High-strength acrylate rubber material and preparation method thereof

Abstract

The invention discloses a high-strength acrylate rubber material and a preparation method thereof, and relates to the technical field of high polymer materials. When the high-strength acrylate rubber material is prepared, polyhydroxy imidazolium salt and phosphorus pentoxide react to prepare a functional flame retardant; reacting the pre-modified glass fiber with hydrazine hydrate to obtain modified glass fiber; the preparation method comprises the following steps: carrying out solution polymerization on ethyl acrylate, butyl acrylate, acryloxy propyl bis (trimethylsiloxy) methylsilane and glycidyl methacrylate to prepare acrylate raw rubber; the high-strength acrylate rubber material is prepared by uniformly mixing acrylate raw rubber, the modified glass fiber, a functional flame retardant and triphenyl phosphine, plastifying and thin-passing. The high-strength acrylate rubber material prepared by the invention has excellent flame-retardant, antibacterial, anti-aging and mechanical properties.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and particularly to a high-strength acrylate rubber material and a preparation method thereof. Background Art

[0002] Acrylate rubber is a type of special rubber copolymerized from one or more acrylates as the main monomers and a small amount of monomers with crosslinking groups. Acrylate rubber has excellent oil resistance and high-temperature resistance, and is very suitable for automotive rubber products, so it has become the key development object of automobile manufacturers. The main components of acrylate rubber are C, H, and O, and its limiting oxygen index is relatively low, making it easy to burn, which brings certain safety hazards to the use of acrylate rubber; in addition, acrylate rubber has non-crystallinity and low self-strength, lower than that of general-purpose rubbers, and this defect also limits the application of acrylate rubber. Based on the above problems, it is necessary to improve the existing technology, develop a high-strength acrylate rubber material with excellent flame retardancy and mechanical properties, enhance the safety of acrylate rubber, extend the service life of acrylate rubber, and broaden the application fields of acrylate rubber. Summary of the Invention

[0003] The purpose of the present invention is to provide a high-strength acrylate rubber material and a preparation method thereof to solve the problems existing in the prior art.

[0004] To solve the above technical problems, the present invention provides the following technical solutions: A high-strength acrylate rubber material, which is prepared by reacting polyhydroxyimidazole salt with phosphorus pentoxide to obtain a functional flame retardant; reacting pre-modified glass fiber with hydrazine hydrate to obtain modified glass fiber; and uniformly mixing acrylate raw rubber, modified glass fiber, functional flame retardant, and triphenylphosphine, followed by plasticizing and thinning. The polyhydroxyimidazole salt is prepared by reacting 1,1-(1,6-hexanediyl)bisimidazole with 2-bromomethyl-2-hydroxymethyl-1,3-propanediol. The pre-modified glass fiber is prepared by reacting 3-isothiocyanatopropyltriethoxysilane with N1-(4-nitrophenyl)benzene-1,4-diamine and glass fiber in sequence. The acrylate raw rubber is prepared by solution polymerization of ethyl acrylate, butyl acrylate, acryloxypropylbis(trimethylsiloxy)methylsilane, and glycidyl methacrylate.

[0005] A preparation method of a high-strength acrylate rubber material, which includes the following preparation steps: (1) Add polyhydroxyimidazole salt and phosphorus pentoxide at a molar ratio of 1:(3 - 4) to deionized water that is 18 - 20 times the mass of the polyhydroxyimidazole salt. Stir and react at 78 - 82 °C and 200 - 300 r / min for 3 - 4 h. Spin - dry the deionized water with a rotary evaporator, wash it 3 - 5 times with absolute ethanol, and dry it at 50 - 60 °C for 8 - 10 h under vacuum conditions to obtain a functional flame retardant; (2) Mix pre - modified glass fiber and absolute ethanol evenly at a mass ratio of 1:(38 - 42), ultrasonically disperse for 20 - 30 min, add palladium / carbon that is 0.2 - 0.3 times the mass of the pre - modified glass fiber. Stir and reflux at 88 - 92 °C and 200 - 300 r / min for 30 - 40 min. Cool down to 58 - 62 °C, and uniformly drip a 50% - 60% hydrazine hydrate aqueous solution that is 3 - 4 times the mass of the pre - modified glass fiber within 20 min. After dripping, raise the temperature to 88 - 92 °C, stir and reflux at 200 - 300 r / min for 7 - 8 h, filter, wash it 3 - 5 times with absolute ethanol and deionized water respectively, and dry it at 60 - 70 °C for 10 - 12 h under vacuum conditions to obtain modified glass fiber; (3) Mix the polymerization monomer and ethyl acetate evenly at a mass ratio of 1:(0.36 - 0.38), place them in a high - pressure reactor, introduce nitrogen to maintain the pressure at 0.26 - 0.3 MPa, stir at 128 - 132 °C and 120 - 130 r / min for 8 - 10 min, add an initiator solution that is 0.02 - 0.03 times the mass of the polymerization monomer, continue to stir and react for 90 - 100 min, discharge the material, place it in a devolatilization extruder for devolatilization, and dry it at 70 - 80 °C for 5 - 6 h under vacuum conditions to obtain acrylate raw rubber; (4) Mix acrylate raw rubber, modified glass fiber, functional flame retardant, and triphenylphosphine evenly, knead them in a mixer, then thin - pass them in an open mill, keep them at 70 - 80 °C for 80 - 90 min, and cool to room temperature to obtain a high - strength acrylate rubber material.

[0006] As an optimization, the preparation method of the polyhydroxyimidazole salt in step (1) is: Add 1,1 - (1,6 - hexanediyl) bisimidazole and 2 - bromomethyl - 2 - hydroxymethyl - 1,3 - propanediol at a molar ratio of 1:2 to chloroform that is 8 - 10 times the mass of 1,1 - (1,6 - hexanediyl) bisimidazole. Stir and react at 48 - 52 °C and 200 - 300 r / min for 7 - 8 h, and dry it at 50 - 60 °C for 8 - 9 h under vacuum conditions to obtain polyhydroxyimidazole salt.

[0007] As an optimization, the rotary evaporation temperature of the rotary evaporator in step (1) is 50 - 60 °C, the rotary evaporation speed is 100 - 120 r / min, and the rotary evaporation time is 60 - 70 min.

[0008] As an optimization, the reaction process of the functional flame retardant described in step (1) is as follows: 。

[0009] As an optimization, the preparation method of the pre-modified glass fiber described in step (2) is: mixing glass fiber and absolute ethanol in a mass ratio of 1:(50 - 60), ultrasonically dispersing for 80 - 90 min, adding a functionalized siloxane reaction solution that is 24 - 26 times the mass of the glass fiber, adding an oxalic acid aqueous solution with a concentration of 1 mol / l that is 5 - 7 times the mass of the glass fiber, stirring and reacting at 60 - 70 °C and 300 - 500 r / min for 5 - 6 h, filtering, washing 3 - 5 times each with absolute ethanol and deionized water, and drying at 70 - 80 °C under vacuum for 8 - 10 h to obtain the pre-modified glass fiber; the single filament diameter of the glass fiber is 10 - 20 μm.

[0010] As an optimization, the preparation method of the functionalized siloxane reaction solution is: adding 3-isothiocyanatopropyltriethoxysilane and N1-(4-nitrophenyl)benzene-1,4-diamine in a molar ratio of 1:(1.1 - 1.3) to absolute ethanol that is 7 - 8 times the mass of 3-isothiocyanatopropyltriethoxysilane, adding dibutyltin dilaurate that is 0.03 - 0.05 times the mass of 3-isothiocyanatopropyltriethoxysilane, reacting under stirring conditions at 50 - 60 °C and 200 - 300 r / min for 5 - 6 h, cooling to room temperature and then continuing to stir and react for 10 - 12 h to obtain the functionalized siloxane reaction solution.

[0011] As an optimization, the CAS number of N1-(4-nitrophenyl)benzene-1,4-diamine is 100990-45-2; the structural formula is: 。

[0012] As an optimization, the reaction process of 3-isothiocyanatopropyltriethoxysilane and N1-(4-nitrophenyl)benzene-1,4-diamine is as follows: 。

[0013] As an optimization, the reaction process of the pre-modified glass fiber described in step (2) and hydrazine hydrate is as follows: 。

[0014] As an optimization, the preparation method of the polymerization monomer described in step (3) is: mixing ethyl acrylate, butyl acrylate, acryloxypropylbis(trimethylsiloxy)methylsilane, and glycidyl methacrylate in a molar ratio of 1:(1.6 - 1.8):(0.6 - 0.8):(0.3 - 0.4) and mixing them evenly to prepare the polymerization monomer.

[0015] As an optimization, the CAS number of the acryloxypropylbis(trimethylsiloxy)methylsilane is 19309-90-1; the structural formula is: .

[0016] As an optimization, the preparation method of the initiator solution in step (3) is: mixing di-tert-butyl peroxide and ethyl acetate in a mass ratio of 1:(6-8) evenly to prepare the initiator solution.

[0017] As an optimization, the process parameters of devolatilization in step (3) are: setting the temperature of the devolatilization extruder to 158-162 °C, the vacuum degree to 0.01-0.02 MPa, and the screw speed to 100-120 r / min.

[0018] As an optimization, the preparation method of the high-strength acrylate rubber material in step (4) is: weighing 98-102 parts by mass of acrylate raw rubber, 6-7 parts of modified glass fiber, 10-12 parts of functional flame retardant, and 1-1.2 parts of triphenylphosphine; mixing the acrylate raw rubber, modified glass fiber, functional flame retardant, and triphenylphosphine evenly, putting them into a mixer, kneading at 150-160 °C and 50-60 r / min for 12-14 min, discharging, passing through a two-roll mill for thin-slicing 5-7 times, keeping warm at 70-80 °C for 80-90 min, and cooling to room temperature to obtain the high-strength acrylate rubber material.

[0019] Compared with the prior art, the beneficial effects achieved by the present invention are: When preparing the high-strength acrylate rubber material in the present invention, 1,1-(1,6-hexanediyl)bisimidazole and 2-bromomethyl-2-hydroxymethyl-1,3-propanediol are reacted to obtain a polyhydroxyimidazole salt; the polyhydroxyimidazole salt and phosphorus pentoxide are reacted to obtain a functional flame retardant; 3-isothiocyanatopropyltriethoxysilane is successively reacted with N1-(4-nitrophenyl)benzene-1,4-diamine and glass fiber to obtain a pre-modified glass fiber; the pre-modified glass fiber and hydrazine hydrate are reacted to obtain a modified glass fiber; ethyl acrylate, butyl acrylate, acryloxypropylbis(trimethylsiloxy)methylsilane, and glycidyl methacrylate are polymerized by solution polymerization to obtain an acrylate raw rubber; the acrylate raw rubber, modified glass fiber, functional flame retardant, and triphenylphosphine are mixed evenly, and plasticized and thin-sliced to obtain the high-strength acrylate rubber material.

[0020] First, 1,1-(1,6-hexanediyl)bis(imidazole) and 2-(bromomethyl)-2-(hydroxymethyl)-1,3-propanediol are reacted to prepare a polyhydroxy imidazolium salt; the polyhydroxy imidazolium salt and phosphorus pentoxide are reacted to prepare a functional flame retardant, on which imidazolium salt and phosphate groups are formed; the imidazolium salt belongs to a cationic antibacterial agent, which can improve the antibacterial performance of the high-strength acrylate rubber material; the phosphate group contains phosphorus element, which can improve the flame retardant performance of the high-strength acrylate rubber material; at the same time, the phosphate group can also react with the epoxy group introduced on the side chain of the acrylate raw rubber molecule to form a phosphate ester bond, forming a crosslinked network and improving the mechanical properties of the high-strength acrylate rubber material.

[0021] Secondly, 3-isothiocyanatopropyltriethoxysilane is successively reacted with N1-(4-nitrophenyl)benzene-1,4-diamine and glass fiber to prepare pre-modified glass fiber, on which an aromatic amine structure, a thiourea structure and a nitro group are introduced; the aromatic amine structure can terminate active free radicals, and the thiourea structure has the ability of anti-ozone aging and scavenging free radicals. Combining these two structures endows the high-strength acrylate rubber material with excellent anti-aging performance; the nitro group on the pre-modified glass fiber is reduced to an amino group with hydrazine hydrate to prepare modified glass fiber, on which an amino group is introduced; the amino group introduced on the modified glass fiber can react with the epoxy group introduced on the side chain of the acrylate raw rubber molecule to form a crosslinked network and improve the mechanical properties of the high-strength acrylate rubber material; glass fiber is an inorganic non-metallic material with high strength and high modulus properties. Adding glass fiber to rubber can improve the mechanical properties of rubber, but directly adding glass fiber has the problem of poor compatibility. Surface modification of glass fiber can improve the compatibility between glass fiber and acrylate rubber, make glass fiber uniformly dispersed in acrylate rubber, give full play to the reinforcing effect of glass fiber, and further improve the mechanical properties of the high-strength acrylate rubber material.

[0022] Finally, ethyl acrylate, butyl acrylate, acryloxypropylbis(trimethylsiloxy)methylsilane and glycidyl methacrylate are prepared into acrylate raw rubber by solution polymerization; a siloxane structure and an epoxy group are introduced on the side chain of the acrylate raw rubber molecule; the introduction of the siloxane structure can promote carbon formation and further improve the flame retardant performance of the high-strength acrylate rubber material. The introduced epoxy group serves as a vulcanization site, which can react with the amino group on the modified glass fiber and can also react with the phosphate group on the functional flame retardant to directly form a crosslinked network, improving the mechanical properties of the high-strength acrylate rubber material, and at the same time eliminating the use of vulcanizing agent. Detailed implementation mode

[0023] 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 the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0024] Embodiment 1: A preparation method of a high-strength acrylate rubber material, the preparation method of the high-strength acrylate rubber material comprising the following preparation steps: (1) Add 1,1-(1,6-hexanediyl)bisimidazole and 2-bromomethyl-2-hydroxymethyl-1,3-propanediol in a molar ratio of 1:2 to chloroform 8 times the mass of 1,1-(1,6-hexanediyl)bisimidazole, stir and react at 48°C and 200 r / min for 8 h, and dry at 50°C for 9 h under vacuum conditions to obtain a polyhydroxy imidazole salt; Add the polyhydroxy imidazole salt and phosphorus pentoxide in a molar ratio of 1:3 to deionized water 18 times the mass of the polyhydroxy imidazole salt, stir and react at 78°C and 200 r / min for 4 h, spin-dry the deionized water with a rotary evaporator, the rotary evaporation temperature is 50°C, the rotary evaporation speed is 100 r / min, and the rotary evaporation time is 70 min. Wash 3 times with absolute ethanol and dry at 50°C for 10 h under vacuum conditions to obtain a functional flame retardant; (2) 3-Isothiopropyltriethoxysilane and N1-(4-nitrophenyl)benzene-1,4-diamine were added to anhydrous ethanol at 7 times the mass of 3-isothiopropyltriethoxysilane in a molar ratio of 1:1.1. Dibutyltin dilaurate at 0.03 times the mass of 3-isothiopropyltriethoxysilane was added. The reaction was carried out at 50 °C under stirring at 200 r / min for 6 h. After cooling to room temperature, the reaction was continued with stirring for 12 h to obtain a functionalized siloxane reaction solution. Glass fiber and anhydrous ethanol were mixed evenly in a mass ratio of 1:50, ultrasonically dispersed for 80 min, and 24 times the mass of the functionalized siloxane reaction solution based on the mass of the glass fiber was added. An aqueous oxalic acid solution with a concentration of 1 mol / l and 5 times the mass of the glass fiber was added. The reaction was carried out at 60 °C under stirring at 300 r / min for 6 h, filtered, washed 3 times each with anhydrous ethanol and deionized water, and dried under vacuum at 70 °C for 10 h to obtain pre-modified glass fiber. The pre-modified glass fiber and anhydrous ethanol were mixed evenly in a mass ratio of 1:38, ultrasonically dispersed for 20 min, and 0.2 times the mass of palladium / carbon based on the mass of the pre-modified glass fiber was added. The mixture was stirred and refluxed at 88 °C under 200 r / min for 40 min, cooled to 58 °C, and an aqueous hydrazine hydrate solution with a mass fraction of 60% and 3 times the mass of the pre-modified glass fiber was added dropwise uniformly within 20 min. After the addition was completed, the temperature was raised to 88 °C, and the mixture was stirred and refluxed at 200 r / min for 8 h, filtered, washed 3 times each with anhydrous ethanol and deionized water, and dried under vacuum at 60 °C for 10 h to obtain modified glass fiber; (3) Ethyl acrylate, butyl acrylate, acryloxypropylbis(trimethylsiloxy)methylsilane, and glycidyl methacrylate were mixed evenly in a molar ratio of 1:1.6:0.6:0.3 to prepare a polymer monomer. Di-tert-butyl peroxide and ethyl acetate were mixed evenly in a mass ratio of 1:6 to prepare an initiator solution. The polymer monomer and ethyl acetate were mixed evenly in a mass ratio of 1:0.36, placed in a high-pressure reactor, and nitrogen was introduced to maintain the pressure at 0.26 MPa. The mixture was stirred at 128 °C and 120 r / min for 10 min, 0.02 times the mass of the initiator solution based on the mass of the polymer monomer was added, and the reaction was continued with stirring for 100 min. The product was discharged and devolatilized in a devolatilizing extruder. The temperature of the devolatilizing extruder was set at 158 °C, the vacuum degree was 0.01 MPa, and the screw speed was 100 r / min. After devolatilization, it was dried under vacuum at 70 °C for 6 h to obtain an acrylate raw rubber; (4) By mass, 98 parts of acrylate raw rubber, 6 parts of modified glass fiber, 10 parts of functional flame retardant, and 1 part of triphenylphosphine were weighed. The acrylate raw rubber, modified glass fiber, functional flame retardant, and triphenylphosphine were mixed evenly, placed in a mixer, kneaded at 150 °C and 50 r / min for 14 min, discharged, passed through a two-roll mill for 5 thin passes, kept warm at 70 °C for 90 min, and cooled to room temperature to obtain a high-strength acrylate rubber material.

[0025] Example 2: A preparation method of a high-strength acrylate rubber material, the preparation method of the high-strength acrylate rubber material comprising the following preparation steps: (1) 1,1-(1,6-Hexanediyl)bisimidazole and 2-(bromomethyl)-2-(hydroxymethyl)-1,3-propanediol are added to chloroform in a molar ratio of 1:2 and 9 times the mass of 1,1-(1,6-hexanediyl)bisimidazole. Stir and react at 50 °C and 250 r / min for 7.5 h, and dry at 55 °C under vacuum for 8.5 h to obtain a polyhydroxy imidazole salt; the polyhydroxy imidazole salt and phosphorus pentoxide are added to deionized water in a molar ratio of 1:3.5 and 19 times the mass of the polyhydroxy imidazole salt. Stir and react at 81 °C and 250 r / min for 3.5 h, spin-dry the deionized water with a rotary evaporator, with a rotary evaporation temperature of 55 °C, a rotary evaporation speed of 110 r / min, and a rotary evaporation time of 65 min. Wash 4 times with absolute ethanol and dry at 55 °C under vacuum for 9 h to obtain a functional flame retardant; (2) 3-Isothiopropyltriethoxysilane and N1-(4-nitrophenyl)benzene-1,4-diamine are added to absolute ethanol in a molar ratio of 1:1.2 and 7.5 times the mass of 3-isothiopropyltriethoxysilane. Add dibutyltin dilaurate at 0.04 times the mass of 3-isothiopropyltriethoxysilane and react under stirring conditions at 55 °C and 250 r / min for 5.5 h. After cooling to room temperature, continue stirring and reacting for 11 h to obtain a functionalized siloxane reaction solution; glass fiber and absolute ethanol are mixed evenly at a mass ratio of 1:55, ultrasonically dispersed for 85 min, add a functionalized siloxane reaction solution 25 times the mass of the glass fiber, add an oxalic acid aqueous solution with a concentration of 1 mol / l and 6 times the mass of the glass fiber, stir and react at 65 °C and 400 r / min for 5.5 h, filter, wash 4 times with absolute ethanol and deionized water respectively, and dry at 75 °C under vacuum for 9 h to obtain pre-modified glass fiber; the pre-modified glass fiber and absolute ethanol are mixed evenly at a mass ratio of 1:40, ultrasonically dispersed for 25 min, add palladium / carbon at 0.25 times the mass of the pre-modified glass fiber, stir and reflux at 90 °C and 250 r / min for 35 min, cool to 60 °C, and uniformly dropwise add an aqueous hydrazine hydrate solution with a mass fraction of 55% and 3.5 times the mass of the pre-modified glass fiber within 20 min. After the addition is complete, raise the temperature to 90 °C and stir and reflux at 250 r / min for 7.5 h, filter, wash 4 times with absolute ethanol and deionized water respectively, and dry at 65 °C under vacuum for 11 h to obtain modified glass fiber; (3) Ethyl acrylate, butyl acrylate, acryloxypropylbis(trimethylsiloxy)methylsilane, and glycidyl methacrylate were mixed evenly in a molar ratio of 1:1.7:0.7:0.35 to prepare a polymer monomer; di-tert-butyl peroxide and ethyl acetate were mixed evenly in a mass ratio of 1:7 to prepare an initiator solution; the polymer monomer and ethyl acetate were mixed evenly in a mass ratio of 1:0.37, placed in a high-pressure reactor, and nitrogen was introduced to maintain the pressure at 0.28 MPa. At 130 °C and 125 r / min, it was stirred for 9 min, an initiator solution 0.025 times the mass of the polymer monomer was added, and the stirring reaction was continued for 95 min. The product was discharged and placed in a devolatilization extruder for devolatilization. The temperature of the devolatilization extruder was set at 160 °C, the vacuum degree was 0.015 MPa, and the screw speed was 110 r / min. After devolatilization, it was dried at 75 °C for 5.5 h under vacuum conditions to obtain an acrylate raw rubber. (4) By mass, 100 parts of acrylate raw rubber, 6.5 parts of modified glass fiber, 11 parts of functional flame retardant, and 1.1 parts of triphenylphosphine were weighed; the acrylate raw rubber, modified glass fiber, functional flame retardant, and triphenylphosphine were mixed evenly and placed in a mixer. It was kneaded at 155 °C and 55 r / min for 13 min, discharged, passed through a two-roll mill for 6 passes, kept warm at 75 °C for 85 min, and cooled to room temperature to obtain a high-strength acrylate rubber material.

[0026] Example 3: A preparation method of a high-strength acrylate rubber material, the preparation method of the high-strength acrylate rubber material includes the following preparation steps: (1) 1,1-(1,6-Hexanediyl)bisimidazole and 2-bromomethyl-2-hydroxymethyl-1,3-propanediol were added to chloroform 10 times the mass of 1,1-(1,6-hexanediyl)bisimidazole in a molar ratio of 1:2, and stirred and reacted at 52 °C and 300 r / min for 7 h. Under vacuum conditions, it was dried at 50 °C for 8 h to obtain a polyhydroxy imidazole salt; the polyhydroxy imidazole salt and phosphorus pentoxide were added to deionized water 20 times the mass of the polyhydroxy imidazole salt in a molar ratio of 1:4, and stirred and reacted at 82 °C and 300 r / min for 3 h. The deionized water was evaporated to dryness with a rotary evaporator, the evaporation temperature was 60 °C, the evaporation speed was 120 r / min, and the evaporation time was 60 min. It was washed 5 times with absolute ethanol and dried at 60 °C for 8 h under vacuum conditions to obtain a functional flame retardant. (2) 3-isothiopropyltriethoxysilane and N1-(4-nitrophenyl)benzene-1,4-diamine were added to absolute ethanol which was 8 times the mass of 3-isothiopropyltriethoxysilane at a molar ratio of 1:1.3. Dibutyltin dilaurate which was 0.05 times the mass of 3-isothiopropyltriethoxysilane was added. The reaction was carried out at 60 °C under stirring at 300 r / min for 5 h. After cooling to room temperature, the reaction was continued with stirring for 10 h to obtain a functionalized siloxane reaction solution; glass fiber and absolute ethanol were mixed evenly at a mass ratio of 1:60, ultrasonically dispersed for 90 min, the functionalized siloxane reaction solution which was 26 times the mass of the glass fiber was added, an oxalic acid aqueous solution with a concentration of 1 mol / l which was 7 times the mass of the glass fiber was added. The reaction was carried out at 70 °C under stirring at 500 r / min for 5 h, filtered, washed 5 times each with absolute ethanol and deionized water, and dried at 80 °C for 8 h under vacuum conditions to obtain pre-modified glass fiber; the pre-modified glass fiber and absolute ethanol were mixed evenly at a mass ratio of 1:42, ultrasonically dispersed for 30 min, palladium / carbon which was 0.3 times the mass of the pre-modified glass fiber was added. The reaction was carried out under reflux with stirring at 92 °C at 300 r / min for 30 min, cooled to 62 °C, and an aqueous solution of hydrazine hydrate with a mass fraction of 50% which was 4 times the mass of the pre-modified glass fiber was added dropwise evenly within 20 min. After the addition was completed, the temperature was raised to 92 °C, and the reaction was carried out under reflux with stirring at 300 r / min for 7 h, filtered, washed 5 times each with absolute ethanol and deionized water, and dried at 70 °C for 10 h under vacuum conditions to obtain modified glass fiber; (3) Ethyl acrylate, butyl acrylate, acryloxypropylbis(trimethylsiloxy)methylsilane, and glycidyl methacrylate were mixed evenly at a molar ratio of 1:1.8:0.8:0.4 to prepare a polymer monomer; di-tert-butyl peroxide and ethyl acetate were mixed evenly at a mass ratio of 1:8 to prepare an initiator solution; the polymer monomer and ethyl acetate were mixed evenly at a mass ratio of 1:0.38, placed in a high-pressure reaction kettle, and nitrogen was introduced to maintain the pressure at 0.3 MPa. The reaction was carried out at 132 °C under stirring at 130 r / min for 8 min, an initiator solution which was 0.03 times the mass of the polymer monomer was added, and the reaction was continued with stirring for 90 min. The product was discharged and subjected to devolatilization in a devolatilizing extruder. The temperature of the devolatilizing extruder was set at 162 °C, the vacuum degree was 0.02 MPa, and the screw speed was 120 r / min. After devolatilization, it was dried at 80 °C for 5 h under vacuum conditions to obtain an acrylate raw rubber; (4) By mass, 102 parts of acrylate raw rubber, 7 parts of modified glass fiber, 12 parts of functional flame retardant, and 1.2 parts of triphenylphosphine were weighed; the acrylate raw rubber, modified glass fiber, functional flame retardant, and triphenylphosphine were mixed evenly, placed in a mixer, and kneaded at 160 °C at 60 r / min for 12 min. The product was discharged and passed through a two-roll mill for 7 thin passes, kept warm at 80 °C for 80 min, and cooled to room temperature to obtain a high-strength acrylate rubber material.

[0027] Comparative Example 1: The preparation method of the high-strength acrylate rubber material in Comparative Example 1 is different from that in Example 2 in that step (1) is not carried out, and step (4) is modified as follows: by mass, 100 parts of acrylate raw rubber, 6.5 parts of modified glass fiber, and 1.1 parts of triphenylphosphine are weighed; the acrylate raw rubber, modified glass fiber, and triphenylphosphine are mixed evenly, placed in a mixer, and kneaded at 155 °C and 55 r / min for 13 min, discharged, passed through a two-roll mill 6 times, kept warm at 75 °C for 85 min, cooled to room temperature, and a high-strength acrylate rubber material is obtained. The remaining steps are the same as those in Example 2.

[0028] Comparative Example 2: The preparation method of the high-strength acrylate rubber material in Comparative Example 2 is different from that in Example 2 in step (2). Step (2) is modified as follows: 3-isothiopropyltriethoxysilane and N1-(4-nitrophenyl)benzene-1,4-diamine are added to anhydrous ethanol 7.5 times the mass of 3-isothiopropyltriethoxysilane at a molar ratio of 1:1.2, and dibutyltin dilaurate 0.04 times the mass of 3-isothiopropyltriethoxysilane is added. The reaction is carried out at 55 °C and 250 r / min for 5.5 h, and after cooling to room temperature, the reaction is continued with stirring for 11 h to obtain a functionalized siloxane reaction solution; glass fiber and anhydrous ethanol are mixed evenly at a mass ratio of 1:55, ultrasonically dispersed for 85 min, a functionalized siloxane reaction solution 25 times the mass of the glass fiber is added, and an oxalic acid aqueous solution with a concentration of 1 mol / l 6 times the mass of the glass fiber is added. The reaction is carried out at 65 °C and 400 r / min for 5.5 h, filtered, washed 4 times each with anhydrous ethanol and deionized water, and dried at 75 °C for 9 h under vacuum conditions to obtain modified glass fiber. The remaining steps are the same as those in Example 2.

[0029] Comparative Example 3: The preparation method of the high-strength acrylate rubber material in Comparative Example 3 is different from that in Example 2 in that step (2) is not carried out, and step (4) is modified as follows: by mass, 100 parts of acrylate raw rubber, 6.5 parts of glass fiber, 11 parts of functional flame retardant, and 1.1 parts of triphenylphosphine are weighed; the acrylate raw rubber, glass fiber, functional flame retardant, and triphenylphosphine are mixed evenly, placed in a mixer, and kneaded at 155 °C and 55 r / min for 13 min, discharged, passed through a two-roll mill 6 times, kept warm at 75 °C for 85 min, cooled to room temperature, and a high-strength acrylate rubber material is obtained. The remaining steps are the same as those in Example 2.

[0030] Comparative Example 4: The preparation method of the high-strength acrylate rubber material of Comparative Example 4 is different from that of Example 2 in step (3). Modify step (3) as follows: Ethyl acrylate, butyl acrylate, and glycidyl methacrylate are mixed evenly according to a molar ratio of 1:2.4:0.35 to prepare a polymer monomer; di-tert-butyl peroxide and ethyl acetate are mixed evenly according to a mass ratio of 1:7 to prepare an initiator solution; the polymer monomer and ethyl acetate are mixed evenly according to a mass ratio of 1:0.37, placed in a high-pressure reactor, and nitrogen is introduced to maintain the pressure at 0.28 MPa. At 130 °C, stir at 125 r / min for 9 min, add an initiator solution 0.025 times the mass of the polymer monomer, continue stirring and reacting for 95 min, discharge, and place it in a devolatilization extruder for devolatilization. Set the temperature of the devolatilization extruder to 160 °C, the vacuum degree to 0.015 MPa, and the screw speed to 110 r / min. After devolatilization, dry it at 75 °C for 5.5 h under vacuum conditions to obtain acrylate raw rubber. The remaining steps are the same as those in Example 2.

[0031] Test Example 1 Test of Flame Retardant Performance Test method: Prepare standard specimens from the examples and comparative examples according to the GB / T5454-1997 standard, and test the limiting oxygen index of the standard specimens. The results are shown in Table 1.

[0032] Table 1 Limiting oxygen index (%) Limiting oxygen index (%) Example 1 30.87 Comparative Example 1 24.67 Example 2 31.32 Comparative Example 2 30.64 Example 3 31.18 Comparative Example 3 30.72 Comparative Example 4 25.38 From the comparison of the experimental data of Examples 1-3 and Comparative Examples 1-4 in Table 1, it can be found that the high-strength acrylate rubber material prepared by the present invention has good flame retardant performance.

[0033] By comparison, the limiting oxygen index of Examples 1-3 is greater than that of Comparative Example 1, indicating that 1,1-(1,6-hexanediyl)bis(imidazole) and 2-bromomethyl-2-hydroxymethyl-1,3-propanediol are reacted to prepare a polyhydroxy imidazole salt, and multiple hydroxyl groups are introduced onto the polyhydroxy imidazole salt; the polyhydroxy imidazole salt and phosphorus pentoxide are reacted to prepare a functional flame retardant, and a phosphate group is formed on the functional flame retardant; the phosphate group contains phosphorus elements, which can improve the flame retardant performance of the high-strength acrylate rubber material.

[0034] By comparison, the limiting oxygen index of Examples 1-3 is greater than that of Comparative Example 4, indicating that acrylate raw rubber is prepared by solution polymerization of ethyl acrylate, butyl acrylate, acryloxypropylbis(trimethylsiloxysilyl)methane, and glycidyl methacrylate; a siloxane structure is introduced onto the side chain of the acrylate raw rubber molecule; the introduction of the siloxane structure can promote carbon formation and further improve the flame retardant performance of the high-strength acrylate rubber material.

[0035] Test Example 2 Testing of Mechanical Properties and Aging Resistance Testing Method: According to the national standard GB / T528 - 2009, the examples and comparative examples were prepared into standard specimens, and the tensile strength M of the standard specimens was tested on an electronic tensile machine; the thickness of the standard specimens was 2.0 ± 0.2 mm, and the tensile speed was 500 mm / min; The standard specimens were subjected to hot - air aging. The testing conditions for hot - air aging were: hot - air aging at 110 °C for 24 h, and the tensile strength N of the standard specimens after hot - air aging was tested according to the national standard GB / T528 - 2009; calculate the performance degradation rate of the standard specimens before and after hot - air aging, and the performance degradation rate = (M - N) / M × 100%. The results are shown in Table 2.

[0036] Table 2 Tensile strength (MPa) Performance degradation rate (%) Tensile strength (MPa) Performance degradation rate (%) Example 1 14.87 2.22 Comparative Example 1 11.38 2.57 Example 2 15.13 2.08 Comparative Example 2 12.02 2.46 Example 3 15.05 2.18 Comparative Example 3 10.23 15.12 Comparative Example 4 14.61 2.39 From the comparison of the experimental data of Examples 1 - 3 and Comparative Examples 1 - 4 in Table 2, it can be found that the high - strength acrylate rubber material prepared by the present invention has good mechanical properties and aging resistance.

[0037] By comparison, the tensile strength of Examples 1 - 3 is greater than that of Comparative Example 1, indicating that polyhydroxyimidazolium salt is prepared by reacting 1,1 - (1,6 - hexanediyl) bisimidazole and 2 - (bromomethyl) - 2 - (hydroxymethyl) - 1,3 - propanediol; a functional flame retardant is prepared by reacting the polyhydroxyimidazolium salt with phosphorus pentoxide, and phosphate groups are generated on the functional flame retardant; the phosphate groups can also react with the epoxy groups introduced on the side chains of acrylate raw rubber molecules to form phosphate ester bonds, forming a cross - linked network, thus improving the mechanical properties of the high - strength acrylate rubber material.

[0038] By comparison, the tensile strength of Examples 1 - 3 is greater than that of Comparative Examples 2 - 3, indicating that pre - modified glass fibers are prepared by reacting 3 - isothiocyanatopropyltriethoxysilane with N1 - (4 - nitrophenyl) benzene - 1,4 - diamine and glass fibers in sequence, and nitro groups are introduced on the pre - modified glass fibers; the nitro groups on the pre - modified glass fibers are reduced to amino groups with hydrazine hydrate to obtain modified glass fibers, and amino groups are introduced on the modified glass fibers; the amino groups introduced on the modified glass fibers can react with the epoxy groups introduced on the side chains of acrylate raw rubber molecules to form a cross - linked network, thus improving the mechanical properties of the high - strength acrylate rubber material; glass fiber is an inorganic non - metallic material with high strength and high modulus properties. Adding glass fiber to rubber can improve the mechanical properties of rubber, but directly adding glass fiber has the problem of poor compatibility. Surface modification of glass fiber can improve the compatibility between glass fiber and acrylate rubber, make glass fiber evenly dispersed in acrylate rubber, and give full play to the reinforcing effect of glass fiber, further improving the mechanical properties of the high - strength acrylate rubber material.

[0039] Test Example 3 Test of Antibacterial Performance Test Method: Prepare the examples and comparative examples into circular thin slices with a thickness of 2 mm and a diameter of 6 mm; use Staphylococcus aureus as the experimental strain, activate Staphylococcus aureus at 37 °C for 24 h, and prepare a bacterial suspension with a concentration of 1×10 7 cfu / mL; use a pipette to transfer 0.2 ml of the bacterial suspension and evenly coat it on the surface of the beef extract peptone agar medium, then invert the circular thin slice on the surface of the medium, place it in a constant temperature incubator, and culture it at 37 °C for 24 h, and measure the diameter of the inhibition zone. The results are shown in Table 3.

[0040] Table 3 Inhibition zone diameter (mm) Inhibition zone diameter (mm) Example 1 13.59 Comparative Example 1 7.28 Example 2 13.87 Comparative Example 2 13.37 Example 3 13.64 Comparative Example 3 13.25 Comparative Example 4 13.42 From the comparison of the experimental data of Examples 1-3 and Comparative Examples 1-4 in Table 3, it can be found that the high-strength acrylate rubber material prepared by the present invention has good antibacterial performance.

[0041] By comparison, the diameter of the inhibition zone of Examples 1-3 is larger than that of Comparative Example 1, indicating that polyhydroxyimidazolium salt is prepared by reacting 1,1-(1,6-hexanediyl)bisimidazole and 2-bromomethyl-2-hydroxymethyl-1,3-propanediol; a functional flame retardant is prepared by reacting the polyhydroxyimidazolium salt and phosphorus pentoxide, and an imidazolium salt is formed on the functional flame retardant; the imidazolium salt belongs to a cationic antibacterial agent, which can improve the antibacterial performance of the high-strength acrylate rubber material.

[0042] The specific embodiments described above further elaborate on the purpose, technical solutions, and beneficial effects of the present invention. It should be understood that the above description is only the specific embodiments of the present invention and is not used to limit the protection scope of the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A high-strength acrylate rubber material, characterized in that, The high-strength acrylate rubber material is prepared by reacting polyhydroxyimidazole salt and phosphorus pentoxide to obtain a functional flame retardant; reacting pre-modified glass fiber and hydrazine hydrate to obtain modified glass fiber; mixing acrylate raw rubber, modified glass fiber, functional flame retardant, and triphenylphosphine evenly, and then performing plastic refining and thin pass rolling. The polyhydroxyimidazole salt is prepared by reacting 1,1-(1,6-hexanediyl)bisimidazole and 2-(bromomethyl)-2-(hydroxymethyl)-1,3-propanediol. The pre-modified glass fiber is prepared by reacting 3-isothiopropyltriethoxysilane with N1-(4-nitrophenyl)benzene-1,4-diamine and glass fiber in sequence. The acrylate raw rubber is prepared by solution polymerization of ethyl acrylate, butyl acrylate, acryloxypropylbis(trimethylsiloxy)methylsilane, and glycidyl methacrylate.

2. A preparation method of a high-strength acrylate rubber material, characterized in that The preparation method of the high-strength acrylate rubber material includes the following preparation steps: (1) Mix polyhydroxyimidazole salt and phosphorus pentoxide at a molar ratio of 1:(3 - 4), react at 78 - 82 °C for 3 - 4 h, wash and dry to obtain a functional flame retardant. (2) Using palladium / carbon as a catalyst, reflux and stir pre-modified glass fiber and aqueous hydrazine hydrate solution at 88 - 92 °C for 7 - 8 h, filter, wash and dry to obtain modified glass fiber. (3) Place the polymerization monomers in a high-pressure reactor, introduce nitrogen to maintain the pressure at 0.26 - 0.3 MPa, stir at 128 - 132 °C for 8 - 10 min, add the initiator solution, continue to stir and react for 90 - 100 min, discharge, remove volatile components, and dry to obtain acrylate raw rubber. (4) Mix acrylate raw rubber, modified glass fiber, functional flame retardant, and triphenylphosphine evenly, knead in a mixer, then perform thin pass rolling on an open mill, and keep warm at 70 - 80 °C for 80 - 90 min to obtain the high-strength acrylate rubber material.

3. The preparation method of a high-strength acrylate rubber material according to claim 2, characterized in that, The preparation method of the polyhydroxyimidazole salt in step (1) is as follows: Add 1,1-(1,6-hexanediyl)bisimidazole and 2-(bromomethyl)-2-(hydroxymethyl)-1,3-propanediol at a molar ratio of 1:2 to chloroform which is 8 - 10 times the mass of 1,1-(1,6-hexanediyl)bisimidazole, stir and react at 48 - 52 °C and 200 - 300 r / min for 7 - 8 h, and dry at 50 - 60 °C under vacuum conditions for 8 - 9 h to obtain polyhydroxyimidazole salt.

4. The preparation method of a high-strength acrylate rubber material according to claim 2, characterized in that, In step (1), the rotary evaporation temperature of the rotary evaporator is 50 - 60 °C, the rotary evaporation speed is 100 - 120 r / min, and the rotary evaporation time is 60 - 70 min.

5. The preparation method of a high-strength acrylate rubber material according to claim 2, characterized in that, The preparation method of the pre-modified glass fiber described in step (2) is as follows: Mix glass fiber and absolute ethanol in a mass ratio of 1:(50 - 60) evenly, perform ultrasonic dispersion for 80 - 90 min, add a functionalized siloxane reaction solution that is 24 - 26 times the mass of the glass fiber, add an oxalic acid aqueous solution with a concentration of 1 mol / l that is 5 - 7 times the mass of the glass fiber, stir and react at 60 - 70 °C and 300 - 500 r / min for 5 - 6 h, filter, wash 3 - 5 times with absolute ethanol and deionized water respectively, and dry at 70 - 80 °C for 8 - 10 h under vacuum conditions to obtain the pre-modified glass fiber; the single filament diameter of the glass fiber is 10 - 20 μm.

6. The preparation method of a high-strength acrylate rubber material according to claim 5, characterized in that, The preparation method of the functionalized siloxane reaction solution is as follows: Add 3-isothiocyanatopropyltriethoxysilane and N1-(4-nitrophenyl)benzene-1,4-diamine in a molar ratio of 1:(1.1 - 1.3) to absolute ethanol that is 7 - 8 times the mass of 3-isothiocyanatopropyltriethoxysilane, add dibutyltin dilaurate that is 0.03 - 0.05 times the mass of 3-isothiocyanatopropyltriethoxysilane, react under stirring conditions at 50 - 60 °C and 200 - 300 r / min for 5 - 6 h, cool to room temperature and continue to stir and react for 10 - 12 h to obtain the functionalized siloxane reaction solution.

7. The preparation method of a high-strength acrylate rubber material according to claim 2, characterized in that, The preparation method of the polymerization monomer described in step (3) is as follows: Mix ethyl acrylate, butyl acrylate, acryloxypropylbis(trimethylsiloxy)methylsilane, and glycidyl methacrylate in a molar ratio of 1:(1.6 - 1.8):(0.6 - 0.8):(0.3 - 0.4) evenly to prepare the polymerization monomer.

8. The preparation method of a high-strength acrylate rubber material according to claim 2, characterized in that The preparation method of the initiator solution described in step (3) is as follows: Mix di-tert-butyl peroxide and ethyl acetate in a mass ratio of 1:(6 - 8) evenly to prepare the initiator solution.

9. The preparation method of a high-strength acrylate rubber material according to claim 2, characterized in that The process parameters of devolatilization in step (3) are as follows: Set the temperature of the devolatilization extruder to 158 - 162 °C, the vacuum degree to 0.01 - 0.02 MPa, and the screw speed to 100 - 120 r / min.

10. The preparation method of a high-strength acrylate rubber material according to claim 2, characterized in that, The preparation method of the high-strength acrylate rubber material described in step (4) is as follows: By mass, weigh 98 - 102 parts of acrylate raw rubber, 6 - 7 parts of modified glass fiber, 10 - 12 parts of functional flame retardant, and 1 - 1.2 parts of triphenylphosphine; mix acrylate raw rubber, modified glass fiber, functional flame retardant, and triphenylphosphine evenly, place them in a mixer, knead at 150 - 160 °C and 50 - 60 r / min for 12 - 14 min, discharge, pass through a two-roll mill for thin rolling 5 - 7 times, keep warm at 70 - 80 °C for 80 - 90 min, and cool to room temperature to obtain the high-strength acrylate rubber material.