A waterproof structure and a method for manufacturing the same, and a waterproof rotary composite material based on the waterproof structure and a method for manufacturing and using the same

Abstract

The application discloses a kind of anti-moisture structures and preparation methods thereof, and preparation and application of anti-moisture rotary composite material based on it.The application belongs to the field of fiber reinforced resin matrix composite material.The purpose of the application is to solve the technical problem of insufficient anti-moisture effect of existing waterproof materials.The preparation of the anti-moisture structure is as follows: S1: mixing multifunctional epoxy resin and modified dicyandiamide, then hot-pressing to obtain a dense resin preformed film;S2: impregnating and winding the resin on carbon fiber felt, then brushing a layer of winding resin to obtain impregnated carbon fiber felt, and then laying the impregnated carbon fiber felt on the surface of the preformed film;S3: coating coupling agent on both sides of the polymer film, then coating adhesive to obtain modified polymer film, and then laying the modified polymer film on the surface of the carbon fiber felt.The molding process of the application can meet the needs of continuous production of fiber winding molding.The anti-moisture structure has little effect on the mechanical properties of the body structure of the composite product, and can greatly improve the anti-moisture performance of the composite product.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of fiber reinforced resin-based composite materials, and particularly relates to a moisture permeation prevention structure and a preparation method thereof, a moisture permeation prevention rotary composite material based on the structure and preparation and application thereof. BACKGROUND

[0002] Fiber reinforced resin-based composite materials have certain pores in the materials, which result in water or water vapor permeating into the materials when the materials are in a water environment or a high humidity environment for a long time. When there are humidity-sensitive components in the composite material container, the water vapor will affect the performance of the components. Therefore, a moisture permeation prevention structure for composite materials needs to be prepared to effectively reduce the influence of water on the internal components and prolong the service life of the internal components.

[0003] There are many types of existing waterproof materials, but pure waterproof materials cannot achieve the effect of preventing moisture permeation. For example, according to the national standard GB / T7350, the maximum sealing degree of waterproof packaging is that there is no water stain or water penetration or leakage in the packaging after 60 minutes of spraying or 120 minutes of immersion. According to GJB1444, the moisture permeability of ammunition soft packaging or hard packaging is not greater than 3g / (m 2 ·30d) for the first level and not greater than 9g / (m 2 ·30d) for the second level, and therefore, the original waterproof materials cannot meet the requirements of preventing moisture permeation. SUMMARY

[0004] The purpose of the present application is to solve the technical problem of insufficient effect of preventing moisture permeation of existing waterproof materials, and to provide a moisture permeation prevention structure and a preparation method thereof, a moisture permeation prevention rotary composite material based on the structure and preparation and application thereof.

[0005] The purpose of the present application is achieved by the following technical solutions:

[0006] One of the purposes of the present application is to provide a preparation method of a moisture permeation prevention structure, which is performed according to the following steps:

[0007] S1: mixing a multifunctional epoxy resin and a modified dicyandiamide, and then hot pressing to obtain a dense resin preformed film;

[0008] S2: dipping and winding the resin on a carbon fiber felt, pressing with a rubber roller, and then brushing a layer of winding resin, repeating 2-3 times to obtain a dipped carbon fiber felt, and then laying the dipped carbon fiber felt on the surface of the dense resin preformed film;

[0009] S3: coating a coupling agent on both sides of a polymer film, and then coating an adhesive to obtain a modified polymer film, and then laying the modified polymer film on the surface of the dipped carbon fiber felt to obtain a moisture permeation prevention structure.

[0010] Further, the mass ratio of the multifunctional epoxy resin and the modified dicyandiamide in S1 is 10:1.

[0011] Further, the multifunctional epoxy resin in S1 is a mixture of tert-PGEE and tri-PGEM with a mass ratio of 1:1.

[0012] Further, the modified dicyandiamide in S1 is a mixture of dicyandiamide and diaminodiphenylmethane with a mass ratio of (4-7):1.

[0013] Further, the thickness of the dense resin preformed film in S1 is 0.3-0.5mm.

[0014] Further, the carbon fiber surface felt in S2 has a specification of 30-50g / m 2 .

[0015] Further, the polymer film in S3 is a polytetrafluoroethylene film, a polyethylene film or a polypropylene film, and has a thickness of 0.3-0.5mm.

[0016] Further, the polymer film is chemically corroded before use.

[0017] Further, the chemical corrosion is specifically soaking in concentrated sulfuric acid for 5-10min.

[0018] Further, the coupling agent in S3 is an organic silicon epoxy mixture.

[0019] Further, the adhesive in S3 is composed of bisphenol F epoxy resin 80 parts, isocyanate solution 5-8 parts and polyamine 15-20 parts by mass fraction.

[0020] The second object of the present application is to provide a moisture permeation resistant structure prepared by the above method, which is composed of a dense resin preformed film, a carbon fiber felt and a modified polymer film stacked from bottom to top.

[0021] The third object of the present application is to provide an application of the moisture permeation resistant structure prepared by the above method in a fiber reinforced resin matrix composite material formed by winding.

[0022] The fourth object of the present application is to provide a preparation method of a moisture permeation resistant rotary composite material, which is performed according to the following steps:

[0023] The above moisture permeation resistant structure is wound on the surface of an uncured fiber reinforced resin matrix composite material formed by wet winding, and then the fiber reinforced resin matrix composite material is continuously formed by wet winding to obtain a moisture permeation resistant rotary composite material.

[0024] The fifth object of the present application is to provide a moisture-proof rotary composite material prepared by the above method.

[0025] The sixth object of the present application is to provide an application of the moisture-proof rotary composite material prepared by the above method in a humidity-sensitive component.

[0026] Compared with the prior art, the present application has the following remarkable effects:

[0027] (1) The present application develops a composite moisture-proof structure, a carbon fiber surface felt forms a high-resin-content tough transition layer between a dense resin preformed film and a polymer film, the outermost polymer film performs a certain degree of water or water vapor isolation, the intermediate layer of the carbon fiber felt with high resin content is tough and can also prevent water or water vapor from penetrating, finally, the high-density resin film can further isolate the water or water vapor that has penetrated through the previous two layers, so that the moisture permeability of the moisture-proof structure is less than or equal to 0.4 g / (m 2 ·30d).

[0028] (2) The forming process of the present application can meet the needs of continuous production of fiber winding forming. The moisture-proof structure has little effect on the mechanical properties of the structural layer of the composite material product, and can greatly improve the moisture-proof performance of the composite material product.

[0029] (3) The present application can be used in various winding-formed rotary structures, and the moisture-proof composite material structure involved is universal and can be applied to various fiber-reinforced resin-based composite materials. DETAILED DESCRIPTION

[0030] In order to make the objects, technical solutions and advantages of the present application clearer, the present application will be further described in detail below with reference to examples. It should be understood that the specific examples described herein are only used to explain the present application and do not limit the present application.

[0031] The experimental methods used in the following examples are conventional methods unless otherwise specified. The materials, reagents, methods and instruments used are conventional materials, reagents, methods and instruments in the art unless otherwise specified, and can be obtained by commercial channels by those skilled in the art.

[0032] The terms "comprising", "including", "having", "containing", or any other variant thereof, used in the following examples, are intended to cover non-exclusive inclusion. For example, a composition, step, method, article or apparatus that comprises a list of elements does not necessarily limit those elements to only those elements, but can include other elements not expressly listed or inherent to such composition, step, method, article or apparatus.

[0033] When equivalent, concentration, or other value or parameter is expressed in a range or a preferred range or a series of ranges of upper preferred values and lower preferred values, it is to be understood that all ranges formed by any pair of any upper range limit or preferred value and any lower range limit or preferred value, even if the ranges are not separately specifically listed, are expressly disclosed. For example, where a range of "1 to 5" is disclosed, the disclosure is to be interpreted to include ranges of "1 to 4," "1 to 3," "1 to 2," "1 to 2 and 4 to 5," "1 to 3 and 5," etc. When numerical ranges are disclosed, unless otherwise stated, the range is intended to include all integers and fractions within the range. In the application, ranges can be combined and / or interchanged, unless otherwise stated, and the ranges include all sub-ranges therein.

[0034] The indefinite articles "a" and "an," as used herein in the specification and in the claims, unless clearly indicated to the contrary, should be understood to mean one or at least one. The use of "or" in the context of "A / B or C" means any of the following: A, B, or C; only A; only B; only C; A and B; A and C; B and C; A, B, and C; only A, B, and C; not A but B and C; not B but A and C; not C but A and B; and A, B, and C.

[0035] The modification process of the impregnated carbon fiber felt and the polymer film in the moisture-proof structure of the following embodiments does not require special equipment, and the prefabricated product can be stored at -18°C for 8h. The dense resin prefabricated film is hot-pressed by a prepreg machine, and then stored at -18°C for 30 days.

[0036] Specific embodiment one: the preparation method of a moisture-proof structure in this embodiment is carried out according to the following steps:

[0037] S1: mixing a multifunctional epoxy resin and a modified dicyandiamide, and then hot-pressing to obtain a dense resin prefabricated film with a thickness of 0.3-0.5mm;

[0038] The multifunctional epoxy resin is mixed by tert-PGEE and tri-PGEM at a mass ratio of 1:1, and the modified dicyandiamide is mixed by dicyandiamide and diaminodiphenylmethane at a mass ratio of (4-7):1.

[0039] S2: impregnating and winding the carbon fiber felt (specification: 30-50g / m 2 ) with resin, and then repeatedly brushing a layer of winding resin after chasing with a rubber roller, to obtain an impregnated carbon fiber felt, which is then laid on the surface of the dense resin prefabricated film;

[0040] S3: coating a coupling agent on both sides of the polymer film with a thickness of 0.3-0.5mm, and then coating an adhesive to obtain a modified polymer film, which is then laid on the surface of the impregnated carbon fiber felt to obtain a moisture-proof structure;

[0041] The high polymer film is a polytetrafluoroethylene film, a polyethylene film or a polypropylene film, and the thickness is 0.3-0.5mm, and the high polymer film is chemically corroded before use, and the chemical corrosion is specifically soaking in concentrated sulfuric acid for 5-10min, the coupling agent is an organic silicon epoxy mixture, and the adhesive is composed of 80 parts of bisphenol F epoxy resin, 5-8 parts of isocyanate solution and 15-20 parts of polyamine by mass fraction.

[0042] Specific implementation method two: the preparation method of the anti-permeable wet rotary composite material of the embodiment is carried out according to the following steps:

[0043] First step, preparation of an anti-permeable wet structure:

[0044] S1: mixing a multifunctional epoxy resin and a modified dicyandiamide, and then hot-pressing to obtain a dense resin preformed film with a thickness of 0.3-0.5mm;

[0045] The multifunctional epoxy resin is mixed by tert-PGEE and tri-PGEM at a mass ratio of 1:1, and the modified dicyandiamide is mixed by dicyandiamide and diaminodiphenylmethane at a mass ratio of (4-7):1.

[0046] S2: dipping and winding the resin on a carbon fiber felt (specification is 30-50g / m 2 ), and then brushing a layer of winding resin after chasing and pressing with a rubber roller, and repeating for 3 times to obtain a resin-dipped carbon fiber felt, and then laying it on the surface of the dense resin preformed film;

[0047] S3: coating a coupling agent on both sides of a high polymer film with a thickness of 0.3-0.5mm, and then coating an adhesive to obtain a modified high polymer film, and then laying it on the surface of the resin-dipped carbon fiber felt to obtain an anti-permeable wet structure;

[0048] The high polymer film is a polytetrafluoroethylene film, a polyethylene film or a polypropylene film, and the thickness is 0.3-0.5mm, and the high polymer film is chemically corroded before use, and the chemical corrosion is specifically soaking in concentrated sulfuric acid for 5-10min, the coupling agent is an organic silicon epoxy mixture, and the adhesive is composed of 80 parts of bisphenol F epoxy resin, 5-8 parts of isocyanate solution and 15-20 parts of polyamine by mass fraction.

[0049] Second step, preparation of an anti-permeable wet rotary composite material:

[0050] S4: wet winding to form a fiber-reinforced resin-based composite material, and then winding the anti-permeable wet structure obtained in the first step on the surface of the composite material before curing;

[0051] S5: continue to wrap the formed fiber reinforced resin matrix composite on the surface of the moisture permeation prevention structure by wet winding to obtain a moisture permeation prevention rotary composite material.

[0052] Example 1:

[0053] The preparation method of the moisture permeation prevention rotary composite material of the present example is carried out in the following steps:

[0054] First step, preparation of the moisture permeation prevention structure:

[0055] S1: first, 5000g of tert-PGEE and 5000g of tri-PGEM are stirred and mixed uniformly to obtain a multifunctional epoxy resin;

[0056] Then, 830g of dicyandiamide and 170g of diamino diphenyl methane are stirred and mixed uniformly to obtain a modified dicyandiamide;

[0057] Next, 10kg of multifunctional epoxy resin and 1kg of modified dicyandiamide are mixed, and then a dense resin preformed film with a thickness of 0.5mm is obtained by hot melt pressing;

[0058] S2: first, the carbon fiber felt (specification 50g / m 2 ) is impregnated with winding resin (E54: 5028B = 100:30, 5028B resin manufacturer is Huibao New Material Technology (Shanghai) Co., Ltd.), and then a layer of winding resin is brushed after being pressed by a rubber roller, and the above steps are repeated for 3 times to obtain a carbon fiber felt impregnated with glue;

[0059] Then, the carbon fiber felt impregnated with glue is laid on the surface of the dense resin preformed film;

[0060] S3: first, the polytetrafluoroethylene film with a thickness of 0.5mm is soaked in concentrated sulfuric acid for 10min, and then the organic silicon epoxy mixture (a mixture of epoxy propoxy trimethoxysilane and BGE in a mass ratio of 1:1) is coated on both sides of the film;

[0061] Then, the adhesive is coated, and the adhesive is composed of 800g of bisphenol F epoxy resin, 50g of isocyanate solution, and 150g of diamino diphenyl methane in mass fraction;

[0062] Subsequently, the modified polymer film is laid on the surface of the carbon fiber felt impregnated with glue to obtain a moisture permeation prevention structure with a thickness of 1.2mm.

[0063] Second step, preparation of the moisture permeation prevention rotary composite material:

[0064] S4: the fiber reinforced resin matrix composite (T700 grade carbon fiber / E54) is formed by wet winding to a thickness of 8mm, and then the moisture permeation prevention structure obtained in the first step is wound on the surface of the composite material before curing;

[0065] S5: Continue to wet winding on the surface of the moisture-proof structure to form the above-mentioned fiber-reinforced resin-based composite material on the moisture-proof structure to a thickness of 1 mm to obtain a moisture-proof rotary composite material.

[0066] Example 2:

[0067] The preparation method of the moisture-proof rotary composite material of the present embodiment is carried out in the following steps:

[0068] First step, preparation of the moisture-proof structure:

[0069] S1: First, 5000g of tert-PGEE and 5000g of tri-PGEM are stirred and mixed uniformly to obtain a multifunctional epoxy resin;

[0070] Then, 830g of dicyandiamide and 170g of diamino diphenyl methane are stirred and mixed uniformly to obtain a modified dicyandiamide;

[0071] Next, 10kg of multifunctional epoxy resin and 1kg of modified dicyandiamide are mixed, and then a dense resin preformed film with a thickness of 0.5mm is obtained by hot melt pressing;

[0072] S2: First, carbon fiber felt (specification 50g / m 2 ) is impregnated with winding resin (E54: 5028B = 100:30, 5028B resin manufacturer is Huibao New Material Technology (Shanghai) Co., Ltd.), and after being pressed with a rubber roller, a layer of winding resin is brushed again, and after repeating 3 times, impregnated carbon fiber felt is obtained;

[0073] Then, the impregnated carbon fiber felt is laid on the surface of the dense resin preformed film;

[0074] S3: First, a polytetrafluoroethylene film with a thickness of 0.5mm is soaked in concentrated sulfuric acid for 10min, and after being taken out, silicone epoxy mixture (a mixture of epoxy propoxy trimethoxysilane and BGE in a mass ratio of 1:1) is coated on both sides;

[0075] Then, an adhesive is coated again, which is composed of 800g of bisphenol F epoxy resin, 60g of isocyanate solution, and 180g of diamino diphenyl methane in mass fraction;

[0076] Subsequently, the modified polymer film is laid on the surface of the impregnated carbon fiber felt to obtain a moisture-proof structure with a thickness of 1.2mm.

[0077] Second step, preparation of the moisture-proof rotary composite material:

[0078] S4: wet winding the fiber reinforced resin matrix composite (glass fiber SC1200 Nanjing Glass Fiber Institute Co., Ltd. / E54) to a thickness of 8 mm, and then winding the moisture-proof structure obtained in the first step on the surface of the composite before curing;

[0079] S5: continue to wet winding the fiber reinforced resin matrix composite on the surface of the moisture-proof structure to a thickness of 1 mm to obtain a moisture-proof rotary composite material.

[0080] Comparative Example 1:

[0081] The difference between this comparative example and Example 1 is that it does not contain a moisture-proof structure. The other steps and parameters are the same as those of Example 1.

[0082] Comparative Example 2:

[0083] The difference between this comparative example and Example 2 is that it does not contain a moisture-proof structure. The other steps and parameters are the same as those of Example 2.

[0084] Detection of moisture-proof effect:

[0085] The composite materials obtained in Examples 1-2 and Comparative Examples 1-2 were prepared into cylinders with a thickness of 8 mm, and metal plugs were used to block the openings. A temperature and humidity test sensor was installed on the metal plug to monitor the changes in temperature and humidity inside the cylinder segment in real time. The cylinder segment was placed in a 90% humidity and 50°C heat test box, and the test lasted for 30 days. The results are shown in Table 1.

[0086] Table 1 Moisture-proof performance

[0087] Test results Example 1 0.4 g / (m 2 · 30 d) Example 2 0.36 g / (m 2 ·30 d) Comparative Example 1 1.6 g / (m 2 ·30 d) Comparative Example 2 1.4 g / (m 2 ·30 d)

[0088] In summary, the fiber surface felt forms a tough transition layer with high resin content between the dense resin preformed film and the polymer film. The outermost layer uses the polymer film to a certain extent to isolate water or water vapor. The intermediate layer of carbon fiber felt with high resin content is tough and can also prevent the penetration of water or water vapor. Finally, the high density can further isolate the water or water vapor that has penetrated through the first two layers from the external environment. The operation method is simple, and the molding process can meet the needs of continuous production of fiber winding molding. The moisture-proof structure has little effect on the mechanical properties of the composite product, and can greatly improve the moisture-proof performance of the composite product.

[0089] The above merely describes preferred specific embodiments of the present application, which are based on different implementations of the overall concept of the present application, and the protection scope of the present application is not limited thereto. Any changes or replacements that are easily conceived by those skilled in the art within the technical scope disclosed by the present application shall be covered by the protection scope of the present application. Therefore, the protection scope of the present application should be subject to the protection scope of the claims.

Claims

1. A method for producing a moisture permeable structure, characterized by, The following steps are taken: S1: mixing the multifunctional epoxy resin and modified dicyandiamide, and then obtaining a dense resin preformed film by hot melt pressing; the multifunctional epoxy resin is obtained by mixing tert-PGEE and tri-PGEM at a mass ratio of 1:1, and the modified dicyandiamide is obtained by mixing dicyandiamide and diaminodiphenylmethane at a mass ratio of (4-7):1; S2: dipping and winding the resin on the carbon fiber felt, pressing it with a rubber roller, and then brushing a layer of winding resin, repeating 2-3 times to obtain a dipped carbon fiber felt, and then laying it on the surface of the dense resin preformed film; S3: coating a coupling agent on both sides of the polymer film, and then coating an adhesive to obtain a modified polymer film, and then laying it on the surface of the dipped carbon fiber felt to obtain a moisture permeation prevention structure; the polymer film is a polytetrafluoroethylene film, a polyethylene film or a polypropylene film, with a thickness of 0.3-0.5 mm, and the polymer film is chemically etched before use, specifically immersed in concentrated sulfuric acid for 5-10 min; the coupling agent is an organic silicon epoxy copolymer, and the adhesive is composed of 80 parts of bisphenol F epoxy resin, 5-8 parts of isocyanate solution and 15-20 parts of polyamine by mass fraction; In S1, the mass ratio of the multifunctional epoxy resin and the modified dicyandiamide is 10:1, and the thickness of the obtained dense resin preformed film is 0.3-0.5 mm.

2. The method of claim 1, wherein, The carbon fiber surface felt specification in S2 is 30-50 g / m 2 .

3. The moisture barrier structure produced by the method of any one of claims 1 or 2, characterized by, It is composed of a dense resin preformed film, a dipped carbon fiber felt and a modified polymer film stacked from bottom to top.

4. The use of the moisture permeation prevention structure prepared by the method of any one of claims 1 or 2 in a wound forming fiber reinforced resin matrix composite.

5. A method for producing a moisture permeation preventing rotary type composite material, characterized by comprising: The following steps are taken: The moisture permeation prevention structure of claim 3 is wound on the surface of an unhardened fiber reinforced resin matrix composite formed by wet winding, and then the fiber reinforced resin matrix composite is continuously formed by wet winding to obtain a moisture permeation prevention rotary composite.

6. The moisture permeation prevention rotary composite prepared by the method of claim 5.

7. The use of the moisture permeation prevention rotary composite prepared by the method of claim 5 in a humidity sensitive device.