Glass fiber modified rubber composite material and preparation method thereof

Abstract

The invention discloses a glass fiber modified rubber composite material and a preparation method thereof. The invention relates to the technical field of rubber composite materials. The rubber composite material comprises the following raw materials in parts by weight: 80-100 parts of a rubber composite matrix, 1-2 parts of a vulcanizing agent DCP, 1-3 parts of a vulcanization accelerator DM, 1-3 parts of stearic acid, 1-3 parts of an antioxidant 1010, 10-15 parts of a plasticizer and 10-20 parts of flame-retardant modified glass fibers. According to the glass fiber modified rubber composite material and the preparation method thereof, impurities and water can be removed through high-temperature pretreatment, so that glass fibers and rubber are combined more tightly, and the tensile strength and tearing strength of the rubber are improved; through modification treatment, compatibility and cohesiveness of the glass fibers and rubber are improved, surface energy of the glass fibers is reduced, the glass fibers are dispersed in the rubber more uniformly, the overall performance of the rubber is improved, meanwhile, a protective film can be formed on the surfaces of the glass fibers, oxygen and heat transfer are isolated, and the flame retardance of the composite material is improved.

Description

Technical Field

[0001] The invention relates to the technical field of rubber composite materials, in particular to a glass fiber modified rubber composite material and a preparation method thereof. Background Art

[0002] Rubber has high elasticity at room temperature, but many of its properties (including tensile strength, hardness, wear resistance, fatigue resistance, conductivity, heat dissipation, etc.) cannot meet the application requirements of polymer materials without reinforcement. It is usually necessary to add fillers (such as carbon black, silica, etc.) to improve its performance. The Chinese patent with publication number CN106366468A discloses a carbon fiber modified rubber composite material, which is composed of the following raw material formula components in mass percentage: 18-20 parts of nano carbon fiber, 10-15 parts of microcrystalline graphene, 5-7 parts of acetylene carbon black, 10-12 parts of glass fiber, 5-8 parts of polyester fiber, 10-12 parts of ceramic fiber cotton, 3-5 parts of polyacrylonitrile fiber, 3-5 parts of fumed silica, 8-10 parts of polytetrafluoroethylene, 15-20 parts of low-density polyethylene , 45-55 parts of butadiene rubber, 50-60 parts of butyl rubber, 20-25 parts of polyethylene polypropylene, 50-55 parts of ethylene propylene diene monomer rubber, 40-50 parts of fluororubber, 20-30 parts of chloroprene rubber, 35-40 parts of polysulfide rubber, 45-50 parts of isoprene rubber; the mechanical properties, electrical and thermal properties of the carbon fiber modified rubber composite material are greatly improved, so that the rubber has better wear resistance, improves the electrical conductivity of the rubber, and further improves the antistatic and heat dissipation effects of the rubber. However, the flame retardant properties of the rubber composite material prepared by the above technical scheme need to be further improved; for this reason, the present invention proposes a glass fiber modified rubber composite material and a preparation method thereof to solve the above-mentioned problems. Summary of the invention

[0003] 1. Technical issues to be solved

[0004] In view of the deficiencies in the prior art, the present invention provides a glass fiber modified rubber composite material and a preparation method thereof, which solves the problems mentioned in the above background technology.

[0005] (II) Technical solution

[0006] To achieve the above object, the present invention is implemented by the following technical scheme: a glass fiber modified rubber composite material, comprising the following raw materials in parts by weight: 80-100 parts of rubber composite matrix, 1-2 parts of vulcanizing agent DCP, 1-3 parts of vulcanization accelerator DM, 1-3 parts of stearic acid, 1-3 parts of antioxidant 1010, 10-15 parts of plasticizer, and 10-20 parts of flame retardant modified glass fiber;

[0007] Wherein, the rubber composite matrix includes nitrile rubber and styrene butadiene rubber.

[0008] Preferably, the preparation method of the flame retardant modified glass fiber is:

[0009] S1. Pour 2.5-4 g of Fe(NO3)3·9H20 into 30 mL of deionized water and stir until it is completely dissolved to prepare solution A;

[0010] S2, pour 2-3.5 g of urea into 25 mL of deionized water and stir until it is completely dissolved to prepare solution B;

[0011] S3, pour 1.8-3g of the modified glass fiber into a high-pressure reactor, and pour solution A and solution B, and then place the high-pressure reactor in a drying oven at 110-120°C for full reaction for 3-4h;

[0012] S4. After the reaction is completed, the reactant is taken out and cooled to room temperature. The reactant is washed with distilled water for 4-6 times, then placed in a drying oven for drying, and then placed in a muffle furnace for calcination at 320-350°C for 1.5-2h to obtain flame retardant modified glass fiber.

[0013] Preferably, in S4, the drying temperature is 70-80° C. and the drying time is 10-12 h.

[0014] Preferably, in S3, the specific modification method of the glass fiber is:

[0015] (1) Pre-treating the glass fiber;

[0016] (2) Pour 1.2-2.5 g of polyvinyl alcohol into 100 mL of deionized water, and heat to 90-95° C. under stirring until it is completely dissolved;

[0017] (3) adding 12-20 g of glass fiber, cooling to 70-72° C., sequentially adding 1-1.7 g of sodium dodecylbenzene sulfonate and 8-15 g of potassium persulfate, and then slowly adding 10-20 mL of vinyl acetate;

[0018] (4) After the addition is complete, add 8-15 g of potassium persulfate, and then add 20-30 mL of vinyl acetate and 5-10 mL of isooctyl methacrylate;

[0019] (5) After the reaction is completed, add the remaining 8-15 g of potassium persulfate and continue stirring the reaction for 30-40 min;

[0020] (6) adjusting the pH of the solution, then standing the solution to separate the layers, washing the precipitate, and drying it in a drying oven at 40-50° C. to obtain the modified glass fiber.

[0021] Preferably, in (1), the pretreatment step of the glass fiber is:

[0022] (11) placing the glass fiber in a muffle furnace at 450-550° C., calcining for 80-100 min, and then cooling with the furnace;

[0023] (12) Soak the sample in an acidic solution for 1-1.5 h, and then wash it with distilled water for 3-5 times. Finally, dry it in an oven at 70-80°C until it reaches a constant weight.

[0024] Preferably, in (12), the acidic solution is a mixed solution of concentrated sulfuric acid and hydrogen peroxide, and the volume ratio thereof is 7:3.

[0025] Preferably, in said (6), hydrochloric acid with a mass fraction of 1% is added dropwise to adjust the pH value of the solution, and the pH value is adjusted to 3-4.

[0026] Preferably, in said (6), the precipitate is washed with water and acetone 3-4 times in sequence.

[0027] (III) Beneficial effects

[0028] The present invention provides a glass fiber modified rubber composite material and a preparation method thereof. Compared with the prior art, the glass fiber modified rubber composite material and the preparation method thereof have the following beneficial effects: the glass fiber modified rubber composite material and the preparation method thereof can remove impurities and moisture through high temperature pretreatment, make the glass fiber and rubber more closely bonded, and improve the tensile strength and tear strength of the rubber; through the modification treatment, the compatibility and adhesion between the glass fiber and the rubber are increased, the surface energy of the glass fiber is reduced, and the glass fiber is dispersed more evenly in the rubber, thereby improving the overall performance of the rubber, and at the same time, a protective film can be formed on the surface of the glass fiber to isolate oxygen and heat transfer, and improve the flame retardancy of the composite material; through further treatment, the rigidity and hardness of the glass fiber are effectively enhanced, thereby improving the hardness and wear resistance of the rubber, and at the same time, the thermal conductivity of the glass fiber can be improved, so that the heat is quickly dissipated, and the surface temperature of the rubber is reduced, so as to achieve the purpose of flame retardancy. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 These are SEM images of the glass fiber and the flame-retardant modified glass fiber provided by the present invention. DETAILED DESCRIPTION

[0030] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0031] Example 1

[0032] (1) Preparation of flame retardant modified glass fiber:

[0033] (11) Modification of glass fiber: Place the glass fiber in a muffle furnace at 450°C, calcine for 80 minutes, and then cool it in the furnace; then soak it in a mixed solution of concentrated sulfuric acid and hydrogen peroxide with a volume ratio of 7:3 for 1 hour, and then wash it with distilled water for 3 times; finally, place it in a 70°C oven to dry to constant weight; pour 1.2g of polyvinyl alcohol into 100mL of deionized water, raise the temperature to 90°C under stirring, until it is completely dissolved; add 12g of dried glass fiber, cool to 70°C, and add 1g of dodecahydrate, Sodium alkylbenzene sulfonate, 8g of potassium persulfate, and then slowly drop 10mL of vinyl acetate; after the dropwise addition is completed, add 8g of potassium persulfate, drop 20mL of vinyl acetate and 5mL of isooctyl methacrylate; after the reaction is completed, add the remaining 8g of potassium persulfate, and continue to stir and react for 30min; drop 1% hydrochloric acid to adjust the pH value of the solution to 3, then stand and separate, wash the precipitate with water and acetone 3 times, and then dry it in a drying oven at 40°C to obtain a modified glass fiber;

[0034] (12) Pour 2.5 g of Fe(NO3)3·9H20 into 30 mL of deionized water and stir until it is completely dissolved to obtain solution A; pour 2 g of urea into 25 mL of deionized water and stir until it is completely dissolved to obtain solution B; pour 1.8 g of the modified glass fiber into a high-pressure reactor, and pour solution A and solution B into it, and then place the high-pressure reactor in a drying oven at 110°C to fully react for 3 hours; after the reaction is completed, take it out and cool it to room temperature, wash the reactant with distilled water 4 times, and then place it in a drying oven at 70°C to dry for 10 hours, and then place it in a muffle furnace at 320°C to calcine for 1.5 hours to obtain flame-retardant modified glass fiber;

[0035] (2) Add 80 g of nitrile rubber and styrene butadiene rubber into an internal mixer at a mixing temperature of 70° C. for 30 min;

[0036] (3) Add 1 g of vulcanizing agent DCP, 1 g of vulcanization accelerator DM, 1 g of stearic acid, 1 g of antioxidant 1010, 10 g of plasticizer, and 10 g of flame retardant modified glass fiber, and continue mixing for 30 min;

[0037] (4) Then, extrusion, rolling and vulcanization are performed in sequence to obtain a glass fiber modified rubber composite material.

[0038] Example 2

[0039] (1) Preparation of flame retardant modified glass fiber:

[0040] (11) Modification of glass fiber: Place the glass fiber in a muffle furnace at 500°C, calcine for 90 minutes, and then cool it in the furnace; then soak it in a mixed solution of concentrated sulfuric acid and hydrogen peroxide with a volume ratio of 7:3 for 1.2 hours, and then wash it with distilled water for 4 times; finally, place it in a 75°C oven to dry to constant weight; pour 2g of polyvinyl alcohol into 100mL of deionized water, raise the temperature to 92°C under stirring, until it is completely dissolved; add 16g of dried glass fiber, cool to 71°C, and add 1.2g of dodecyl Sodium benzenesulfonate, 12g of potassium persulfate, and then slowly add 15mL of vinyl acetate; after the addition is completed, add 11g of potassium persulfate, add 25mL of vinyl acetate and 8mL of isooctyl methacrylate; after the reaction is completed, add the remaining 12g of potassium persulfate, and continue to stir and react for 35min; add 1% hydrochloric acid by mass fraction to adjust the pH value of the solution to 3.5, then stand and separate, wash the precipitate with water and acetone 4 times, and then dry it in a drying oven at 45°C to obtain modified glass fiber;

[0041] (12) Pour 3.2 g of Fe(NO3)3·9H20 into 30 mL of deionized water and stir until it is completely dissolved to obtain solution A; pour 3 g of urea into 25 mL of deionized water and stir until it is completely dissolved to obtain solution B; pour 2.4 g of the modified glass fiber into a high-pressure reactor, and pour solution A and solution B into it, and then place the high-pressure reactor in a drying oven at 115°C to fully react for 3.5 hours; after the reaction is completed, take it out and cool it to room temperature, wash the reactant with distilled water 5 times, and then place it in a drying oven at 75°C to dry for 11 hours, and then place it in a muffle furnace at 330°C to calcine for 1.8 hours to obtain flame-retardant modified glass fiber;

[0042] (2) Add 90 g of nitrile rubber and styrene butadiene rubber into an internal mixer at a mixing temperature of 70° C. for 30 min;

[0043] (3) Add 1.5 g of vulcanizing agent DCP, 2 g of vulcanization accelerator DM, 2 g of stearic acid, 2 g of antioxidant 1010, 12 g of plasticizer, and 15 g of flame retardant modified glass fiber, and continue mixing for 30 min;

[0044] (4) Then, extrusion, rolling and vulcanization are performed in sequence to obtain a glass fiber modified rubber composite material.

[0045] Example 3

[0046] (1) Preparation of flame retardant modified glass fiber:

[0047] (11) Modification of glass fiber: Place the glass fiber in a muffle furnace at 550°C, calcine for 100 minutes, and then cool it in the furnace; then soak it in a mixed solution of concentrated sulfuric acid and hydrogen peroxide with a volume ratio of 7:3 for 1.5 hours, and then wash it with distilled water for 5 times; finally, place it in an oven at 80°C and dry it to constant weight; pour 2.5g of polyvinyl alcohol into 100mL of deionized water, raise the temperature to 95°C under stirring, until it is completely dissolved; add 20g of dried glass fiber, cool it to 72°C, and add 1.7g of dodecahydrate in turn. Sodium alkylbenzene sulfonate, 15g of potassium persulfate, and then slowly drop 20mL of vinyl acetate; after the dropwise addition is completed, add 15g of potassium persulfate, drop 30mL of vinyl acetate and 10mL of isooctyl methacrylate; after the reaction is completed, add the remaining 15g of potassium persulfate, and continue stirring and reacting for 40min; drop 1% hydrochloric acid to adjust the pH value of the solution to 4, then stand and separate, wash the precipitate with water and acetone in turn 4 times, and then dry it in a drying oven at 50°C to obtain a modified glass fiber;

[0048] (12) Pour 4 g of Fe(NO3)3·9H20 into 30 mL of deionized water and stir until it is completely dissolved to obtain solution A; pour 3.5 g of urea into 25 mL of deionized water and stir until it is completely dissolved to obtain solution B; pour 3 g of the modified glass fiber into a high-pressure reactor, and pour solution A and solution B into it, and then place the high-pressure reactor in a drying oven at 120°C to fully react for 4 hours; after the reaction is completed, take it out and cool it to room temperature, wash the reactant with distilled water 6 times, and then place it in a drying oven at 80°C to dry for 12 hours, and then place it in a muffle furnace at 350°C to calcine for 2 hours to obtain flame-retardant modified glass fiber;

[0049] (2) Add 100 g of nitrile rubber and styrene butadiene rubber into an internal mixer at a mixing temperature of 70° C. for 30 min;

[0050] (3) Add 2 g of vulcanizing agent DCP, 3 g of vulcanization accelerator DM, 3 g of stearic acid, 3 g of antioxidant 1010, 15 g of plasticizer, and 20 g of flame retardant modified glass fiber, and continue mixing for 30 min;

[0051] (4) Then, extrusion, rolling and vulcanization are performed in sequence to obtain a glass fiber modified rubber composite material.

[0052] Comparative Example 1

[0053] Compared with the embodiment, the flame retardant modified glass fiber in embodiment 1 is replaced by modified glass fiber; the rest remains unchanged.

[0054] Comparative Example 2

[0055] Compared with the example, the flame retardant modified glass fiber in Example 1 is replaced by glass fiber; the rest remains unchanged.

[0056] Tensile performance test: the test environment is 23±2℃, the temperature is 50±5%, the stretching speed is 50mm / min, and the sample size is 150mm×20mm×4mm; the results are shown in Table 1.

[0057] Wear rate test: placed in a corrosion and wear testing machine at 960r / min, abraded in 20-30 mesh mortar for 4h, the sample size is 70mm×25mm×4mm; the results are shown in Table 1.

[0058] Limiting oxygen index test: The test was carried out using a JF-3 oxygen index instrument with a sample size of 80 mm × 10 mm × 4 mm. The results are shown in Table 1.

[0059] Vertical combustion grade test: The test was conducted using a CZF-5 horizontal vertical combustion tester with a sample size of 125 mm × 12.5 mm × 3.2 mm. The results are shown in Table 1.

[0060] Table 1

[0061]

[0062] like Figure 1 As shown, the surface of the untreated glass fiber is smooth, while the surface of the treated glass fiber becomes rough due to the adsorption of Fe2O3 nanoparticles.

[0063] Meanwhile, the contents not described in detail in this specification belong to the prior art known to those skilled in the art.

[0064] It should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device.

[0065] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A glass fiber modified rubber composite material, characterized in that: The invention comprises the following raw materials in parts by weight: 80-100 parts of rubber composite matrix, 1-2 parts of vulcanizing agent DCP, 1-3 parts of vulcanization accelerator DM, 1-3 parts of stearic acid, 1-3 parts of antioxidant 1010, 10-15 parts of plasticizer, and 10-20 parts of flame retardant modified glass fiber; Wherein, the rubber composite matrix includes nitrile rubber and styrene butadiene rubber.

2. A glass fiber modified rubber composite material according to claim 1, characterized in that: The preparation method of the flame retardant modified glass fiber is: S1. Pour 2.5-4 g of Fe(NO3)3·9H20 into 30 mL of deionized water and stir until it is completely dissolved to prepare solution A; S2, pour 2-3.5 g of urea into 25 mL of deionized water and stir until it is completely dissolved to prepare solution B; S3, pour 1.8-3g of the modified glass fiber into a high-pressure reactor, and pour solution A and solution B, and then place the high-pressure reactor in a drying oven at 110-120°C for full reaction for 3-4h; S4. After the reaction is completed, the reactant is taken out and cooled to room temperature. The reactant is washed with distilled water for 4-6 times, then placed in a drying oven for drying, and then placed in a muffle furnace for calcination at 320-350°C for 1.5-2h to obtain flame retardant modified glass fiber.

3. A glass fiber modified rubber composite material according to claim 2, characterized in that: In S4, the drying temperature is 70-80° C. and the drying time is 10-12 hours.

4. The glass fiber modified rubber composite material according to claim 2, characterized in that: In S3, the specific modification method of the glass fiber is: (1) Pre-treating the glass fiber; (2) Pour 1.2-2.5 g of polyvinyl alcohol into 100 mL of deionized water, and heat to 90-95° C. under stirring until it is completely dissolved; (3) adding 12-20 g of glass fiber, cooling to 70-72° C., sequentially adding 1-1.7 g of sodium dodecylbenzene sulfonate and 8-15 g of potassium persulfate, and then slowly adding 10-20 mL of vinyl acetate; (4) After the addition is complete, add 8-15 g of potassium persulfate, and then add 20-30 mL of vinyl acetate and 5-10 mL of isooctyl methacrylate; (5) After the reaction is completed, add the remaining 8-15 g of potassium persulfate and continue stirring the reaction for 30-40 min; (6) adjusting the pH of the solution, then standing the solution to separate the layers, washing the precipitate, and drying it in a drying oven at 40-50° C. to obtain the modified glass fiber.

5. The glass fiber modified rubber composite material according to claim 4, characterized in that: In the above (1), the pretreatment step of the glass fiber is: (11) placing the glass fiber in a muffle furnace at 450-550° C., calcining for 80-100 min, and then cooling in the furnace; (12) Soak the sample in an acidic solution for 1-1.5 h, and then wash it with distilled water for 3-5 times. Finally, dry it in an oven at 70-80°C until it reaches a constant weight.

6. The glass fiber modified rubber composite material according to claim 5, characterized in that: In (12), the acidic solution is a mixed solution of concentrated sulfuric acid and hydrogen peroxide, and the volume ratio thereof is 7:

3.

7. The glass fiber modified rubber composite material according to claim 4, characterized in that: In the step (6), 1% hydrochloric acid is added dropwise to adjust the pH value of the solution to 3-4.

8. The glass fiber modified rubber composite material according to claim 4, characterized in that: In the step (6), the precipitate is washed with water and acetone 3-4 times in sequence.

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