Preparation method of high-toughness flame-retardant epoxy resin adhesive

Abstract

The invention relates to the technical field of adhesive production, in particular to a preparation method of a high-toughness flame-retardant epoxy resin adhesive. The high-toughness flame-retardant epoxy resin adhesive is prepared from the following raw materials in parts by weight: 35 to 40 parts of bisphenol F type epoxy resin, 8 to 10 parts of functional additive, 10 to 14 parts of reinforcing filler, 10 to 12 parts of curing agent, 8 to 10 parts of accelerant and 5 to 8 parts of benzyl alcohol, the high-toughness flame-retardant epoxy resin adhesive is prepared by mixing the bisphenol F type epoxy resin and the functional additive, adding the reinforcing filler into the mixture, continuously mixing, adding the curing agent, the accelerant and the benzyl alcohol, and mixing. The high-toughness flame-retardant epoxy resin adhesive prepared by the preparation method disclosed by the invention not only has better mechanical properties, but also has excellent flame retardance, and the quality of the high-toughness flame-retardant epoxy resin adhesive is effectively ensured.

Description

Technical Field

[0001] The present invention relates to the technical field of adhesive production, and specifically to a preparation method of a high-toughness flame-retardant epoxy resin adhesive. Background Technique

[0002] Epoxy resin is a widely used thermosetting resin, which is widely used in many fields such as construction, flooring, automobiles, aerospace, adhesives, etc., especially in the field of adhesives.

[0003] Traditional epoxy resin adhesives have some obvious defects, which limit their application in more special scenarios. On the one hand, their toughness is insufficient, and when subjected to external force impact, cracks or even fractures are likely to occur; on the other hand, the flame-retardant performance is poor. With the continuous improvement of people's awareness of fire safety, higher requirements for the flame-retardant performance of materials are put forward in many application scenarios. Especially in the fields of electronic appliances and construction, in the event of a fire, ordinary epoxy resin adhesives may burn rapidly, fueling the spread of the fire and causing serious casualties and property losses.

[0004] Based on this, the present invention provides a preparation method of a high-toughness flame-retardant epoxy resin adhesive to solve the above-mentioned technical problems. Summary of the Invention

[0005] The purpose of the present invention is to provide a preparation method of a high-toughness flame-retardant epoxy resin adhesive. The high-toughness flame-retardant epoxy resin adhesive prepared by the present invention not only has good mechanical properties, but also has excellent flame-retardant properties, effectively ensuring its quality and quality.

[0006] To achieve the above purpose, the present invention provides the following technical solutions:

[0007] The present invention provides a preparation method of a high-toughness flame-retardant epoxy resin adhesive. The high-toughness flame-retardant epoxy resin adhesive is composed of the following raw materials in parts by weight: 35-40 parts of bisphenol F type epoxy resin, 8-10 parts of functional additives, 10-14 parts of reinforcing fillers, 10-12 parts of curing agents, 8-10 parts of accelerators, and 5-8 parts of benzyl alcohol;

[0008] The preparation method of the high-toughness flame-retardant epoxy resin adhesive includes the following steps:

[0009] Accurately weigh bisphenol F type epoxy resin, functional additives, reinforcing fillers, curing agents, accelerators, and benzyl alcohol, and set aside;

[0010] Mix bisphenol F type epoxy resin and functional additives at 550-650 r / min for 8-10 min, then add reinforcing fillers thereto, and mix at 120-220 r / min for 40-50 min;

[0011] Under the condition of 20 - 30 °C, a curing agent, an accelerator and benzyl alcohol are added, and they are mixed for 30 - 40 min under the condition of 300 - 400 r / min to prepare a high-toughness flame-retardant epoxy resin adhesive.

[0012] A further setting of the present invention is as follows: The preparation process of the functional additive is as follows:

[0013] Bisphenol A and potassium carbonate are mixed according to a mass ratio of 1:1.12 - 1.34 to obtain a premix;

[0014] The premix is placed in N,N-dimethylacetamide according to a dosage ratio of 0.12 - 0.22 g / mL, and stirred for 10 - 15 min under a nitrogen atmosphere and at 200 - 300 r / min, then heated to 160 - 170 °C and heat-preserved for 120 - 150 min. 4,4'-difluorobenzophenone accounting for 95 - 98% of the mass of bisphenol A is added thereto, and heat preservation is continued for 6 - 8 h to obtain a first base material;

[0015] The compound solution and the compound ingredients are stirred for 30 - 60 min under the condition of 120 - 200 r / min according to a mass ratio of 0.5 - 1:1. After suction filtration, they are dried at 80 - 90 °C for 3 - 5 h to obtain a second base material;

[0016] The second base material and the first base material are stirred and mixed for 60 - 100 min under the conditions of 300 - 380 r / min and 80 - 90 °C according to a mass ratio of 0.15 - 0.25:1. Epichlorohydrin accounting for 6 - 10% of the mass of the first base material is added dropwise thereto. After the addition is completed, the temperature is raised to 100 - 110 °C and heat preservation is carried out for 4 - 6 h. After cooling to room temperature, a preparation product is obtained. Deionized water accounting for 300 - 400% of the mass of the preparation product is added thereto, and it is stirred for 20 - 30 min under the condition of 120 - 220 r / min. After suction filtration, it is washed with deionized water 2 - 4 times, and then vacuum dried at 60 - 80 °C for 22 - 24 h to obtain the functional additive.

[0017] A further setting of the present invention is as follows: The compound solution is compounded from γ-glycidoxypropyltrimethoxysilane and absolute ethanol according to a mass ratio of 1:40 - 48.

[0018] A further setting of the present invention is as follows: The compound ingredients are compounded from aluminum hydroxide and melamine polyphosphate according to a mass ratio of 2 - 3:1.

[0019] A further setting of the present invention is as follows: The preparation process of the reinforcing filler is as follows:

[0020] Place basalt fibers in a KH550 ethanol solution with a volume concentration of 2-4% at a dosage ratio of 0.05-0.15 g / mL, carry out condensation reflux at 80-90 °C for 120-140 min, after suction filtration, dry at 100-120 °C for 12-14 h to obtain pretreated basalt fibers;

[0021] Place the pretreated basalt fibers in dimethyl sulfoxide at a dosage ratio of 0.22-0.32 g / mL and carry out ultrasonic treatment for 20-30 min to obtain a first solution;

[0022] Place p-phenylenediamine in dimethyl sulfoxide at a dosage ratio of 0.08-0.12 g / mL and carry out ultrasonic treatment for 5-10 min to obtain a second solution;

[0023] Under the condition of 120-140 r / min, add the second solution dropwise to the first solution at a mass ratio of 0.25-0.35:1, then add phosphorus oxychloride and pyridine thereto, continue stirring at 50-70 °C for 10-14 h, carry out suction filtration, and wash with dimethyl sulfoxide and acetone 2-4 times respectively, dry at 80-90 °C for 12-14 h to obtain an enhanced filler.

[0024] A further setting of the present invention is that: the added mass of the pyridine is 65-85% of the p-phenylenediamine.

[0025] A further setting of the present invention is that: the added mass of the phosphorus oxychloride is 170-180% of the p-phenylenediamine.

[0026] A further setting of the present invention is that: the curing agent is selected from any one of diethylenetriamine and ethylenediamine.

[0027] A further setting of the present invention is that: the accelerator is selected from any one of 1,1-dimethyl-3-phenylurea and 1,3-dimethyl-2-imidazolidinone.

[0028] Compared with the prior art, the beneficial effects of the present invention are:

[0029] In the present invention, using bisphenol F type epoxy resin, functional additives, enhanced filler, curing agent, accelerator and benzyl alcohol as raw materials, by mixing bisphenol F type epoxy resin and functional additives, then adding enhanced filler thereto and continuing to mix, and then adding curing agent, accelerator and benzyl alcohol to mix, a high-toughness flame-retardant epoxy resin adhesive is prepared. The high-toughness flame-retardant epoxy resin adhesive prepared by the present invention not only has good mechanical properties, but also has excellent flame-retardant properties, effectively ensuring its quality and quality. The preparation method of the high-toughness flame-retardant epoxy resin adhesive provided by the present invention has a broader market prospect and is more suitable for popularization. Specific embodiments

[0030] Next, in combination with the embodiments of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts belong to the scope of protection of the present invention.

[0031] Embodiment 1

[0032] This embodiment provides a preparation method of a high-toughness flame-retardant epoxy resin adhesive. The high-toughness flame-retardant epoxy resin adhesive is composed of the following raw materials in parts by weight: 35 parts of bisphenol F-type epoxy resin, 8 parts of functional additives, 10 parts of reinforcing fillers, 10 parts of curing agents, 8 parts of accelerators, and 5 parts of benzyl alcohol.

[0033] In this embodiment, it should be noted that the bisphenol F-type epoxy resin is purchased from Shandong Duopoly Chemical Co., Ltd.

[0034] Among them, the preparation process of the functional additives is as follows:

[0035] Bisphenol A and potassium carbonate are mixed in a mass ratio of 1:1.12 to obtain a premix;

[0036] The premix is placed in N,N-dimethylacetamide at a dosage ratio of 0.12 g / mL, stirred at 200 r / min under a nitrogen atmosphere for 10 min, heated to 160 °C, and kept warm for 120 min. 4,4'-difluorobenzophenone accounting for 95% of the mass of bisphenol A is added thereto, and the mixture is continuously kept warm for 6 h to obtain a first base material;

[0037] The compound solution and the compound ingredients are stirred at a mass ratio of 0.5:1 at 120 r / min for 30 min, filtered by suction, and then dried at 80 °C for 3 h to obtain a second base material;

[0038] The second base material and the first base material are stirred and mixed at a mass ratio of 0.15:1 at 300 r / min and 80 °C for 60 min. Epichlorohydrin accounting for 6% of the mass of the first base material is added dropwise thereto. After the addition is completed, the temperature is raised to 100 °C and kept warm for 4 h. After cooling to room temperature, a prepared product is obtained. Deionized water accounting for 300% of the mass of the prepared product is added thereto, and the mixture is stirred at 120 r / min for 20 min, filtered by suction, washed twice with deionized water, and then vacuum-dried at 60 °C for 22 h to obtain the functional additives.

[0039] Furthermore, the compound solution is compounded from γ-glycidoxypropyltrimethoxysilane and absolute ethanol in a mass ratio of 1:40.

[0040] The compounding ingredient is compounded from aluminum hydroxide and melamine polyphosphate according to a mass ratio of 2:1.

[0041] In this embodiment, it should be noted that bisphenol A is purchased from Shandong Kunteng Chemical Co., Ltd.

[0042] Among them, the preparation process of the reinforcing filler is as follows:

[0043] Place basalt fibers in a KH550 ethanol solution with a volume concentration of 2% according to a dosage ratio of 0.05 g / mL, carry out condensation reflux at 80 °C for 120 min, after suction filtration, dry at 100 °C for 12 h to obtain pretreated basalt fibers;

[0044] Place the pretreated basalt fibers in dimethyl sulfoxide according to a dosage ratio of 0.22 g / mL and ultrasonically treat for 20 min to obtain a first solution;

[0045] Place p-phenylenediamine in dimethyl sulfoxide according to a dosage ratio of 0.08 g / mL and ultrasonically treat for 5 min to obtain a second solution;

[0046] Under the condition of 120 r / min, add the second solution dropwise to the first solution according to a mass ratio of 0.25:1, then add phosphorus oxychloride and pyridine thereto, continue stirring at 50 °C for 10 h, carry out suction filtration, and wash twice with dimethyl sulfoxide and acetone respectively, and dry at 80 °C for 12 h to obtain the reinforcing filler.

[0047] Furthermore, the added mass of pyridine is 65% of that of p-phenylenediamine.

[0048] The added mass of phosphorus oxychloride is 170% of that of p-phenylenediamine.

[0049] In this embodiment, it should be noted that basalt fibers are purchased from Hebei Hengguang Mineral Products Co., Ltd.

[0050] Among them, the curing agent is selected as diethylenetriamine.

[0051] The accelerator is selected as 1,1-dimethyl-3-phenylurea.

[0052] In addition, this embodiment also provides a preparation method of the above high-toughness flame-retardant epoxy resin adhesive, including the following steps:

[0053] Accurately weigh bisphenol F-type epoxy resin, functional additives, reinforcing filler, curing agent, accelerator and benzyl alcohol, and set aside;

[0054] Mix bisphenol F-type epoxy resin and functional additives at 550 r / min for 8 min, then add the reinforcing filler thereto and mix at 120 r / min for 40 min;

[0055] Under the condition of 20 °C, a curing agent, an accelerator and benzyl alcohol were added, and they were mixed for 30 min under the condition of 300 r / min to prepare a high-toughness flame-retardant epoxy resin adhesive.

[0056] Example 2

[0057] The preparation method of the high-toughness flame-retardant epoxy resin adhesive provided in this example is basically the same as that in Example 1, except that: the specific raw material composition and the specific preparation method of the high-toughness flame-retardant epoxy resin adhesive in this example are different; the specific raw material composition and the specific preparation method of the high-toughness flame-retardant epoxy resin adhesive in this example are as follows:

[0058] A preparation method of a high-toughness flame-retardant epoxy resin adhesive, and the high-toughness flame-retardant epoxy resin adhesive is composed of the following raw materials in parts by weight: 37 parts of bisphenol F-type epoxy resin, 9 parts of functional additives, 12 parts of reinforcing filler, 11 parts of curing agent, 9 parts of accelerator and 7 parts of benzyl alcohol.

[0059] In this example, it should be noted that the bisphenol F-type epoxy resin was purchased from Shandong Duoju Chemical Co., Ltd.

[0060] Among them, the preparation process of the functional additives is as follows:

[0061] Bisphenol A and potassium carbonate were mixed according to a mass ratio of 1:1.23 to obtain a premix;

[0062] The premix was placed in N,N-dimethylacetamide according to a dosage ratio of 0.17 g / mL, and stirred for 12 min under the conditions of a nitrogen atmosphere and 250 r / min, heated to 165 °C, and heat-insulated for 135 min. 4,4'-difluorobenzophenone accounting for 96% of the mass of bisphenol A was added thereto, and heat-insulation treatment was continued for 7 h to obtain a first base material;

[0063] The compound solution and the compounding material were stirred for 45 min under the condition of 160 r / min according to a mass ratio of 0.7:1. After filtration, they were dried at 85 °C for 4 h to obtain a second base material;

[0064] The second base material and the first base material were stirred and mixed for 80 min under the conditions of 340 r / min and 85 °C according to a mass ratio of 0.2:1. Epichlorohydrin accounting for 8% of the mass of the first base material was added dropwise thereto. After the addition was completed, the temperature was raised to 105 °C and heat-insulated for 5 h. After cooling to room temperature, a prepared product was obtained. Deionized water accounting for 350% of the mass of the prepared product was added thereto, and it was stirred for 25 min under the condition of 170 r / min. After filtration, it was washed 3 times with deionized water, and then vacuum-dried at 70 °C for 23 h to obtain the functional additives.

[0065] Further, the compound solution is prepared by compounding γ-glycidyletheroxypropyltrimethoxysilane and absolute ethanol in a mass ratio of 1:44.

[0066] The compounding material is prepared by compounding aluminum hydroxide and melamine polyphosphate in a mass ratio of 3:1.

[0067] In this embodiment, it should be noted that bisphenol A is purchased from Shandong Kunteng Chemical Co., Ltd.

[0068] Among them, the preparation process of the reinforcing filler is as follows:

[0069] Place basalt fibers in a KH550 ethanol solution with a volume concentration of 3% at a dosage ratio of 0.1 g / mL, carry out condensation reflux at 85 °C for 130 min, after suction filtration, dry at 110 °C for 13 h to obtain pretreated basalt fibers;

[0070] Place the pretreated basalt fibers in dimethyl sulfoxide at a dosage ratio of 0.27 g / mL and perform ultrasonic treatment for 25 min to obtain a first solution;

[0071] Place p-phenylenediamine in dimethyl sulfoxide at a dosage ratio of 0.08 - 0.12 g / mL and perform ultrasonic treatment for 7 min to obtain a second solution;

[0072] Under the condition of 130 r / min, add the second solution dropwise to the first solution at a mass ratio of 0.3:1, then add phosphorus oxychloride and pyridine thereto, continue stirring at 60 °C for 12 h, perform suction filtration, and wash with dimethyl sulfoxide and acetone 3 times respectively, and dry at 85 °C for 13 h to obtain the reinforcing filler.

[0073] Further, the added mass of pyridine is 75% of that of p-phenylenediamine.

[0074] The added mass of phosphorus oxychloride is 175% of that of p-phenylenediamine.

[0075] In this embodiment, it should be noted that basalt fibers are purchased from Hebei Hengguang Mineral Products Co., Ltd.

[0076] Among them, the curing agent is selected as ethylenediamine.

[0077] The accelerator is selected as 1,3-dimethyl-2-imidazolidinone.

[0078] In addition, this embodiment also provides a preparation method of the above high-toughness flame-retardant epoxy resin adhesive, including the following steps:

[0079] Accurately weigh bisphenol F-type epoxy resin, functional additives, reinforcing filler, curing agent, accelerator and benzyl alcohol, and set aside;

[0080] Mix bisphenol F epoxy resin and functional additives at 600 r / min for 9 min, then add reinforcing filler thereto and mix at 170 r / min for 45 min;

[0081] At 25 °C, add curing agent, accelerator and benzyl alcohol, and mix at 350 r / min for 35 min to prepare a high-toughness flame-retardant epoxy resin adhesive.

[0082] Example 3

[0083] The preparation method of the high-toughness flame-retardant epoxy resin adhesive provided in this example is basically the same as that of Example 1, except that: the specific raw material composition and the specific preparation method of the high-toughness flame-retardant epoxy resin adhesive in this example are different; the specific raw material composition and the specific preparation method of the high-toughness flame-retardant epoxy resin adhesive in this example are as follows:

[0084] A preparation method of a high-toughness flame-retardant epoxy resin adhesive, and the high-toughness flame-retardant epoxy resin adhesive is composed of the following raw materials in parts by weight: 40 parts of bisphenol F epoxy resin, 10 parts of functional additives, 14 parts of reinforcing filler, 12 parts of curing agent, 10 parts of accelerator and 8 parts of benzyl alcohol.

[0085] In this example, it should be noted that the bisphenol F epoxy resin is purchased from Shandong Duoju Chemical Co., Ltd.

[0086] Among them, the preparation process of the functional additives is as follows:

[0087] Mix bisphenol A and potassium carbonate according to a mass ratio of 1:1.34 to obtain a premix;

[0088] Place the premix in N,N-dimethylacetamide according to a dosage ratio of 0.22 g / mL, stir at 300 r / min under a nitrogen atmosphere for 15 min, heat up to 170 °C, and keep warm for 150 min. Add 4,4′-difluorobenzophenone which is 98% of the mass of bisphenol A thereto, and continue to keep warm for 8 h to obtain a first base material;

[0089] Stir the compounding solution and the compounding ingredients according to a mass ratio of 1:1 at 200 r / min for 360 min, perform suction filtration, and then dry at 90 °C for 5 h to obtain a second base material;

[0090] The second base material and the first base material are stirred and mixed at 380 r / min and 90 °C for 100 min according to a mass ratio of 0.25:1. Then, epichlorohydrin accounting for 10% of the mass of the first base material is dropped into it. After the dropping is completed, the temperature is raised to 110 °C and heat preservation treatment is carried out for 6 h. After cooling to room temperature, a formulated product is obtained. Deionized water accounting for 400% of the mass of the formulated product is added to it, and it is stirred for 30 min under the condition of 220 r / min. After suction filtration, it is washed 4 times with deionized water, and then placed under the condition of 80 °C for vacuum drying for 24 h to obtain a functional auxiliary agent.

[0091] Further, the compounding solution is compounded from γ-glycidyl ether oxypropyltrimethoxysilane and absolute ethanol according to a mass ratio of 1:48.

[0092] The compounding material is compounded from aluminum hydroxide and melamine polyphosphate according to a mass ratio of 3:1.

[0093] In this embodiment, it should be noted that bisphenol A is purchased from Shandong Kunteng Chemical Co., Ltd.

[0094] Among them, the preparation process of the reinforcing filler is as follows:

[0095] The basalt fiber is placed in a KH550 ethanol solution with a volume concentration of 4% according to a dosage ratio of 0.15 g / mL, and is subjected to condensation reflux at 90 °C for 140 min. After suction filtration, it is placed under the condition of 120 °C for drying for 14 h to obtain pretreated basalt fiber;

[0096] The pretreated basalt fiber is placed in dimethyl sulfoxide and ultrasonically treated for 30 min according to a dosage ratio of 0.32 g / mL to obtain a first solution; p-phenylenediamine is placed in dimethyl sulfoxide and ultrasonically treated for 10 min according to a dosage ratio of 0.12 g / mL to obtain a second solution;

[0097] Under the condition of 140 r / min, the second solution is dropped into the first solution according to a mass ratio of 0.35:1, and then phosphorus oxychloride and pyridine are added to it respectively. It is continuously stirred and treated at 70 °C for 14 h, suction filtered, and washed 4 times with dimethyl sulfoxide and acetone respectively, and placed under the condition of 90 °C for drying for 14 h to obtain a reinforcing filler.

[0098] Further, the added mass of pyridine is 85% of that of p-phenylenediamine.

[0099] The added mass of phosphorus oxychloride is 180% of that of p-phenylenediamine.

[0100] In this embodiment, it should be noted that the basalt fiber is purchased from Hebei Hengguang Mineral Products Co., Ltd.

[0101] Among them, the curing agent is selected as diethylenetriamine.

[0102] The accelerator selected is 1,1-dimethyl-3-phenylurea.

[0103] In addition, this embodiment also provides a preparation method for the above high-toughness flame-retardant epoxy resin adhesive, including the following steps:

[0104] Accurately weigh bisphenol F epoxy resin, functional additives, reinforcing fillers, curing agents, accelerators, and benzyl alcohol, and set aside;

[0105] Mix bisphenol F epoxy resin and functional additives at 650 r / min for 10 min, then add reinforcing fillers thereto and mix at 220 r / min for 50 min;

[0106] At 30 °C, add the curing agent, accelerator, and benzyl alcohol, and mix at 400 r / min for 40 min to prepare a high-toughness flame-retardant epoxy resin adhesive.

[0107] Comparative Example 1: The difference from Example 1 is that in this example, an equal amount of polyethylene glycol 600 (purchased from Jinan Xinke Chemical Co., Ltd.) is used to replace the functional additive.

[0108] Comparative Example 2: The difference from Example 1 is that in this example, an equal amount of basalt fiber is used to replace the reinforcing filler.

[0109] Performance test: The high-toughness flame-retardant epoxy resin adhesive samples provided in Examples 1 to 3 and Comparative Examples 1 to 2 are respectively labeled as Examples 1 to 3 and Comparative Examples 1 to 2; and the following tests are respectively carried out on the relevant performances of the high-toughness flame-retardant epoxy resin adhesives provided in Examples 1 to 3 and Comparative Examples 1 to 2:

[0110] 1. Mechanical property test: The test method is to conduct tensile strength test according to the standard of GB / T528-1998; conduct tensile shear strength test according to the standard of GB / T7124-2008ISO4587:2003; conduct shear impact strength test according to the standard of GB / T6328-1999.

[0111] 2. Flame retardancy test: The test method is to conduct a flame retardancy test according to the standard of GB / T2406.2-2009.

[0112] The obtained test data are recorded in Table 1 and Table 2 below:

[0113] Table 1 Test results of the mechanical properties of each group of epoxy resin adhesives

[0114]

[0115]

[0116] Table 2 Test Results of Flame Retardant Properties of Epoxy Resin Adhesives in Each Group

[0117] Group Limiting oxygen index (%) Example 1 group 32 Example 2 group 31 Example 3 group 33 Control 1 group 23 Control 2 group 25

[0118] By comparing and analyzing the relevant data in Table 1 and Table 2, it can be seen that the high-toughness flame-retardant epoxy resin adhesive prepared by the present invention not only has good mechanical properties, but also has excellent flame-retardant properties, effectively ensuring its quality and quality. This shows that the preparation method of the high-toughness flame-retardant epoxy resin adhesive provided by the present invention has a broader market prospect and is more suitable for popularization.

[0119] In the description of this specification, the descriptions referring to terms such as "one embodiment", "example", "specific example", etc. mean that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in a suitable manner in any one or more embodiments or examples.

[0120] The preferred embodiments of the present invention disclosed above are only used to help explain the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific embodiments described. Obviously, many modifications and variations can be made according to the content of this specification. The present specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and utilize the present invention well. The present invention is only limited by the claims and their full scope and equivalents.

Claims

1. A method for preparing a high-toughness flame-retardant epoxy resin adhesive, characterized in that: The high-toughness flame-retardant epoxy resin adhesive is composed of the following raw materials in parts by weight: 35 to 40 parts of bisphenol F epoxy resin, 8 to 10 parts of functional additives, 10 to 14 parts of reinforcing fillers, 10 to 12 parts of curing agents, 8 to 10 parts of accelerators and 5 to 8 parts of benzyl alcohol; The preparation method of the high-toughness flame-retardant epoxy resin adhesive comprises the following steps: Accurately weigh bisphenol F epoxy resin, functional additives, reinforcing fillers, curing agents, accelerators and benzyl alcohol and set aside; Mix the bisphenol F epoxy resin and the functional additive at 550-650 r / min for 8-10 minutes, add the reinforcing filler therein, and mix at 120-220 r / min for 40-50 minutes; A curing agent, an accelerator and benzyl alcohol were added at 20-30° C. and mixed at 300-400 r / min for 30-40 min to prepare a high-toughness flame-retardant epoxy resin adhesive.

2. The method for preparing a high-toughness flame-retardant epoxy resin adhesive according to claim 1, characterized in that: The preparation process of the functional additive is as follows: Bisphenol A and potassium carbonate are mixed in a mass ratio of 1:1.12-1.34 to obtain a premix; The premix is ​​placed in N,N-dimethylacetamide at a dosage ratio of 0.12-0.22 g / mL, stirred for 10-15 min under a nitrogen atmosphere at 200-300 r / min, heated to 160-170° C., and heat-treated for 120-150 min, 4,4′-difluorobenzophenone in an amount of 95-98% of the mass of bisphenol A is added thereto, and heat-treated for 6-8 h to obtain a first base material; The compound solution and the compound ingredients are stirred at 120 to 200 r / min for 30 to 60 min in a mass ratio of 0.5 to 1:1, filtered, and dried at 80 to 90° C. for 3 to 5 h to obtain a second base material; The second base material and the first base material are stirred and mixed at a mass ratio of 0.15 to 0.25:1 at 300 to 380 r / min and 80 to 90°C for 60 to 100 minutes, 6 to 10% of epichlorohydrin by mass of the first base material is added dropwise thereto, the temperature is raised to 100 to 110°C after the addition is completed, the temperature is kept for 4 to 6 hours, and the prepared product is obtained after cooling to room temperature, deionized water of 300 to 400% by mass of the prepared product is added thereto, the product is stirred at 120 to 220 r / min for 20 to 30 minutes, filtered, washed with deionized water for 2 to 4 times, and then dried in vacuo at 60 to 80°C for 22 to 24 hours to obtain a functional additive.

3. The method for preparing a high-toughness flame-retardant epoxy resin adhesive according to claim 2, characterized in that: The compound solution is compounded by mixing γ-glycidyloxypropyltrimethoxysilane and anhydrous ethanol in a mass ratio of 1:40-48.

4. The method for preparing a high-toughness flame-retardant epoxy resin adhesive according to claim 2, characterized in that: The compound material is prepared by compounding aluminum hydroxide and melamine polyphosphate in a mass ratio of 2 to 3:

1.

5. The method for preparing a high-toughness flame-retardant epoxy resin adhesive according to claim 1, characterized in that: The preparation process of the reinforcing filler is as follows: The basalt fiber is placed in a KH550 ethanol solution with a volume concentration of 2-4% at a dosage ratio of 0.05-0.15 g / mL, condensed and refluxed at 80-90° C. for 120-140 min, filtered, and dried at 100-120° C. for 12-14 h to obtain pretreated basalt fiber; The basalt fiber pretreated at a dosage ratio of 0.22 to 0.32 g / mL is placed in dimethyl sulfoxide for ultrasonic treatment for 20 to 30 minutes to obtain a first solution; p-phenylenediamine is placed in dimethyl sulfoxide at a dosage of 0.08 to 0.12 g / mL and subjected to ultrasonic treatment for 5 to 10 minutes to obtain a second solution; At 120-140 r / min, add the second solution dropwise into the first solution at a mass ratio of 0.25-0.35:1, then add phosphorus oxychloride and pyridine respectively, continue stirring at 50-70°C for 10-14 hours, filter, wash with dimethyl sulfoxide and acetone for 2-4 times respectively, and dry at 80-90°C for 12-14 hours to obtain a reinforced filler.

6. The method for preparing a high-toughness flame-retardant epoxy resin adhesive according to claim 5, characterized in that: The added mass of the pyridine is 65-85% of the p-phenylenediamine.

7. The method for preparing a high-toughness flame-retardant epoxy resin adhesive according to claim 5, characterized in that: The added mass of the phosphorus oxychloride is 170-180% of p-phenylenediamine.

8. The method for preparing a high-toughness flame-retardant epoxy resin adhesive according to claim 1, characterized in that: The curing agent is selected from any one of diethylenetriamine and ethylenediamine.

9. The method for preparing a high-toughness flame-retardant epoxy resin adhesive according to claim 1, characterized in that: The accelerator is selected from any one of 1,1-dimethyl-3-phenylurea and 1,3-dimethyl-2-imidazolidinone.

Images