CN112920519A - Lightweight porous rubber material and preparation method thereof - Google Patents

Lightweight porous rubber material and preparation method thereof Download PDF

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CN112920519A
CN112920519A CN202110113410.7A CN202110113410A CN112920519A CN 112920519 A CN112920519 A CN 112920519A CN 202110113410 A CN202110113410 A CN 202110113410A CN 112920519 A CN112920519 A CN 112920519A
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stirring
rubber material
temperature
reaction kettle
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蔡丽慈
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C08L23/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefins
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/6574—Esters of oxyacids of phosphorus
    • C07F9/65742—Esters of oxyacids of phosphorus non-condensed with carbocyclic rings or heterocyclic rings or ring systems
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/2224—Magnesium hydroxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/14—Applications used for foams

Abstract

The invention discloses a light porous rubber material and a preparation method thereof, wherein the rubber material comprises the following raw materials in parts by weight: 20-30 parts of butyl rubber, 50-80 parts of dichloromethane, 3-5 parts of flame-retardant filler and 8-10 parts of pore-foaming agent; when the rubber material burns, oxyacid of phosphorus in the flame-retardant filler dehydrates into carbon in catalysis of hydroxyl-containing compounds, and then produces the coke layer on the surface of the material, the coke layer can separate oxygen, insulate against heat and then make flame extinguish, and the comburent can be attached to the material surface and does not produce the drippage, the inside inorganic particle of flame-retardant filler can release a large amount of water vapor when burning simultaneously, and then dilute the concentration of combustible gas, and then prevent the burning, make rubber material further carbonization simultaneously, thereby make the smoke and dust that the burning produced absorbed, and then reduced the smoke and dust production, environmental pollution has been avoided.

Description

Lightweight porous rubber material and preparation method thereof
Technical Field
The invention relates to the technical field of rubber material preparation, in particular to a light porous rubber material and a preparation method thereof.
Background
The porous rubber material integrates the characteristics of rubber and a foam material, not only has excellent high and low temperature resistance, radiation resistance, chemical stability, electrical insulation and the like of the rubber, but also has the properties of light weight, high strength, sound insulation, heat insulation, damping and the like of the foam material, so that the porous rubber material is more and more widely applied to the technical fields of aerospace, advanced weapons, automobiles, electronic industry and the like as a damping vibration damping material, a sound insulation and heat insulation material, a precision device packaging material and the like.
The existing light porous rubber material has certain flame retardant capability, but the extinguishing time of open fire on the surface of rubber is longer, and drops can appear during combustion, which easily causes secondary fire, and simultaneously, a large amount of smoke and dust can be released during combustion, thus having great influence on environmental pollution.
Disclosure of Invention
The invention aims to provide a lightweight porous rubber material and a preparation method thereof.
The technical problems to be solved by the invention are as follows:
the existing light porous rubber material has certain flame retardant capability, but the extinguishing time of open fire on the surface of rubber is longer, and drops can appear during combustion, which easily causes secondary fire, and simultaneously, a large amount of smoke and dust can be released during combustion, thus having great influence on environmental pollution.
The purpose of the invention can be realized by the following technical scheme:
a light porous rubber material comprises the following raw materials in parts by weight: 20-30 parts of butyl rubber, 50-80 parts of dichloromethane, 3-5 parts of flame-retardant filler and 8-10 parts of pore-foaming agent;
the rubber material is prepared by the following steps:
step S1: adding nitrile rubber and dichloromethane into a stirring kettle, stirring for 15-30min at the rotation speed of 500-800r/min, adding flame-retardant filler and pore-forming agent, and performing ultrasonic treatment for 10-15min at the frequency of 3-5MHz to obtain a composite glue solution;
step S2: standing the composite glue solution prepared in the step S1 for 1-2h, and defoaming for 10-15min under the condition that the vacuum degree is 0.2-0.5MPa to prepare a defoaming solution;
step S3: and adding the defoaming solution into a mold, standing for 20-30min at the temperature of 40-60 ℃, heating to the temperature of 110-130 ℃, and curing for 15-20min to obtain the rubber material.
Further, the pore-foaming agent is one or two of polyvinylpyrrolidone and polyethylene glycol which are mixed in any proportion.
Further, the flame-retardant filler is prepared by the following steps:
step A1: adding diphenylphosphinic chloride into a reaction kettle, stirring and adding aluminum trichloride and liquefied methane chloride under the conditions that the rotating speed is 150-200r/min and the temperature is 50-60 ℃, reacting for 3-5h to obtain an intermediate 1, adding the intermediate 1, deionized water and potassium permanganate into the reaction kettle, and performing reflux reaction for 4-5h under the conditions that the temperature is 110-120 ℃ to obtain an intermediate 2;
the reaction process is as follows:
Figure BDA0002919788020000021
step A2: adding diphenylamine into a reaction kettle, stirring and adding mixed acid for stirring under the condition that the rotation speed is 120-plus-150 r/min, heating to the temperature of 50-55 ℃ at the heating speed of 5 ℃/min, reacting for 2-3h to obtain an intermediate 3, dissolving cyanuric chloride into ether, adding the intermediate 3 under the conditions that the rotation speed is 200-plus-300 r/min and the temperature is 80-90 ℃, reacting for 4-6h to obtain an intermediate 4, adding the intermediate 4, 4-nitrobenzol and benzene into the reaction kettle, stirring under the condition that the rotation speed is 200-plus-300 r/min until the intermediate 4 is completely dissolved, adding sodium hydroxide and glucose solution, reacting for 20-30min under the temperature of 70-80 ℃, introducing air, standing for 2-3h, after the pH value of the reaction kettle is adjusted to 5-6, benzene is removed to prepare an intermediate 5;
the reaction process is as follows:
Figure BDA0002919788020000031
Figure BDA0002919788020000041
step A3: adding the intermediate 2, tetrahydrofuran and triethylamine into a reaction kettle, stirring and adding the intermediate 5 under the conditions of the rotation speed of 150-, to prepare an intermediate 8;
the reaction process is as follows:
Figure BDA0002919788020000042
Figure BDA0002919788020000051
step A4: adding 4,4 '-dihydroxy benzophenone and dichloromethane into a reaction kettle, stirring at the rotation speed of 300r/min and the temperature of 25-30 ℃ until the 4,4' -dihydroxy benzophenone is completely dissolved, adding triethylamine and diphenyl chlorophosphate, stirring for 30-40min to obtain an intermediate 9, adding the intermediate 9 and ethanol into the reaction kettle, stirring at the rotation speed of 200r/min until the intermediate 9 is completely dissolved, adding sodium borohydride, continuing to react for 4-6h to obtain an intermediate 10, dissolving the intermediate 10 into toluene, adding triethylamine and the intermediate 8, and performing reflux reaction for 3-5h at the temperature of 120-130 ℃ to obtain an intermediate 11;
the reaction process is as follows:
Figure BDA0002919788020000061
Figure BDA0002919788020000071
step A5: adding brucite powder and ethanol into a reaction kettle, stirring for 10-15min at the rotation speed of 500-600r/min, adding ethyl orthosilicate and deionized water, reacting for 10-15h at the temperature of 60-70 ℃, adding graphene and an intermediate 11, carrying out ultrasonic treatment for 1-1.5h at the frequency of 8-10MHz, filtering to remove filtrate, and drying a filter cake to obtain the flame-retardant filler.
Further, the molar ratio of the diphenylphosphine chloride to the monochloromethane in the step A1 is 1:2, the amount of the aluminum trichloride is 10-15% of the mass of the diphenylphosphine chloride, and the amount ratio of the intermediate 1, the deionized water and the potassium permanganate is 2g:50mL:4.5 g.
Further, the dosage ratio of diphenylamine and mixed acid in the step A2 is 1g:5mL, the mixed acid is formed by mixing 68% by mass of nitric acid and 95% by mass of sulfuric acid in a volume ratio of 1:1.2, the dosage molar ratio of cyanuric chloride to the intermediate 3 is 1:3, the dosage ratio of the intermediate 4, 4-nitrobenzol, sodium hydroxide and glucose solution is 5mol:30mol:2mol:100mL, and the mass fraction of the glucose solution is 40%.
Further, the molar ratio of the intermediate 2, the intermediate 5 and triethylamine in the step A3 is 1:6:1, the molar ratio of glycerol to phosphorus oxychloride is 1:1, the molar ratio of the intermediate 6 to the intermediate 7 is 1:6, and the amount of concentrated sulfuric acid is 20-25% of the mass of the intermediate 6.
Further, the molar ratio of the 4,4' -dihydroxybenzophenone, triethylamine, diphenyl chlorophosphate in step a4 is 1:2.2:2, the molar ratio of the intermediate 9 to sodium borohydride is 1:0.6, and the molar ratio of the intermediate 10, the intermediate 8, triethylamine is 6:1: 1.2.
Further, the amount ratio of the brucite powder, ethanol, ethyl orthosilicate, deionized water, graphene and the intermediate 11 in the step A5 is 5g to 15mL to 3mL to 30mL to 5g to 2.5 g.
A preparation method of a light porous rubber material specifically comprises the following steps:
step S1: adding nitrile rubber and dichloromethane into a stirring kettle, stirring for 15-30min at the rotation speed of 500-800r/min, adding flame-retardant filler and pore-forming agent, and performing ultrasonic treatment for 10-15min at the frequency of 3-5MHz to obtain a composite glue solution;
step S2: standing the composite glue solution prepared in the step S1 for 1-2h, and defoaming for 10-15min under the condition that the vacuum degree is 0.2-0.5MPa to prepare a defoaming solution;
step S3: and adding the defoaming solution into a mold, standing for 20-30min at the temperature of 40-60 ℃, heating to the temperature of 110-130 ℃, and curing for 15-20min to obtain the rubber material.
The invention has the beneficial effects that: the invention discloses a preparing method of light porous rubber material, which comprises preparing a flame-retardant filler, reacting diphenylphosphine chloride as raw material with methane chloride under the action of aluminum trichloride to obtain an intermediate 1, oxidizing the intermediate 1 with potassium permanganate to convert methyl into carboxyl to obtain an intermediate 2, reacting diphenylamine with mixed acid to graft nitro group at benzene ring para-position to obtain an intermediate 3, reacting the intermediate 3 with cyanuric chloride to obtain an intermediate 4, reacting the intermediate 4 with 4-nitrobenzyl alcohol, reacting with air to obtain an intermediate 5, reacting the intermediate 2 with the intermediate 5 to obtain an intermediate 6, reacting glycerol with phosphorus oxychloride to obtain an intermediate 7, reacting the intermediate 6 with the intermediate 7 to obtain an intermediate 8, and reacting the intermediate 4,4' -dihydroxy benzophenone and diphenyl chlorophosphate react under the action of triethylamine to prepare an intermediate 9, the intermediate 9 is treated by sodium borohydride to prepare an intermediate 10, the intermediate 10 and the intermediate 8 react under the action of triethylamine to prepare an intermediate 11, brucite powder is dispersed in ethanol, ethyl orthosilicate and deionized water are added, the ethyl orthosilicate is hydrolyzed on the surface of brucite to form silicon dioxide, and then the silicon dioxide is ultrasonically treated with graphene and the intermediate 11 to prepare the flame-retardant filler, when a rubber material burns, oxyacid of phosphorus in the flame-retardant filler catalyzes a hydroxyl-containing compound to dehydrate into carbon, so that a coke layer is generated on the surface of the material, the coke layer can insulate oxygen and heat to extinguish flame, and a combustion product can be attached to the surface of the material without dripping, and simultaneously inorganic particles in the flame-retardant filler can release a large amount of water vapor during burning, and then dilute the concentration of combustible gas, and then prevent the burning, make rubber material further carbonization simultaneously to make the smoke and dust that the burning produced absorbed, and then reduced the smoke and dust and produced, avoided environmental pollution.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A light porous rubber material comprises the following raw materials in parts by weight: 20 parts of butyl rubber, 50 parts of dichloromethane, 3 parts of flame-retardant filler and 8 parts of polyvinylpyrrolidone;
the rubber material is prepared by the following steps:
step S1: adding nitrile rubber and dichloromethane into a stirring kettle, stirring for 15min at the rotation speed of 500r/min, adding flame-retardant filler and polyvinylpyrrolidone, and performing ultrasonic treatment for 10min at the frequency of 3MHz to obtain a composite glue solution;
step S2: standing the composite glue solution prepared in the step S1 for 1h, and defoaming for 10min under the condition that the vacuum degree is 0.2MPa to prepare a defoaming solution;
step S3: and adding the defoaming solution into a mold, standing for 20min at the temperature of 40 ℃, heating to the temperature of 110 ℃, and curing for 15min to obtain the rubber material.
The flame-retardant filler is prepared by the following steps:
step A1: adding diphenylphosphinic chloride into a reaction kettle, stirring and adding aluminum trichloride and liquefied methane chloride under the conditions that the rotating speed is 150r/min and the temperature is 50 ℃, reacting for 3 hours to obtain an intermediate 1, adding the intermediate 1, deionized water and potassium permanganate into the reaction kettle, and performing reflux reaction for 4 hours at the temperature of 110 ℃ to obtain an intermediate 2;
step A2: adding diphenylamine into a reaction kettle, stirring and adding mixed acid for stirring under the condition that the rotating speed is 120r/min, heating to the temperature of 50 ℃ at the heating speed of 5 ℃/min, reacting for 2 hours to obtain an intermediate 3, dissolving cyanuric chloride in diethyl ether, adding the intermediate 3 under the conditions that the rotating speed is 200r/min and the temperature is 80 ℃, reacting for 4 hours to obtain an intermediate 4, adding the intermediate 4, 4-nitrobenzyl alcohol and benzene into the reaction kettle, stirring under the condition that the rotating speed is 200r/min until the intermediate 4 is completely dissolved, adding sodium hydroxide and glucose solution, reacting for 20 minutes under the condition that the temperature is 70 ℃, introducing air, standing for 2 hours, adjusting the pH value of the reaction kettle to be 5, and removing benzene to obtain an intermediate 5;
step A3: adding the intermediate 2, tetrahydrofuran and triethylamine into a reaction kettle, stirring and adding the intermediate 5 under the conditions that the rotation speed is 150r/min and the temperature is 3 ℃, stirring for 1.5h, heating to the temperature of 60 ℃, continuing to react for 5h to obtain an intermediate 6, adding glycerol and chloroform into the reaction kettle, stirring and dropwise adding phosphorus oxychloride under the conditions that the rotation speed is 200r/min and the temperature is 35 ℃, dropwise adding for 1h, reacting for 2h to obtain an intermediate 7, adding the intermediate 6, the intermediate 7 and tetrahydrofuran into the reaction kettle, stirring and adding concentrated sulfuric acid under the conditions that the rotation speed is 150r/min and the temperature is 70 ℃, and reacting for 2h to obtain an intermediate 8;
step A4: adding 4,4 '-dihydroxy benzophenone and dichloromethane into a reaction kettle, stirring until the 4,4' -dihydroxy benzophenone is completely dissolved at the rotation speed of 200r/min and the temperature of 25 ℃, adding triethylamine and diphenyl chlorophosphate, stirring for 30min to obtain an intermediate 9, adding the intermediate 9 and ethanol into the reaction kettle, stirring until the intermediate 9 is completely dissolved at the rotation speed of 150r/min, adding sodium borohydride, continuing to react for 4h to obtain an intermediate 10, dissolving the intermediate 10 in toluene, adding triethylamine and the intermediate 8, and performing reflux reaction for 3h at the temperature of 120 ℃ to obtain an intermediate 11;
step A5: adding brucite powder and ethanol into a reaction kettle, stirring for 10min at the rotation speed of 500r/min, adding ethyl orthosilicate and deionized water, reacting for 10h at the temperature of 60 ℃, adding graphene and an intermediate 11, carrying out ultrasonic treatment for 1h at the frequency of 8MHz, filtering to remove filtrate, and drying a filter cake to obtain the flame-retardant filler.
Example 2
A light porous rubber material comprises the following raw materials in parts by weight: 23 parts of butyl rubber, 60 parts of dichloromethane, 4 parts of flame-retardant filler and 9 parts of polyvinylpyrrolidone;
the rubber material is prepared by the following steps:
step S1: adding nitrile rubber and dichloromethane into a stirring kettle, stirring for 30min at the rotation speed of 500r/min, adding flame-retardant filler and polyvinylpyrrolidone, and performing ultrasonic treatment for 15min at the frequency of 3MHz to obtain a composite glue solution;
step S2: standing the composite glue solution prepared in the step S1 for 1h, and defoaming for 10min under the condition that the vacuum degree is 0.5MPa to prepare a defoaming solution;
step S3: and adding the defoaming solution into a mold, standing for 20min at the temperature of 60 ℃, heating to 130 ℃, and curing for 15min to obtain the rubber material.
The flame-retardant filler is prepared by the following steps:
step A1: adding diphenylphosphinic chloride into a reaction kettle, stirring and adding aluminum trichloride and liquefied methane chloride under the conditions of the rotating speed of 200r/min and the temperature of 50 ℃, reacting for 5 hours to obtain an intermediate 1, adding the intermediate 1, deionized water and potassium permanganate into the reaction kettle, and performing reflux reaction for 5 hours at the temperature of 110 ℃ to obtain an intermediate 2;
step A2: adding diphenylamine into a reaction kettle, stirring and adding mixed acid for stirring under the condition that the rotating speed is 120r/min, heating to 55 ℃ at the heating speed of 5 ℃/min, reacting for 2 hours to obtain an intermediate 3, dissolving cyanuric chloride in diethyl ether, adding the intermediate 3 under the conditions that the rotating speed is 300r/min and the temperature is 80 ℃, reacting for 6 hours to obtain an intermediate 4, adding the intermediate 4, 4-nitrobenzyl alcohol and benzene into the reaction kettle, stirring under the condition that the rotating speed is 200r/min until the intermediate 4 is completely dissolved, adding sodium hydroxide and glucose solution, reacting for 20 minutes under the condition that the temperature is 80 ℃, introducing air, standing for 3 hours, adjusting the pH value of the reaction kettle to 5, and removing benzene to obtain an intermediate 5;
step A3: adding the intermediate 2, tetrahydrofuran and triethylamine into a reaction kettle, stirring and adding the intermediate 5 under the conditions of the rotation speed of 200r/min and the temperature of 3 ℃, stirring for 2 hours, heating to the temperature of 60 ℃, continuing to react for 6 hours to obtain an intermediate 6, adding glycerol and chloroform into the reaction kettle, stirring and dropwise adding phosphorus oxychloride under the conditions of the rotation speed of 200r/min and the temperature of 40 ℃, dropwise adding for 1 hour, reacting for 3 hours to obtain an intermediate 7, adding the intermediate 6, the intermediate 7 and tetrahydrofuran into the reaction kettle, stirring and adding concentrated sulfuric acid under the conditions of the rotation speed of 150r/min and the temperature of 80 ℃ to react for 2 hours to obtain an intermediate 8;
step A4: adding 4,4 '-dihydroxy benzophenone and dichloromethane into a reaction kettle, stirring until the 4,4' -dihydroxy benzophenone is completely dissolved at the rotation speed of 300r/min and the temperature of 25 ℃, adding triethylamine and diphenyl chlorophosphate, stirring for 40min to obtain an intermediate 9, adding the intermediate 9 and ethanol into the reaction kettle, stirring until the intermediate 9 is completely dissolved at the rotation speed of 150r/min, adding sodium borohydride, continuing to react for 6h to obtain an intermediate 10, dissolving the intermediate 10 in toluene, adding triethylamine and the intermediate 8, and performing reflux reaction for 3h at the temperature of 120 ℃ to obtain an intermediate 11;
step A5: adding brucite powder and ethanol into a reaction kettle, stirring for 10min at the rotating speed of 600r/min, adding ethyl orthosilicate and deionized water, reacting for 10h at the temperature of 70 ℃, adding graphene and an intermediate 11, carrying out ultrasonic treatment for 1h at the frequency of 10MHz, filtering to remove filtrate, and drying a filter cake to obtain the flame-retardant filler.
Example 3
A light porous rubber material comprises the following raw materials in parts by weight: 28 parts of butyl rubber, 70 parts of dichloromethane, 4 parts of flame-retardant filler and 9 parts of polyvinylpyrrolidone;
the rubber material is prepared by the following steps:
step S1: adding nitrile rubber and dichloromethane into a stirring kettle, stirring for 15min at the rotation speed of 800r/min, adding flame-retardant filler and polyvinylpyrrolidone, and performing ultrasonic treatment for 10min at the frequency of 5MHz to obtain a composite glue solution;
step S2: standing the composite glue solution prepared in the step S1 for 2h, and defoaming for 15min under the condition that the vacuum degree is 0.2MPa to prepare a defoaming solution;
step S3: and adding the defoaming solution into a mold, standing for 30min at the temperature of 40 ℃, heating to the temperature of 110 ℃, and curing for 20min to obtain the rubber material.
The flame-retardant filler is prepared by the following steps:
step A1: adding diphenylphosphinic chloride into a reaction kettle, stirring and adding aluminum trichloride and liquefied methane chloride under the conditions that the rotating speed is 150r/min and the temperature is 60 ℃, reacting for 3 hours to obtain an intermediate 1, adding the intermediate 1, deionized water and potassium permanganate into the reaction kettle, and performing reflux reaction for 4 hours at the temperature of 120 ℃ to obtain an intermediate 2;
step A2: adding diphenylamine into a reaction kettle, stirring and adding mixed acid for stirring under the condition that the rotating speed is 150r/min, heating to 50 ℃ at the heating speed of 5 ℃/min, reacting for 3 hours to obtain an intermediate 3, dissolving cyanuric chloride in diethyl ether, adding the intermediate 3 under the conditions that the rotating speed is 200r/min and the temperature is 90 ℃, reacting for 4 hours to obtain an intermediate 4, adding the intermediate 4, 4-nitrobenzyl alcohol and benzene into the reaction kettle, stirring under the condition that the rotating speed is 300r/min until the intermediate 4 is completely dissolved, adding sodium hydroxide and glucose solution, reacting for 30 minutes under the condition that the temperature is 70 ℃, introducing air, standing for 2 hours, adjusting the pH value of the reaction kettle to be 6, and removing benzene to obtain an intermediate 5;
step A3: adding the intermediate 2, tetrahydrofuran and triethylamine into a reaction kettle, stirring and adding the intermediate 5 under the conditions that the rotation speed is 150r/min and the temperature is 5 ℃, stirring for 1.5h, heating to 70 ℃, continuing to react for 5h to obtain an intermediate 6, adding glycerol and chloroform into the reaction kettle, stirring and dropwise adding phosphorus oxychloride under the conditions that the rotation speed is 300r/min and the temperature is 35 ℃, dropwise adding for 1.5h, reacting for 2h to obtain an intermediate 7, adding the intermediate 6, the intermediate 7 and tetrahydrofuran into the reaction kettle, stirring and adding concentrated sulfuric acid under the conditions that the rotation speed is 200r/min and the temperature is 70 ℃, and reacting for 3h to obtain an intermediate 8;
step A4: adding 4,4 '-dihydroxy benzophenone and dichloromethane into a reaction kettle, stirring until the 4,4' -dihydroxy benzophenone is completely dissolved at the rotation speed of 200r/min and the temperature of 30 ℃, adding triethylamine and diphenyl chlorophosphate, stirring for 30min to obtain an intermediate 9, adding the intermediate 9 and ethanol into the reaction kettle, stirring until the intermediate 9 is completely dissolved at the rotation speed of 200r/min, adding sodium borohydride, continuing to react for 4h to obtain an intermediate 10, dissolving the intermediate 10 in toluene, adding triethylamine and the intermediate 8, and performing reflux reaction for 5h at the temperature of 130 ℃ to obtain an intermediate 11;
step A5: adding brucite powder and ethanol into a reaction kettle, stirring for 15min at the rotation speed of 500r/min, adding ethyl orthosilicate and deionized water, reacting for 15h at the temperature of 60 ℃, adding graphene and an intermediate 11, carrying out ultrasonic treatment for 1.5h at the frequency of 8MHz, filtering to remove filtrate, and drying a filter cake to obtain the flame-retardant filler.
Example 4
A light porous rubber material comprises the following raw materials in parts by weight: 30 parts of butyl rubber, 80 parts of dichloromethane, 5 parts of flame-retardant filler and 10 parts of polyvinylpyrrolidone;
the rubber material is prepared by the following steps:
step S1: adding nitrile rubber and dichloromethane into a stirring kettle, stirring for 30min at the rotation speed of 800r/min, adding flame-retardant filler and polyvinylpyrrolidone, and performing ultrasonic treatment for 5min at the frequency of 5MHz to obtain a composite glue solution;
step S2: standing the composite glue solution prepared in the step S1 for 2h, and defoaming for 15min under the condition that the vacuum degree is 0.5MPa to prepare a defoaming solution;
step S3: and adding the defoaming solution into a mold, standing for 30min at the temperature of 60 ℃, heating to 130 ℃, and curing for 20min to obtain the rubber material.
The flame-retardant filler is prepared by the following steps:
step A1: adding diphenylphosphinic chloride into a reaction kettle, stirring and adding aluminum trichloride and liquefied methane chloride under the conditions that the rotating speed is 200r/min and the temperature is 60 ℃, reacting for 5 hours to obtain an intermediate 1, adding the intermediate 1, deionized water and potassium permanganate into the reaction kettle, and performing reflux reaction for 5 hours at the temperature of 120 ℃ to obtain an intermediate 2;
step A2: adding diphenylamine into a reaction kettle, stirring and adding mixed acid for stirring under the condition that the rotating speed is 150r/min, heating to 55 ℃ at the heating speed of 5 ℃/min, reacting for 3 hours to obtain an intermediate 3, dissolving cyanuric chloride in diethyl ether, adding the intermediate 3 under the conditions that the rotating speed is 300r/min and the temperature is 90 ℃, reacting for 6 hours to obtain an intermediate 4, adding the intermediate 4, 4-nitrobenzyl alcohol and benzene into the reaction kettle, stirring under the condition that the rotating speed is 300r/min until the intermediate 4 is completely dissolved, adding sodium hydroxide and glucose solution, reacting for 30 minutes under the condition that the temperature is 80 ℃, introducing air, standing for 3 hours, adjusting the pH value of the reaction kettle to 6, and removing benzene to obtain an intermediate 5;
step A3: adding the intermediate 2, tetrahydrofuran and triethylamine into a reaction kettle, stirring and adding the intermediate 5 under the conditions of the rotation speed of 200r/min and the temperature of 5 ℃, stirring for 2 hours, heating to the temperature of 70 ℃, continuing to react for 6 hours to obtain an intermediate 6, adding glycerol and chloroform into the reaction kettle, stirring and dropwise adding phosphorus oxychloride under the conditions of the rotation speed of 300r/min and the temperature of 40 ℃, dropwise adding for 1.5 hours, reacting for 3 hours to obtain an intermediate 7, adding the intermediate 6, the intermediate 7 and tetrahydrofuran into the reaction kettle, stirring and adding concentrated sulfuric acid under the conditions of the rotation speed of 200r/min and the temperature of 80 ℃ to react for 3 hours to obtain an intermediate 8;
step A4: adding 4,4 '-dihydroxy benzophenone and dichloromethane into a reaction kettle, stirring until the 4,4' -dihydroxy benzophenone is completely dissolved at the rotation speed of 300r/min and the temperature of 30 ℃, adding triethylamine and diphenyl chlorophosphate, stirring for 40min to obtain an intermediate 9, adding the intermediate 9 and ethanol into the reaction kettle, stirring until the intermediate 9 is completely dissolved at the rotation speed of 200r/min, adding sodium borohydride, continuing to react for 6h to obtain an intermediate 10, dissolving the intermediate 10 in toluene, adding triethylamine and the intermediate 8, and performing reflux reaction for 5h at the temperature of 130 ℃ to obtain an intermediate 11;
step A5: adding brucite powder and ethanol into a reaction kettle, stirring for 15min at the rotating speed of 600r/min, adding ethyl orthosilicate and deionized water, reacting for 15h at the temperature of 70 ℃, adding graphene and an intermediate 11, carrying out ultrasonic treatment for 1.5h at the frequency of 10MHz, filtering to remove filtrate, and drying a filter cake to obtain the flame-retardant filler.
Comparative example
The comparative example is a common rubber material on the market.
The rubber materials obtained in examples 1 to 4 and comparative example were subjected to the performance test, and the test results are shown in table 1 below;
TABLE 1
Figure BDA0002919788020000161
As is apparent from Table 1 above, the rubber materials obtained in examples 1 to 4 exhibited burning times of 4 to 5S, no generation of dripping during burning, and soot formation rates of 0.079 to 0.084m2/s2The rubber material obtained in comparative example had a burning time of 8S, a small amount of dripping during burning, and a smoke generation rate of 0.372m2/s2The rubber material prepared by the invention has good flame retardant effect, and little smoke is generated during combustion.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.

Claims (9)

1. A lightweight cellular rubber material characterized by: the feed comprises the following raw materials in parts by weight: 20-30 parts of butyl rubber, 50-80 parts of dichloromethane, 3-5 parts of flame-retardant filler and 8-10 parts of pore-foaming agent;
the rubber material is prepared by the following steps:
step S1: adding nitrile rubber and dichloromethane into a stirring kettle, stirring for 15-30min at the rotation speed of 500-800r/min, adding flame-retardant filler and pore-forming agent, and performing ultrasonic treatment for 10-15min at the frequency of 3-5MHz to obtain a composite glue solution;
step S2: standing the composite glue solution prepared in the step S1 for 1-2h, and defoaming for 10-15min under the condition that the vacuum degree is 0.2-0.5MPa to prepare a defoaming solution;
step S3: and adding the defoaming solution into a mold, standing for 20-30min at the temperature of 40-60 ℃, heating to the temperature of 110-130 ℃, and curing for 15-20min to obtain the rubber material.
2. The lightweight cellular rubber material according to claim 1, wherein: the pore-foaming agent is one or two of polyvinylpyrrolidone and polyethylene glycol which are mixed in any proportion.
3. The lightweight cellular rubber material according to claim 1, wherein: the flame-retardant filler is prepared by the following steps:
step A1: adding diphenylphosphinic chloride into a reaction kettle, stirring and adding aluminum trichloride and liquefied methane chloride under the conditions that the rotating speed is 150-200r/min and the temperature is 50-60 ℃, reacting for 3-5h to obtain an intermediate 1, adding the intermediate 1, deionized water and potassium permanganate into the reaction kettle, and performing reflux reaction for 4-5h under the conditions that the temperature is 110-120 ℃ to obtain an intermediate 2;
step A2: adding diphenylamine into a reaction kettle, stirring and adding mixed acid for stirring under the condition that the rotation speed is 120-plus-150 r/min, heating to the temperature of 50-55 ℃ at the heating speed of 5 ℃/min, reacting for 2-3h to obtain an intermediate 3, dissolving cyanuric chloride into ether, adding the intermediate 3 under the conditions that the rotation speed is 200-plus-300 r/min and the temperature is 80-90 ℃, reacting for 4-6h to obtain an intermediate 4, adding the intermediate 4, 4-nitrobenzol and benzene into the reaction kettle, stirring under the condition that the rotation speed is 200-plus-300 r/min until the intermediate 4 is completely dissolved, adding sodium hydroxide and glucose solution, reacting for 20-30min under the temperature of 70-80 ℃, introducing air, standing for 2-3h, after the pH value of the reaction kettle is adjusted to 5-6, benzene is removed to prepare an intermediate 5;
step A3: adding the intermediate 2, tetrahydrofuran and triethylamine into a reaction kettle, stirring and adding the intermediate 5 under the conditions of the rotation speed of 150-, to prepare an intermediate 8;
step A4: adding 4,4 '-dihydroxy benzophenone and dichloromethane into a reaction kettle, stirring at the rotation speed of 300r/min and the temperature of 25-30 ℃ until the 4,4' -dihydroxy benzophenone is completely dissolved, adding triethylamine and diphenyl chlorophosphate, stirring for 30-40min to obtain an intermediate 9, adding the intermediate 9 and ethanol into the reaction kettle, stirring at the rotation speed of 200r/min until the intermediate 9 is completely dissolved, adding sodium borohydride, continuing to react for 4-6h to obtain an intermediate 10, dissolving the intermediate 10 into toluene, adding triethylamine and the intermediate 8, and performing reflux reaction for 3-5h at the temperature of 120-130 ℃ to obtain an intermediate 11;
step A5: adding brucite powder and ethanol into a reaction kettle, stirring for 10-15min at the rotation speed of 500-600r/min, adding ethyl orthosilicate and deionized water, reacting for 10-15h at the temperature of 60-70 ℃, adding graphene and an intermediate 11, carrying out ultrasonic treatment for 1-1.5h at the frequency of 8-10MHz, filtering to remove filtrate, and drying a filter cake to obtain the flame-retardant filler.
4. A lightweight cellular rubber material according to claim 3, wherein: the molar ratio of the diphenyl phosphinic chloride to the monochloromethane in the step A1 is 1:2, the dosage of the aluminum trichloride is 10-15% of the mass of the diphenyl phosphinic chloride, and the dosage ratio of the intermediate 1, the deionized water and the potassium permanganate is 2g:50mL:4.5 g.
5. A lightweight cellular rubber material according to claim 3, wherein: the dosage ratio of diphenylamine and mixed acid in the step A2 is 1g:5mL, the mixed acid is formed by mixing 68% by mass of nitric acid and 95% by mass of sulfuric acid in a volume ratio of 1:1.2, the dosage molar ratio of cyanuric chloride to the intermediate 3 is 1:3, the dosage ratio of the intermediate 4, 4-nitrobenzol, sodium hydroxide and glucose solution is 5mol:30mol:2mol:100mL, and the mass fraction of the glucose solution is 40%.
6. A lightweight cellular rubber material according to claim 3, wherein: the molar ratio of the intermediate 2, the intermediate 5 and the triethylamine in the step A3 is 1:6:1, the molar ratio of the glycerol to the phosphorus oxychloride is 1:1, the molar ratio of the intermediate 6 to the intermediate 7 is 1:6, and the amount of concentrated sulfuric acid is 20-25% of the mass of the intermediate 6.
7. A lightweight cellular rubber material according to claim 3, wherein: the molar ratio of the 4,4' -dihydroxy benzophenone, the triethylamine and the diphenyl chlorophosphate in the step A4 is 1:2.2:2, the molar ratio of the intermediate 9 to the sodium borohydride is 1:0.6, and the molar ratio of the intermediate 10 to the intermediate 8 to the triethylamine is 6:1: 1.2.
8. A lightweight cellular rubber material according to claim 3, wherein: the using amount ratio of the brucite powder, the ethanol, the ethyl orthosilicate, the deionized water, the graphene and the intermediate 11 in the step A5 is 5g to 15mL to 3mL to 30mL to 5g to 2.5 g.
9. The method for preparing a lightweight and porous rubber material according to claim 1, wherein the method comprises the following steps: the method specifically comprises the following steps:
step S1: adding nitrile rubber and dichloromethane into a stirring kettle, stirring for 15-30min at the rotation speed of 500-800r/min, adding flame-retardant filler and pore-forming agent, and performing ultrasonic treatment for 10-15min at the frequency of 3-5MHz to obtain a composite glue solution;
step S2: standing the composite glue solution prepared in the step S1 for 1-2h, and defoaming for 10-15min under the condition that the vacuum degree is 0.2-0.5MPa to prepare a defoaming solution;
step S3: and adding the defoaming solution into a mold, standing for 20-30min at the temperature of 40-60 ℃, heating to the temperature of 110-130 ℃, and curing for 15-20min to obtain the rubber material.
CN202110113410.7A 2021-01-27 2021-01-27 Lightweight porous rubber material and preparation method thereof Pending CN112920519A (en)

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Publication number Priority date Publication date Assignee Title
CN113603652A (en) * 2021-08-19 2021-11-05 上海麦豪新材料科技有限公司 Organic flame-retardant structure and application thereof in organic silicon surfactant and polyurethane material

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CN105348592A (en) * 2015-11-24 2016-02-24 安徽南洋新材料科技股份有限公司 High-strength oil-resistant flame-retardant cable for oil paint industry

Patent Citations (1)

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Publication number Priority date Publication date Assignee Title
CN105348592A (en) * 2015-11-24 2016-02-24 安徽南洋新材料科技股份有限公司 High-strength oil-resistant flame-retardant cable for oil paint industry

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113603652A (en) * 2021-08-19 2021-11-05 上海麦豪新材料科技有限公司 Organic flame-retardant structure and application thereof in organic silicon surfactant and polyurethane material

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