4

[0039] The difference between the anti-corrosion primer for bonding titanium alloy and composite material in this example and Example 2 is that the primer in this example is composed of the following raw materials by weight:

[0040] 100 parts of epoxy resin, 35 parts of amine curing agent, 80 parts of thermoplastic resin, 9 parts of corrosion inhibitor, 1500 parts of mixed solvent.

[0041] In this embodiment, the epoxy resin in the anti-corrosion primer for bonding titanium alloy and composite material is composed of bisphenol A epoxy resin of E-51 type, brominated epoxy resin and 3,3',5,5'-tetramethylbiphenyl diglycidyl ether in a weight ratio of 3:0.5:0.8, that is, 70 parts of bisphenol A epoxy resin, 11.5 parts of brominated epoxy resin and 18.5 parts of 3,3',5,5'-tetramethylbiphenyl diglycidyl ether;

[0042] The amine curing agent in this embodiment is composed of 4,4'-diaminodiphenyl sulfone, 4,4'-oxydianiline and 1,6-diaminohexane in a weight ratio of 3:2:1;

[0043] The thermoplastic resin in this embodiment is composed of polyether ketone ketone and heteroarylene biphenyl copolyarylether sulfone in a weight ratio of 1:1.

[0044] The corrosion inhibitor in this embodiment is composed of tetramethylammonium chloride and tetramethylammonium nitrate in a weight ratio of 2:1; the mixed solvent is prepared from chloroform and cyclohexanone in a weight ratio of 1:1.

[0045] The preparation method of an anti-corrosion primer for bonding titanium alloy and composite material in this embodiment is as follows:

[0046] S1. Weigh 70 parts of epoxy resin of E-51 type, 11.5 parts of brominated epoxy resin, 18.5 parts of 3,3',5,5'-tetramethylbiphenyl diglycidyl ether, 17.5 parts of 4,4'-diaminodiphenyl sulfone, 11.7 parts of 4,4'-oxydianiline, 5.8 parts of 1,6-diaminohexane, 40 parts of polyether ketone ketone, 40 parts of heteroarylene biphenyl copolyarylether sulfone, 6 parts of tetramethylammonium chloride, 3 parts of tetramethylammonium nitrate, 750 parts of chloroform and 750 parts of cyclohexanone by weight;

[0047] S2. Take the epoxy resin and corrosion inhibitor (weight ratio 1:1) weighed in step S1 and set aside. First, mix them roughly, and then disperse them evenly through a three-roll mill to obtain a dispersion of the corrosion inhibitor and epoxy resin.

[0048] S3. Dissolve the thermoplastic resin in chloroform under stirring at room temperature. After complete dissolution, add the dispersion of the corrosion inhibitor and epoxy resin and epoxy resin prepared in step S2, dissolve and stir, and set aside after being uniform.

[0049] S4. Uniformly disperse and dissolve the amine curing agent in another solvent. After complete dissolution, stir and disperse it evenly with the mixed liquid prepared in step S3 to prepare a slow-release primer.

[0050] The test results of the performance of the anti-corrosion primer and the adhesive film bonded specimen in this embodiment:

[0051] The room temperature shear strength of the anti-corrosion primer and film adhesively bonded to the titanium alloy composite specimen can reach 40.4 MPa, and the shear strength at 177 °C can reach 15.1 MPa. Its glass transition temperature reaches 190.5 °C, demonstrating high strength and high temperature resistance characteristics; for the anti-corrosion primer and film adhesively bonded to the aluminum alloy specimen used for bonding titanium alloy and composite materials in this example, the plate-to-plate floating roller peel strength reaches 60 N / cm (the film surface density is about 390 g / m 2 ), and the honeycomb sandwich structure drum peel strength reaches 143.6 N·m / m (the film surface density is about 390 g / m 2 ), and the honeycomb sandwich structure plane tensile strength reaches 9.1 MPa (the film surface density is 390 g / m 2 ), demonstrating the high toughness characteristics of the adhesive bonding system; for the anti-corrosion primer and film adhesively bonded to the titanium alloy-composite material specimen used for bonding titanium alloy and composite materials in this example, after undergoing the thermal aging performance assessment at 175 °C × 3000 h, it still maintains relatively high mechanical properties, and its shear strengths at room temperature and 177 °C still reach relatively high values of 25.8 MPa and 10.0 MPa. At the same time, another primer and the same film were selected for the 177 °C × 3000 h thermal aging performance assessment, and the shear strengths at room temperature and 177 °C after aging are 19.2 MPa and 4.9 MPa. Through data comparison, it can be seen that the room temperature and high temperature strengths of the anti-corrosion primer and film adhesively bonded to the titanium alloy and composite materials in this example after aging are significantly higher than those of another primer and film, indicating that the primer and film adhesively bonded specimens in this example have outstanding high temperature resistance and durability, verifying that the primer in this example forms a strong and stable protective interface on the surface of the titanium alloy, with excellent anti-corrosion and durability performance.

[0052] Example 5

[0053] The difference between the anti-corrosion primer for bonding titanium alloy and composite materials in this example and that in Example 2 is that the primer in this example is composed of the following raw materials in parts by weight:

[0054] 90 parts of epoxy resin, 30 parts of amine curing agent, 70 parts of thermoplastic resin, 6 parts of corrosion inhibitor, and 1300 parts of mixed solvent.

[0055] The epoxy resin in this example is composed of bisphenol A epoxy resin of E-51 type, brominated epoxy resin, and 3,3',5,5'-tetramethylbiphenyl diglycidyl ether in a weight ratio of 2:0.4:0.8;

[0056] The amine curing agent in this example is composed of 4,4'-diaminodiphenyl sulfone, 4,4'-oxydianiline, and 1,6-diaminohexane in a weight ratio of 2:2:1;

[0057] The thermoplastic resin in this embodiment is composed of polyphenylene sulfide and poly(phthalazinone ether sulfone ketone) in a weight ratio of 1:1.

[0058] The corrosion inhibitor in this embodiment is composed of tetramethylammonium chloride and tetramethylammonium nitrate in a weight ratio of 1:1; the mixed solvent is prepared from chloroform and cyclohexanone in a weight ratio of 1:1.

[0059] Example 6

[0060] The difference between the anti-corrosion primer for bonding titanium alloy and composite material in this embodiment and that in Example 2 is that the primer in this embodiment is composed of the following raw materials in parts by weight:

[0061] 80 parts of epoxy resin, 25 parts of amine curing agent, 60 parts of thermoplastic resin, 4 parts of corrosion inhibitor, and 1200 parts of mixed solvent.

[0062] The epoxy resin in this embodiment is composed of bisphenol A epoxy resin of E-20 type, brominated epoxy resin, and 3,3',5,5'-tetramethylbiphenyl diglycidyl ether in a weight ratio of 1:0.3:0.8;

[0063] The amine curing agent in this embodiment is composed of 4,4'-diaminodiphenyl sulfone, 4,4'-oxydianiline, and 1,6-diaminohexane in a weight ratio of 3:1:1;

[0064] The thermoplastic resin in this embodiment is composed of polyphenylene sulfide and polyether ketone ketone in a weight ratio of 1:1.

[0065] The corrosion inhibitor in this embodiment is composed of tetramethylammonium chloride and tetramethylammonium nitrate in a weight ratio of 2:1; the mixed solvent is prepared from chloroform and cyclohexanone in a weight ratio of 1:1.

[0066] Example 7

[0067] The difference between the anti-corrosion primer for bonding titanium alloy and composite material in this embodiment and that in Example 2 is that the primer in this embodiment is composed of the following raw materials in parts by weight: 100 parts of bisphenol A epoxy resin, 30 parts of 4,4'-diaminodiphenyl sulfone, 60 parts of polysulfone, 5 parts of strontium chromate (corrosion inhibitor), and 1000 parts of chloroform.

[0068] An anti-corrosion primer for bonding titanium alloy and composite material and its preparation method, which relates to the field of anti-corrosion primer coatings. The anti-corrosion primer of the present invention is composed of epoxy resin, amine curing agent, thermoplastic resin, corrosion inhibitor and mixed solvent according to weight parts. The epoxy resin and the corrosion inhibitor are roughly mixed and uniformly dispersed by a three-roll mill. At room temperature, the thermoplastic resin is dissolved in the solvent under stirring. After complete dissolution, the dispersion of the corrosion inhibitor and the epoxy resin and the epoxy resin are added and dissolved and stirred. The amine curing agent is uniformly dispersed and dissolved in another solvent. After complete dissolution, it is stirred and dispersed uniformly with the mixed liquid to prepare a slow-release primer. The anti-corrosion primer coating of the present invention can greatly improve the corrosion resistance and durability of titanium alloy, and is used for the bonding manufacturing of composite material blades and titanium alloy edges of power equipment.

[0069] Table 1 Performance test results of primer and adhesive film bonded specimens in different embodiments

[0070]

Claims

1. An anti-corrosion primer for bonding titanium alloy and composite material, characterized in that, It is composed of 70 - 100 parts by weight of epoxy resin, 25 - 35 parts by weight of amine curing agent, 60 - 80 parts by weight of thermoplastic resin, 4 - 9 parts by weight of corrosion inhibitor and 1100 - 1500 parts by weight of mixed solvent.

2. The anti-corrosion primer for bonding titanium alloy and composite material according to claim 1, characterized in that, The anti - corrosion primer is composed of 85 - 95 parts by weight of epoxy resin, 28 - 32 parts by weight of amine curing agent, 65 - 75 parts by weight of thermoplastic resin, 5 - 8 parts by weight of corrosion inhibitor and 1300 - 1400 parts by weight of mixed solvent.

3. An anti-corrosion primer for bonding titanium alloy and composite material according to claim 1, characterized in that, The epoxy resin is composed of bisphenol A epoxy resin, brominated epoxy resin and 3,3',5,5'-tetramethylbiphenyl diglycidyl ether in a weight ratio of (1 - 3):(0.3 - 0.5):0.

8.

4. An anti-corrosion primer for bonding titanium alloy and composite materials according to claim 1 or 3, characterized in that, The epoxy resin is composed of bisphenol A epoxy resin, brominated epoxy resin and 3,3',5,5'-tetramethylbiphenyl diglycidyl ether in a weight ratio of (1 - 3):(0.3 - 0.5):0.8; the bisphenol A epoxy resin is bisphenol A epoxy resin of E - 51, E - 20 or E - 44 type.

5. An anti-corrosion primer for bonding titanium alloy and composite material according to claim 1, characterized in that, The amine curing agent is composed of 4,4’-diaminodiphenyl sulfone, 4,4’-oxydianiline, 1,6 - diaminohexane in a weight ratio of (1 - 3):(1 - 2):

1.

6. The anti-corrosion primer for bonding titanium alloy and composite material according to claim 1, characterized in that, The thermoplastic resin is one or more of polyetherketoneketone, polyphenylene sulfide and heterocyclic naphthalene - biphenyl copolymerized polyarylether sulfone.

7. An anti-corrosion primer for bonding titanium alloy and composite material according to claim 1, characterized in that, The corrosion inhibitor is a mixture of tetramethylammonium chloride and tetramethylammonium nitrate in a mass ratio of 1 - 3:

1.

8. An anti-corrosion primer for bonding titanium alloy and composite material according to claim 1, characterized in that, The mixed solvent is prepared from chloroform and cyclohexanone.

9. A method for preparing an anti-corrosion primer for bonding titanium alloy and composite materials as described in claim 1, characterized in that, The method is as follows: S1. Weigh 70 - 100 parts by weight of epoxy resin, 25 - 35 parts by weight of amine curing agent, 60 - 80 parts by weight of thermoplastic resin, 4 - 9 parts by weight of corrosion inhibitor and 1100 - 1500 parts by weight of mixed solvent respectively by weight; S2. Take the same amount of epoxy resin and corrosion inhibitor weighed in step S1 for standby. First, mix them roughly, and then disperse them evenly through a three - roll mill to obtain a dispersion of corrosion inhibitor and epoxy resin. S3. At room temperature, dissolve the thermoplastic resin in the mixed solvent under stirring. After complete dissolution, add the dispersion of corrosion inhibitor and epoxy resin and epoxy resin prepared in step B2, dissolve and stir until uniform, and then set aside. S4. Uniformly disperse the amine curing agent in the solvent. After complete dissolution, stir and disperse it evenly with the mixed liquid prepared in step S3 to prepare the slow - release primer.

10. A method for an anti-corrosion primer for bonding titanium alloy and composite material according to claim 9, characterized in that, The solvent is prepared from chloroform and cyclohexanone.

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