Halogen-free flame-retardant build-up resin and method for preparing the same

Abstract

The application provides a halogen-free flame-retardant laminated resin prepared from component A and component B, wherein the component A comprises modified high phosphorus-containing epoxy resin, dimethyl methylphosphonate, non-crystalline epoxy resin, silane defoaming agent, fluorosilicon defoaming agent and silane coupling agent, and the component B comprises polyether amine, isophorone amine and triethanolamine. The application also provides a preparation method of the halogen-free flame-retardant laminated resin. The halogen-free flame-retardant laminated resin provided by the application has the advantages of low viscosity, good fiber wetting, high hardness, normal-temperature curing, high transparency and good flame-retardant effect due to the selection of specific contents of components and the interaction between the components.

Description

Technical Field

[0001] This invention relates to the field of resin technology, and in particular to a halogen-free flame-retardant laminated resin and its preparation method. Background Technology

[0002] Resin Transfer Molding (RTM) is a common advanced molding process for carbon fiber reinforced composites. Because of its relatively low cost, especially the low cost of molds, and its ability to produce large, complex structures, RTM is widely used in the composite materials industry, regardless of size. It is particularly advantageous for small and medium-sized enterprises in the composite materials industry producing small-volume, large-shaped products such as engine hoods, front and rear bumpers, and fenders, offering a cost-effective solution and producing products with a smooth finish and fewer pinholes. However, there are relatively few flame-retardant resins available, making it difficult to meet the requirements for flame-retardant products. Existing flame-retardant laminating resins on the market often have poor flame-retardant properties, resulting in a candle-wick effect when laminated with carbon fiber; or they have poor wetting and penetration, causing whitening and numerous pinholes that negatively impact the appearance and performance of the finished product. Summary of the Invention

[0003] The technical problem solved by the present invention is to provide a halogen-free flame-retardant laminated resin, which has the advantages of good physical properties, good flame retardant effect and high resin transparency.

[0004] In view of this, this application provides a halogen-free flame-retardant laminated resin, prepared from component A and component B:

[0005] Component A includes:

[0006]

[0007] Component B includes:

[0008] 40-60 parts by weight of polyetheramine;

[0009] Isophoroneamine 30-50 parts by weight;

[0010] 5-15 parts by weight of triethanolamine.

[0011] Preferably, the preparation method of the modified high phosphorus content epoxy resin is as follows: triphosphazene is added to the epoxy resin monomer at a molar ratio of 1:0.8, and the mixture is heated and refluxed at 120°C for 2 hours.

[0012] Preferably, the amorphous epoxy resin is selected from South Asia NPEL-128s.

[0013] Preferably, the silane defoamer is selected from Deqian 6800, and the fluorosilicone defoamer is selected from Entropy Energy DF280.

[0014] Preferably, the content of the modified high-phosphorus epoxy resin is 60-70 parts by weight.

[0015] Preferably, the content of dimethyl methyl phosphate is 10 to 15 parts by weight.

[0016] Preferably, the content of the non-crystalline epoxy resin is 18 to 22 parts by weight.

[0017] Preferably, the content of the polyetheramine is 45-55 parts by weight, the content of the isophoroneamine is 35-45 parts by weight, and the content of the triethanolamine is 8-12 parts by weight.

[0018] This application also provides a method for preparing the aforementioned halogen-free flame-retardant laminated resin, comprising the following steps:

[0019] According to the component ratio, the modified high-phosphorus epoxy resin and dimethyl methyl phosphate were mixed and heated to obtain the initial mixture;

[0020] The initial mixture and amorphous epoxy resin were mixed, cooled, and then silane defoamer, fluorosilicone defoamer and silane coupling agent were added. After vacuuming, the mixture was cooled and filtered to obtain component A.

[0021] Polyetheramine, isophoroneamine and triethanolamine were mixed and reacted, and then vacuum was applied to obtain component B.

[0022] Components A and B are mixed and cured to obtain a halogen-free flame-retardant laminated resin.

[0023] This application also provides a fiber-reinforced composite material, comprising a resin and fibers, wherein the resin is the halogen-free flame-retardant laminated resin described above or the halogen-free flame-retardant laminated resin prepared by the preparation method described above.

[0024] This application provides a halogen-free flame-retardant laminated resin, which is prepared from component A and component B. Component A includes modified high-phosphorus epoxy resin, dimethyl methyl phosphate, non-crystalline epoxy resin, silane defoamer, fluorosilicone defoamer, and silane coupling agent. Component B includes polyetheramine, isophoroneamine, and triethanolamine. The halogen-free flame-retardant laminated resin provided by this application, by using specific amounts of components, can achieve room temperature curing, high resin transparency, high overall strength, and good flame-retardant effect. When compounded with fiber-reinforced materials, it imparts excellent impact resistance and high hardness to the product, and has good wetting properties to the fiber-reinforced materials, without white spots or whitish discoloration, while maintaining high transparency. Detailed Implementation

[0025] To further understand the present invention, preferred embodiments of the present invention are described below in conjunction with examples. However, it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention, and are not intended to limit the scope of the claims of the present invention.

[0026] In view of the technical problems of poor flame retardant effect and unsatisfactory appearance of existing flame-retardant laminated resins, this application provides a two-component halogen-free flame-retardant laminated resin and its preparation method. By selecting the components and their contents, the resulting halogen-free flame-retardant laminated resin exhibits good physical properties, good flame retardant effect, and high resin transparency. Specifically, this invention discloses a halogen-free flame-retardant laminated resin prepared from component A and component B:

[0027] Component A includes:

[0028]

[0029] Component B includes:

[0030] 40-60 parts by weight of polyetheramine;

[0031] Isophoroneamine 30-50 parts by weight;

[0032] 5-15 parts by weight of triethanolamine.

[0033] Specifically, the halogen-free flame-retardant laminated resin provided in this application is prepared from component A and component B, wherein component A includes a specific ratio of modified high-phosphorus epoxy resin, dimethyl methyl phosphate, non-crystalline epoxy resin, silane defoamer, fluorosilicone defoamer and silane coupling agent, and component B includes polyetheramine, isophoroneamine and triethanolamine.

[0034] The modified high-phosphorus epoxy resin is the main film-forming component and has flame-retardant properties. The preparation method of the modified high-phosphorus epoxy resin specifically involves adding triphosphazene to the epoxy resin monomer at a molar ratio of 1:0.8 and heating under reflux at 120°C for 2 hours. The content of the modified high-phosphorus epoxy resin is 55–75 parts by weight. Specifically, the content of the modified high-phosphorus epoxy resin is 60–70 parts by weight, and more specifically, the content of the modified high-phosphorus epoxy resin is 62–68 parts by weight.

[0035] The dimethyl methyl phosphate can further enhance the flame retardant effect, and its content is 5 to 20 parts by weight, specifically, the content of the dimethyl methyl phosphate is 10 to 15 parts by weight.

[0036] The amorphous epoxy resin effectively prevents crystallization and solves the problem of resin whitening during curing. In a specific embodiment, the amorphous epoxy resin is selected from Nan Ya NPEL-128s. The content of the amorphous epoxy resin is 15-25 parts by weight, specifically 18-22 parts by weight.

[0037] The silane defoamer is used to eliminate bubbles generated during the production process. It can be selected from [specific sources], and in this embodiment, the silane defoamer is selected from Deqian 6800. The content of the silane defoamer is 0.1 to 0.5 parts by weight, specifically, the content of the silane defoamer is 0.2 to 0.4 parts by weight.

[0038] The fluorosilicone defoamer can further eliminate bubbles generated during the production process. In this embodiment, the fluorosilicone defoamer can be selected from Entropy Energy DF280. The content of the fluorosilicone defoamer is 0.1 to 1.0 parts by weight, specifically, the content of the fluorosilicone defoamer is 0.2 to 0.8 parts by weight.

[0039] The silane coupling agent is used to increase adhesion. In a specific embodiment, the silane coupling agent is selected from Dow Corning 1121. The content of the silane coupling agent is 0.1 to 1.0 parts by weight, specifically, the content of the silane coupling agent is 0.3 to 0.8 parts by weight.

[0040] The polyetheramine can improve the transparency and curing speed of the resin; in a specific embodiment, the polyetheramine is selected from Huntsman T403. The content of the polyetheramine is 40 to 60 parts by weight, specifically, the content of the polyetheramine is 45 to 55 parts by weight, and more specifically, the content of the polyetheramine is 48 to 52 parts by weight.

[0041] The isophoroneamine is used to improve the overall performance of the resin after curing, and its content is 30 to 50 parts by weight. Specifically, the content of the isophoroneamine is 35 to 45 parts by weight, and more specifically, the content of the isophoroneamine is 38 to 42 parts by weight.

[0042] The triethanolamine enables rapid initial curing of the resin, and its content is 5 to 15 parts by weight, more specifically, the content of the triethanolamine is 8 to 12 parts by weight.

[0043] This application does not impose any particular restrictions on the source of the specific components in component A and component B; they can be prepared or commercially available products prepared in accordance with methods well known to those skilled in the art.

[0044] This application also provides a method for preparing a halogen-free flame-retardant laminated resin, comprising the following steps:

[0045] According to the component ratio, the modified high-phosphorus epoxy resin and dimethyl methyl phosphate were mixed and heated to obtain the initial mixture;

[0046] The initial mixture and amorphous epoxy resin were mixed, cooled, and then silane defoamer, fluorosilicone defoamer and silane coupling agent were added. After vacuuming, the mixture was cooled and filtered to obtain component A.

[0047] Polyetheramine, isophoroneamine and triethanolamine were mixed and reacted, and then vacuum was applied to obtain component B.

[0048] Components A and B are mixed and cured to obtain a halogen-free flame-retardant laminated resin.

[0049] In the preparation process of halogen-free flame-retardant laminated resin, this application first adds modified high-phosphorus epoxy resin and dimethyl methyl phosphate into a vacuum mixing tank according to the component ratio, stirs at 50-100 rpm, and heats to 80-120°C to obtain an initial mixture.

[0050] According to the present invention, the non-crystalline epoxy resin is then added to the above-mentioned vacuum mixing tank, the temperature is maintained and the mixture is stirred at a speed of 50-100 rpm for 30-60 min. After cooling to below 30-50°C, silane defoamer, fluorosilicone defoamer and silane coupling agent are added, and the mixture is stirred at a speed of 50-100 rpm for 10-20 min while vacuuming. Finally, the mixture is cooled to 30-50°C and filtered to obtain component A.

[0051] Meanwhile, polyetheramine, isophoroneamine, and triethanolamine can be added to a vacuum mixing tank according to the component ratio, and stirred at 20-30°C and 100-500 rpm for 10-30 minutes. Then, the speed is reduced by 10-50 rpm and vacuum is applied for 10-20 minutes to obtain component B.

[0052] In the end, the obtained components A and B are mixed and cured to obtain a halogen-free flame-retardant laminated resin.

[0053] This application also provides a fiber-reinforced composite material comprising a resin and fibers, wherein the resin is the inorganic flame-retardant laminated resin described in the above-described scheme.

[0054] The fibers in the fiber-reinforced composite materials described in this application are fibers well known to those skilled in the art, such as carbon fiber, glass fiber, or aramid fiber.

[0055] To further understand the present invention, the following detailed description of the halogen-free flame-retardant laminated resin and its preparation method provided by the present invention is provided in conjunction with embodiments. The scope of protection of the present invention is not limited by the following embodiments.

[0056] Example 1

[0057] (1) Raw material ratio:

[0058] 1. A two-component, room-temperature thermosetting halogen-free flame-retardant epoxy laminate resin, made from raw materials including the following components:

[0059] Component A:

[0060]

[0061] Component B:

[0062] Polyetheramine T403 55 parts by weight;

[0063] 40 parts by weight of isoflurane;

[0064] 5 parts by weight of triethanolamine;

[0065] (2) The preparation method steps are as follows:

[0066] After accurately weighing the modified high-phosphorus epoxy resin and dimethyl methyl phosphate, add them to a vacuum mixing tank, stir at 80 rpm, and heat to 90℃.

[0067] After accurately weighing the non-crystalline epoxy resin raw material, gradually add it into the mixing tank, maintain the temperature at 90℃ and the speed at 60 rpm. After the raw material is completely dissolved, continue stirring for 30 minutes. After cooling to below 40℃, add silane defoamer, fluorosilicone defoamer and silane coupling agent. Maintain the stirring speed at 60 rpm for 15 minutes, and simultaneously apply a vacuum.

[0068] After passing the test, the product is cooled to below 40℃ and then filtered through a 200-mesh filter before packaging to obtain component A;

[0069] The polyetheramine, isophoroneamine, and triethanolamine were accurately weighed and added into a vacuum stirring tank. The stirring temperature was 25℃~30℃, the stirring speed was 200rpm, and the time was 18min. Then the stirring speed was reduced by 30rpm and a vacuum was drawn for 10min to obtain component B.

[0070] Component A and component B are mixed and cured to obtain a laminated resin.

[0071] Example 2

[0072] The raw material ratio and preparation method provided in Example 1 are used, except that: 70 parts by weight of bisphenol A epoxy resin and 0 parts by weight of modified high phosphorus content epoxy resin.

[0073] Example 3

[0074] The raw material ratio and preparation method provided in Example 1 are used, with the difference being: 55 parts by weight of modified high phosphorus epoxy resin and 40 parts by weight of bisphenol A epoxy resin (an additional component is added based on Example 1).

[0075] Comparative Example 1: Flame-retardant epoxy laminated resin (NO.1) purchased from the market.

[0076] Comparative Example 2: Flame-retardant epoxy resin (FR05) purchased from the market.

[0077] The performance of the products provided in Examples 1-3 and Comparative Examples 1-2 was tested. The specific tests and test methods included:

[0078] (1) Carbon fiber impregnation test: 25×25×0.5mm dry carbon fiber cloth, resin was introduced on the left and vacuum was applied on the right; compare the time it took for the carbon fiber to be completely impregnated and the appearance after curing.

[0079] (2) Bending test: The cured resin is made into a specimen of 80×25×0.5mm and the bending modulus is tested by a universal tensile testing machine.

[0080] (3) Hardness test: Shore D hardness tester;

[0081] (4) Flame retardant effect test: After the resin block is cured and composited with carbon fiber, it is ignited with a windproof lighter for 20 seconds, and then the fire source is removed. Observe whether the flame of the resin block is extinguished within 10 seconds.

[0082] The test results for the above items are shown in Table 1.

[0083] Table 1. Performance data of the resins prepared in Examples 1-3 and Comparative Examples 1-2

[0084]

[0085]

[0086] The above description of the embodiments is only for the purpose of helping to understand the method and core ideas of the present invention. It should be noted that those skilled in the art can make several improvements and modifications to the present invention without departing from the principles of the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.

[0087] The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A halogen-free flame-retardant laminated resin, prepared from component A and component B: Component A includes: Component B includes: 40-60 parts by weight of polyetheramine; Isophoroneamine 30-50 parts by weight; 5-15 parts by weight of triethanolamine; The specific preparation method of the modified high phosphorus content epoxy resin is as follows: triphosphazene is added to the epoxy resin monomer at a molar ratio of 1:0.8, and the mixture is heated and refluxed at 120°C for 2 hours. The non-crystalline epoxy resin is selected from South Asia NPEL-128s.

2. The halogen-free flame-retardant laminated resin according to claim 1, characterized in that, The silane defoamer is selected from Deqian 6800, and the fluorosilicone defoamer is selected from Entropy Energy DF280.

3. The halogen-free flame-retardant laminated resin according to claim 1, characterized in that, The modified high-phosphorus epoxy resin content is 60-70 parts by weight.

4. The halogen-free flame-retardant laminated resin according to claim 1, characterized in that, The content of dimethyl methyl phosphate is 10 to 15 parts by weight.

5. The halogen-free flame-retardant laminated resin according to claim 1, characterized in that, The content of the non-crystalline epoxy resin is 18 to 22 parts by weight.

6. The halogen-free flame-retardant laminated resin according to claim 1, characterized in that, The content of the polyetheramine is 45-55 parts by weight, the content of the isophoroneamine is 35-45 parts by weight, and the content of the triethanolamine is 8-12 parts by weight.

7. A method for preparing the halogen-free flame-retardant laminated resin according to any one of claims 1 to 6, comprising the following steps: According to the component ratio, the modified high-phosphorus epoxy resin and dimethyl methyl phosphate were mixed and heated to obtain the initial mixture; The initial mixture and amorphous epoxy resin were mixed, cooled, and then silane defoamer, fluorosilicone defoamer and silane coupling agent were added. After vacuuming, the mixture was cooled and filtered to obtain component A. Polyetheramine, isophoroneamine and triethanolamine were mixed and reacted, and then vacuum was applied to obtain component B. Components A and B are mixed and cured to obtain a halogen-free flame-retardant laminated resin.

8. A fiber-reinforced composite material, comprising resin and fiber, characterized in that, The resin is the halogen-free flame-retardant laminated resin according to any one of claims 1 to 6 or the halogen-free flame-retardant laminated resin prepared by the preparation method according to claim 7.

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