Smoke suppressant and epoxy resin material

Abstract

The invention discloses a smoke suppressant and an epoxy resin material, and belongs to the technical field of epoxy resin materials. The smoke suppressant is prepared by heating and mixing a copper-containing compound, citric acid, a calcium-containing compound and water to obtain a gelatinous substance, drying the gelatinous substance and then calcining the gelatinous substance, the molar ratio of the copper-containing compound to the citric acid is (1-5): 1; the molar ratio of copper in the copper-containing compound to calcium in the calcium-containing compound is (6-15): 1; the heating and mixing temperature is 40 DEG C to 100 DEG C. Through the combined action of the smoke suppressant, the epoxy resin, the liquid phosphorus flame retardant and the curing agent, the prepared epoxy resin material can reduce the heat release rate peak value and the total smoke generation amount during combustion at the same time, and then the flame retardant property of the epoxy resin material is improved.

Description

Technical Field

[0001] The present invention relates to the technical field of epoxy resin materials, and particularly relates to a smoke suppressant and an epoxy resin material. Background Art

[0002] Epoxy resin, as a common thermosetting resin, has many excellent properties. With the increasingly strict environmental protection regulations, many industries such as aerospace, electronics and electrical, etc. have higher requirements for the combustion performance of materials. However, epoxy resin itself is flammable, and when burning, it will release a large amount of heat, increasing the fire risk. The generated smoke and harmful gases (such as carbon monoxide, etc.) are harmful to the environment and human health. By reducing the heat release and smoke generation of epoxy resin, the fire safety can be significantly improved, the danger during a fire can be reduced, the combustion performance can be improved, the application range can be broadened, and higher industry requirements can be met.

[0003] Flame retardant modification is the main method to reduce the heat and smoke released during the combustion of epoxy resin. Common flame retardants include halogen-based, phosphorus-based, nitrogen-based and metal hydroxide flame retardants, etc. Among them, phosphorus-based flame retardants have the advantages of diverse structural designs, high flame retardant efficiency and being more environmentally friendly, and are halogen-free flame retardants that have received more attention in recent years. However, these flame retardants are usually in solid form and are prone to clogging the resin delivery pipeline when preparing fiber flame retardant cured products by vacuum-assisted resin infusion molding process, affecting the processing of products. Some liquid phosphorus-based flame retardants will also cause an increase in smoke generation while reducing the heat release. Therefore, many researchers adopt the strategy of compounding a synergist with a phosphorus-based flame retardant to simultaneously reduce the heat release and smoke release. Chen et al. [Ind Eng Chem Res, 2015, 54: 12705] prepared flame retardant EP composites by using different mass fractions of Cu2O and microencapsulated ammonium polyphosphate (MAPP). Compared with pure EP, the peak heat release rate and total smoke generation amount of EP / 18% MAPP / 2% Cu2O were reduced by 59% and 64% respectively, but the addition amount of solid flame retardant was large.

[0004] Therefore, the synergistic system based on liquid phosphorus-based flame retardants that can simultaneously reduce the heat release and smoke generation of epoxy resin is still a difficult point in development. Summary of the Invention

[0005] In view of this, the technical problem to be solved by the present invention is to provide a smoke suppressant and an epoxy resin material. The smoke suppressant, through the combined action with a liquid phosphorus-based flame retardant, enables the prepared epoxy resin material to simultaneously reduce the heat release and smoke generation amount.

[0006] To achieve the above object, the technical solution adopted by the present invention is as follows:

[0007] The present invention provides a smoke suppressant, which is obtained by heating and mixing a copper-containing compound, citric acid, a calcium-containing compound and water to obtain a gel-like substance, and then calcining after drying;

[0008] The molar ratio of the copper-containing compound to citric acid is (1-5):1; more preferably 3:1.

[0009] The molar ratio of copper in the copper-containing compound to calcium in the calcium-containing compound is (6-15):1; more preferably 7:1.

[0010] The temperature of the heating and mixing is 40°C-100°C; more preferably 80°C.

[0011] Preferably in the present invention, the calcination temperature is 300°C-700°C; more preferably 500°C-700°C. In some specific embodiments of the present invention, it is preferably 700°C.

[0012] Preferably in the present invention, the copper-containing compound is selected from one or more of copper nitrate, copper chloride, copper sulfate, copper acetate; more preferably copper nitrate or copper chloride. In some specific embodiments of the present invention, it is preferably copper nitrate.

[0013] Preferably, the calcium-containing compound is selected from one or more of calcium oxide, calcium carbonate, calcium titanate, calcium silicate.

[0014] The present invention also provides an epoxy resin material, which is prepared by mixing and curing an epoxy resin, a curing agent, a liquid phosphorus-based flame retardant and the above-mentioned smoke suppressant;

[0015] The temperature of the curing is preferably 100°C-160°C.

[0016] In some specific embodiments of the present invention, the curing is sequentially carried out at 100°C and 160°C.

[0017] Before the curing, it also includes vacuum degassing of the mixture of the epoxy resin, the curing agent, the liquid phosphorus-based flame retardant and the above-mentioned smoke suppressant.

[0018] The epoxy resin material uses the epoxy resin as the matrix and the curing agent as the cross-linking agent, so that the epoxy resin, the liquid phosphorus-based flame retardant and the above-mentioned smoke suppressant carry out a cross-linking reaction to obtain the epoxy resin material.

[0019] Preferably in the present invention, the liquid phosphorus-based flame retardant is selected from one or more of dimethyl methylphosphonate, tert-butylphenyl diphenyl phosphate, triisopropylphenyl phosphate, resorcinol bis(diphenyl phosphate), bisphenol A bis(diphenyl phosphate); more preferably one or more of dimethyl methylphosphonate, tert-butylphenyl diphenyl phosphate, triisopropylphenyl phosphate.

[0020] Preferably, the epoxy resin of the present invention is selected from bisphenol A epoxy resin E-44 or bisphenol A epoxy resin E-51;

[0021] Preferably, the curing agent of the present invention is selected from diaminodiphenylmethane, diaminodiphenylsulfone, and m-phenylenediamine; more preferably diaminodiphenylmethane.

[0022] The epoxy resin material of the present invention has a small addition amount of the liquid phosphorus-based flame retardant as a reaction raw material, so that compared with the pure epoxy resin material without adding a flame retardant, the peak value of the heat release rate of the epoxy resin material can be reduced by more than 70%, and the total heat release amount can be reduced by more than 40%. This is due to the combined action of the liquid phosphorus-based flame retardant, the above-mentioned smoke suppressant, epoxy resin, and curing agent in the reaction raw materials of the epoxy resin material of the present invention.

[0023] Preferably, the mass ratio of the sum of the masses of the epoxy resin and the curing agent to the mass of the liquid phosphorus-based flame retardant is (90 - 95):(5 - 10); more preferably 14.2:1.

[0024] Preferably, the mass ratio of the sum of the masses of the epoxy resin and the curing agent to the mass of the smoke suppressant is (97 - 99):(1 - 3); more preferably 56.7:1.

[0025] More preferably, the liquid phosphorus-based flame retardant of the present invention is selected from dimethyl methylphosphonate;

[0026] The epoxy resin is selected from bisphenol A epoxy resin E-51;

[0027] The curing agent is selected from diaminodiphenylmethane.

[0028] Further preferably, the mass ratio of dimethyl methylphosphonate to bisphenol A epoxy resin E-51 is 1:10.

[0029] Compared with the prior art, the smoke suppressant provided by the present invention is obtained by heating and mixing a copper-containing compound, citric acid, a calcium-containing compound, and water to obtain a gel-like substance, drying it, and then calcining it; the molar ratio of the copper-containing compound to citric acid is (1 - 5):1; the molar ratio of copper in the copper-containing compound to calcium in the calcium-containing compound is (6 - 15):1; the temperature of the heating and mixing is 40°C - 100°C. Through the combined action of the smoke suppressant with the epoxy resin, liquid phosphorus-based flame retardant, and curing agent, the prepared epoxy resin material can reduce the peak value of the heat release rate and the total smoke generation amount during combustion, thereby improving the flame retardant performance of the epoxy resin material. Detailed Description of the Invention

[0030] In order to further illustrate the present invention, the smoke suppressant and epoxy resin material provided by the present invention are described in detail below in conjunction with examples.

[0031] The following experimental raw materials can all be purchased on the market or prepared according to the conventional preparation methods well-known to those skilled in the art. Among them, some of the raw materials and their sources are shown in Table 1 below:

[0032] Table 1 Some Raw Materials and Their Sources

[0033] Chemical Name Purchasing Manufacturer Epoxy Resin CYD-128 Baleng Petrochemical Co., Ltd. 4,4'-Diaminodiphenylmethane TCI Chemical Industry Development Co., Ltd. Copper Nitrate Trihydrate Beijing InnoChem Technology Co., Ltd. Calcium Carbonate Beijing InnoChem Technology Co., Ltd. Citric Acid Beijing InnoChem Technology Co., Ltd. Calcium Oxide Beijing InnoChem Technology Co., Ltd. Calcium Titanate Beijing InnoChem Technology Co., Ltd. Calcium Silicate Beijing InnoChem Technology Co., Ltd.

[0034] Example 1

[0035] 1) Preparation of the smoke suppressant

[0036] Take 0.06 mol of copper nitrate and 0.02 mol of citric acid and dissolve them in 100 ml of deionized water. Add 0.01 mol of calcium carbonate to it and stir for 10 minutes. Stir and volatilize at 80 °C for 10 hours. Dry the resulting gel overnight in an oven at 100 °C. Grind the dried product into a powder and calcine it in air at 700 °C for 4 hours to obtain the smoke suppressant.

[0037] 2) Preparation of the epoxy resin material:

[0038] Mix 90 parts by weight of E-51 epoxy resin, 23.4 parts by weight of diaminodiphenylmethane, 8 parts by weight of dimethyl methylphosphonate flame retardant DMMP, and 2 parts by weight of the smoke suppressant obtained above at room temperature. After vacuum degassing, pour it into a stainless-steel mold and cure it at 100 °C for 2 h and at 160 °C for 3 h to obtain the epoxy resin cured product.

[0039] Test results: The peak heat release rate (PHRR) is 392 kW / m 2 , and the total heat release (THR) is 48 MJ / m 2 , and the total smoke production (TSP) is 32 m 2 .

[0040] Example 2

[0041] 1) Preparation of the smoke suppressant

[0042] Take 0.15 mol of copper nitrate and 0.03 mol of citric acid and dissolve them in 100 ml of deionized water. Add 0.01 mol of calcium carbonate to it and stir for 10 minutes. Stir and volatilize at 80 °C for 10 hours. Dry the resulting gel overnight in an oven at 100 °C. Grind the dried product into a powder and calcine it in air at 700 °C for 4 hours to obtain the smoke suppressant.

[0043] 2) Preparation of the epoxy resin material:

[0044] Mix 90 parts by weight of E-51 epoxy resin, 23.4 parts by weight of diaminodiphenylmethane, 8 parts by weight of dimethyl methylphosphonate flame retardant DMMP, and 2 parts by weight of the smoke suppressant obtained above at room temperature. After vacuum degassing, pour it into a stainless steel mold and cure it at 100 °C for 2 h and then at 160 °C for 3 h to obtain an epoxy resin cured product.

[0045] Test results: The peak heat release rate is 391 kW / m 2 , and the total heat release is 57 MJ / m 2 , and the total smoke production is 33 m 2 .

[0046] Example 3

[0047] 1) Preparation of smoke suppressant

[0048] Dissolve 0.07 mol of copper nitrate and 0.24 mol of citric acid in 100 ml of deionized water, add 0.01 mol of calcium carbonate to it, and stir for 10 minutes. Stir and evaporate at 80 °C for 10 h, and dry the resulting gel in an oven at 100 °C overnight. Grind the dried product into powder and calcine it in air at 700 °C for 4 h to obtain the smoke suppressant.

[0049] 2) Preparation of epoxy resin material:

[0050] Mix 90 parts by weight of E-51 epoxy resin, 23.4 parts by weight of diaminodiphenylmethane, 8 parts by weight of dimethyl methylphosphonate flame retardant DMMP, and 2 parts by weight of the smoke suppressant obtained above at room temperature. After vacuum degassing, pour it into a stainless steel mold and cure it at 100 °C for 2 h and then at 160 °C for 3 h to obtain an epoxy resin cured product.

[0051] Test results: The peak heat release rate is 332 kW / m 2 , and the total heat release is 49 MJ / m 2 , and the total smoke production is 33 m 2 .

[0052] Example 4

[0053] 1) Preparation of smoke suppressant

[0054] Dissolve 0.07 mol of copper nitrate and 0.03 mol of citric acid in 100 ml of deionized water, add 0.01 mol of calcium titanate to it, and stir for 10 minutes. Stir and evaporate at 80 °C for 10 h, and dry the resulting gel in an oven at 100 °C overnight. Grind the dried product into powder and calcine it in air at 700 °C for 4 h to obtain the smoke suppressant.

[0055] 2) Preparation of epoxy resin material:

[0056] Mix 90 parts by weight of E-51 epoxy resin, 23.4 parts by weight of diaminodiphenylmethane, 8 parts by weight of dimethyl methylphosphonate flame retardant DMMP, and 2 parts by weight of the smoke suppressant obtained above at room temperature. After vacuum degassing, pour it into a stainless steel mold, cure at 100 °C for 2 h, and then cure at 160 °C for 3 h to obtain an epoxy resin cured product.

[0057] Test results: The peak heat release rate is 368 kW / m 2 , and the total heat release is 52 MJ / m 2 , and the total smoke production is 35 m 2 .

[0058] Example 5

[0059] Dissolve 0.15 mol of copper nitrate and 0.03 mol of citric acid in 100 ml of deionized water, add 0.01 mol of calcium oxide to it, and stir for 10 minutes. Stir and evaporate at 80 °C for 10 hours, and dry the resulting gel in an oven at 100 °C overnight. Grind the dried product into powder and calcine in air at 700 °C for 4 hours to obtain a smoke suppressant.

[0060] 2) Preparation of epoxy resin material:

[0061] Mix 90 parts by weight of E-51 epoxy resin, 23.4 parts by weight of diaminodiphenylmethane, 8 parts by weight of dimethyl methylphosphonate flame retardant DMMP, and 2 parts by weight of the smoke suppressant obtained above at room temperature. After vacuum degassing, pour it into a stainless steel mold, cure at 100 °C for 2 h, and then cure at 160 °C for 3 h to obtain an epoxy resin cured product.

[0062] Test results: The peak heat release rate is 387 kW / m 2 , and the total heat release is 54 MJ / m 2 , and the total smoke production is 35 m 2 .

[0063] Example 6

[0064] Dissolve 0.15 mol of copper nitrate and 0.03 mol of citric acid in 100 ml of deionized water, add 0.01 mol of calcium carbonate to it, and stir for 10 minutes. Stir and evaporate at 80 °C for 10 hours, and dry the resulting gel in an oven at 100 °C overnight. Grind the dried product into powder and calcine in air at 700 °C for 4 hours to obtain a smoke suppressant.

[0065] 2) Preparation of epoxy resin material:

[0066] Mix 90 parts by weight of E-51 epoxy resin, 23.4 parts by weight of diaminodiphenylmethane, 9 parts by weight of dimethyl methylphosphonate flame retardant DMMP, and 1 part by weight of the smoke suppressant obtained above at room temperature. After vacuum degassing, pour it into a stainless steel mold, cure at 100 °C for 2 h, and then cure at 160 °C for 3 h to obtain an epoxy resin cured product.

[0067] Test results: The peak heat release rate is 414 kW / m 2 , and the total heat release is 55 MJ / m 2 , and the total smoke production is 34 m 2 .

[0068] Example 7

[0069] Dissolve 0.15 mol of copper nitrate and 0.03 mol of citric acid in 100 ml of deionized water, add 0.01 mol of calcium silicate to it, and stir for 10 minutes. Stir and evaporate at 80 °C for 10 hours, and dry the resulting gel overnight in an oven at 100 °C. Grind the dried product into powder and calcine in air at 700 °C for 4 hours to obtain a smoke suppressant.

[0070] 2) Preparation of epoxy resin material:

[0071] Mix 90 parts by weight of E-51 epoxy resin, 23.4 parts by weight of diaminodiphenylmethane, 9 parts by weight of dimethyl methylphosphonate flame retardant DMMP, and 1 part by weight of the smoke suppressant obtained above at room temperature. After vacuum degassing, pour it into a stainless steel mold, cure at 100 °C for 2 h, and then cure at 160 °C for 3 h to obtain an epoxy resin cured product.

[0072] Test results: The peak heat release rate is 399 kW / m 2 , and the total heat release is 50 MJ / m 2 , and the total smoke production is 31 m 2 .

[0073] Comparative Example 1

[0074] Preparation of epoxy resin material:

[0075] Mix 100 parts by weight of E-51 epoxy resin and 26 parts by weight of diaminodiphenylmethane at room temperature. After vacuum degassing, pour it into a stainless steel mold, cure at 100 °C for 2 h, and then cure at 160 °C for 3 h to obtain an epoxy resin cured product.

[0076] Test results: The peak heat release rate is 1191 kW / m 2 , and the total heat release is 88 MJ / m 2 , and the total smoke production is 38 m 2 .

[0077] Comparative Example 2

[0078] Preparation of Epoxy Resin Material Containing Dimethyl Methylphosphonate

[0079] Mix 90 parts by weight of E-51 epoxy resin, 23.4 parts by weight of diaminodiphenylmethane, and 10 parts by weight of dimethyl methylphosphonate flame retardant DMMP at room temperature. After vacuum degassing, pour the mixture into a stainless steel mold, cure it at 100 °C for 2 h, and then cure it at 160 °C for 3 h to obtain an epoxy resin cured product.

[0080] Test Results: The peak heat release rate is 425 kW / m 2 , and the total heat release is 54 MJ / m 2 , and the total smoke production is 41 m 2 .

[0081] Performance Test

[0082] Perform cone calorimetry tests on the epoxy resin cured products obtained in Examples 1-7 and Comparative Examples 1-2. The test method is as follows:

[0083] Cone Calorimetry Test: Conducted according to ISO5660 standard, with the sample thickness of 3 mm and the surface heat flux of 50 kW / m 2 .

[0084] The test results are shown in Table 2 (where PHRR represents the peak heat release rate, THR represents the total heat release, and TSP represents the total smoke production):

[0085] Table 2 Performance Test Results of Epoxy Resin Cured Products Obtained in Examples 1-7 and Comparative Examples 1-2

[0086] Group <![CDATA[PHRR (kW / m 2 )]]> <![CDATA[THR(MJ / m 2 )]]> <![CDATA[TSP(m 2 )]]> Example 1 392 48 32 Example 2 391 57 33 Example 3 332 49 33 Example 4 368 52 35 Example 5 387 54 35 Example 6 414 55 34 Example 7 399 50 31 Comparative Example 1 1191 88 38 Comparative Example 2 425 54 41

[0087] The results in Table 2 above show that the epoxy resin materials prepared in Examples 1-7 of the present invention have significantly lower peak heat release rates, total heat releases, and total smoke productions than the epoxy resin materials prepared without liquid phosphorus-based flame retardants (Comparative Example 1), and also have significantly lower peak heat release rates and total smoke productions than the epoxy resin materials prepared with only liquid phosphorus-based flame retardants without the smoke suppressant of the present invention (Comparative Example 2). This indicates that only by simultaneously using the smoke suppressant and liquid phosphorus-based flame retardant of the present invention can the flame retardant performance of the epoxy resin materials of the present invention be significantly improved.

[0088] The description of the above embodiments is only used to help understand the method and its core idea of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and modifications can be made to the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.

Claims

1. A smoke suppressant, characterized in that: The gel-like substance is obtained by heating and mixing a copper-containing compound, citric acid, a calcium-containing compound and water, drying and then calcining; The molar ratio of the copper-containing compound to citric acid is (1-5):1; The molar ratio of copper in the copper-containing compound to calcium in the calcium-containing compound is (6-15):1; The temperature of the heating and mixing is 40°C-100°C.

2. The smoke suppressant according to claim 1, characterized in that: The calcination temperature is 300°C-700°C.

3. The smoke suppressant according to claim 1, characterized in that: The copper-containing compound is selected from one or more of copper nitrate, copper chloride, copper sulfate, and copper acetate; The calcium-containing compound is selected from one or more of calcium oxide, calcium carbonate, calcium titanate and calcium silicate.

4. An epoxy resin material, characterized in that: The invention is prepared by mixing and curing epoxy resin, curing agent, liquid phosphorus flame retardant and the smoke suppressant according to any one of claims 1 to 3.

5. The epoxy resin material according to claim 4, characterized in that: The liquid phosphorus-based flame retardant is selected from one or more of dimethyl methylphosphonate, tert-butylbenzene diphenyl phosphate, triisopropylphenyl phosphate, resorcinol bisphosphate, and bisphenol A bis(diphenyl phosphate).

6. The epoxy resin material according to claim 4, characterized in that: The epoxy resin is selected from bisphenol A epoxy resin E-44 or bisphenol A epoxy resin E-51.

7. The epoxy resin material according to claim 4, characterized in that: The curing agent is selected from diaminodiphenylmethane, diaminodiphenyl sulfone, and meta-phenylenediamine.

8. The epoxy resin material according to claim 4, characterized in that: The mass ratio of the sum of the mass of the epoxy resin and the curing agent to the mass of the liquid phosphorus-based flame retardant is (90-95):(5-10).

9. The epoxy resin material according to claim 4, characterized in that: The mass ratio of the sum of the mass of the epoxy resin and the curing agent to the mass of the smoke suppressant is (97-99):(1-3).

10. The epoxy resin material according to any one of claims 4 to 8, characterized in that: The liquid phosphorus flame retardant is selected from dimethyl methylphosphonate; The epoxy resin is selected from bisphenol A epoxy resin E-51; The curing agent is selected from diaminodiphenylmethane.