Coating type polymer flame-retardant material

Abstract

The invention discloses a coating type high-molecular flame-retardant material. The composite material is prepared from the following components: organic silicon modified epoxy resin, a bio-based castor oil derivative, hydroxyapatite, carbon nanofibers, expanded graphite, ammonium polyphosphate, zinc borate, nano silicon dioxide, molybdenum oxide, microencapsulated red phosphorus, magnesium hydroxide, melamine cyanurate, aluminum diethylphosphinate, pentaerythritol, trihydroxymethyl phosphine oxide and a silane coupling agent. The coating is prepared from a titanate coupling agent, stearic acid, polyethylene glycol, 2, 6-butylated hydroxytoluene, triphenyl phosphite, 2, 4-dihydroxybenzophenone, sebacic diester, polytetrafluoroethylene micro powder, a modified polydimethylsiloxane flatting agent, organic montmorillonite, a polyether modified silicon defoaming agent and a solvent. The invention has the beneficial effects of high flame retardant efficiency, environmental friendliness, excellent comprehensive performance and excellent processability.

Description

Technical Field

[0001] The present invention relates to the technical field of flame - retardant materials, and particularly to a coated polymer flame - retardant material. Background Art

[0002] In modern industry and daily life, due to their excellent comprehensive properties, such as light weight, corrosion resistance, good processability, etc., polymer materials have been extremely widely used in many fields such as construction, electronics, transportation, aerospace, etc. Taking the construction industry as an example, polymer materials are widely used in thermal insulation materials, decorative materials, and pipe manufacturing; in the electronics field, shells and insulating components made of various polymer materials ensure the stable operation of electronic devices; in the transportation field, the interiors and some structural components of vehicles such as cars and ships also rely on polymer materials.

[0003] However, most polymer materials are flammable or combustible substances, which pose significant fire safety hazards during their use. Once a fire occurs, polymer materials burn rapidly, not only causing huge property losses but also threatening people's lives. Therefore, improving the flame - retardant performance of polymer materials has become an important research direction in the materials field, and coated polymer flame - retardant materials have emerged as the times require. These materials form a flame - retardant protective layer on the surface of polymer materials, effectively preventing the spread of flames, reducing the combustion rate of materials, and thus improving the fire safety of materials.

[0004] Although coated polymer flame - retardant materials have, to a certain extent, solved the problem of flammability of polymer materials, there are still many deficiencies in the current market products. On the one hand, the flame - retardant efficiency of some flame - retardant materials is poor, and a large amount of flame - retardant agents need to be added to achieve a certain flame - retardant effect. The addition of a large amount of flame - retardant agents not only significantly increases the cost of materials but also may have a negative impact on the original physical and mechanical properties of materials, such as flexibility and strength, restricting the application range of materials. On the other hand, many traditional coated polymer flame - retardant materials perform poorly in terms of durability, and the flame - retardant coatings are prone to phenomena such as peeling and cracking, making it difficult to maintain effective flame - retardant performance for a long time. In addition, some flame - retardant agents contain halogen elements, which will release toxic and harmful gases such as dioxins during combustion, posing a serious threat to the environment and human health.

[0005] With the continuous improvement of people's environmental awareness and the increasingly strict requirements for fire safety, it has become an urgent task to develop a coated polymer flame - retardant material that not only has high flame - retardant performance but also good durability and environmental friendliness. This not only helps to promote the safe application of polymer materials in various fields but also reduces the harm caused by fire accidents and promotes the sustainable development of society. Based on this situation, the present invention aims to develop a new coated polymer flame - retardant material to overcome the deficiencies of the prior art. Summary of the invention

[0006] In order to solve the above problems, especially to address the deficiencies in the prior art, the present invention provides a coated polymer flame retardant material that can solve the above problems.

[0007] To achieve the above purpose, the present invention adopts the following technical means:

[0008] A coated polymer flame retardant material, composed of the following components by weight:

[0009] Polymer matrix

[0010] 20-40 parts of silicone modified epoxy resin, 10-20 parts of bio-based castor oil derivative;

[0011] Inorganic non-metallic matrix

[0012] 5-15 parts of hydroxyapatite, 3-8 parts of carbon nanofibers;

[0013] Inorganic flame retardants

[0014] 8-15 parts of expanded graphite, 10-20 parts of ammonium polyphosphate, 5-10 parts of zinc borate, 3-8 parts of nano silicon dioxide, 2-5 parts of molybdenum oxide, 5-10 parts of microencapsulated red phosphorus, and 10-20 parts of magnesium hydroxide;

[0015] Organic flame retardants

[0016] 8-15 parts of melamine cyanurate, 5-10 parts of aluminum diethylphosphinate, 3-8 parts of pentaerythritol, and 3-8 parts of trihydroxymethylphosphine oxide;

[0017] Adhesion promoter

[0018] 2-5 parts of silane coupling agent, 2-5 parts of titanate coupling agent;

[0019] Dispersants

[0020] 1-3 parts of stearic acid, 1-3 parts of polyethylene glycol;

[0021] Antioxidants

[0022] 1-3 parts of 2,6-di-tert-butyl-p-cresol, 1-3 parts of triphenyl phosphite;

[0023] Light Stabilizer

[0024] 1-3 parts of 2,4-dihydroxybenzophenone, 1-3 parts of sebacate;

[0025] Leveling agent

[0026] 2-5 parts of polytetrafluoroethylene micropowder and 2-5 parts of modified polydimethylsiloxane leveling agent;

[0027] Rheology modifier

[0028] 3 - 8 parts of organic montmorillonite;

[0029] Defoamer

[0030] 1 - 3 parts of polyether - modified silicone defoamer;

[0031] 30 - 50 parts of solvent.

[0032] A further solution of the present invention is that, by mass parts, it consists of the following components: 20 parts of organosilicon - modified epoxy resin, 10 parts of bio - based castor oil derivative, 5 parts of hydroxyapatite, 3 parts of carbon nanofibers, 8 parts of expanded graphite, 10 parts of ammonium polyphosphate, 5 parts of zinc borate, 3 parts of nano - silica, 2 parts of molybdenum oxide, 5 parts of micro - encapsulated red phosphorus, 10 parts of magnesium hydroxide, 8 parts of melamine cyanurate, 5 parts of aluminum diethyl phosphinate, 3 parts of pentaerythritol, 3 parts of trimethylol phosphine oxide, 2 parts of silane coupling agent, 2 parts of titanate coupling agent, 1 part of stearic acid, 1 part of polyethylene glycol, 1 part of 2,6 - di - tert - butyl - p - cresol, 1 part of triphenyl phosphite, 1 part of 2,4 - dihydroxybenzophenone, 1 part of sebacic acid diester, 2 parts of polytetrafluoroethylene micropowder, 2 parts of modified polydimethylsiloxane leveling agent, 3 parts of organic montmorillonite, 1 part of polyether - modified silicone defoamer, and 30 parts of solvent.

[0033] A further solution of the present invention is that, by mass parts, it consists of the following components: 30 parts of organosilicon - modified epoxy resin, 15 parts of bio - based castor oil derivative, 10 parts of hydroxyapatite, 6 parts of carbon nanofibers, 12 parts of expanded graphite, 15 parts of ammonium polyphosphate, 8 parts of zinc borate, 6 parts of nano - silica, 3 parts of molybdenum oxide, 8 parts of micro - encapsulated red phosphorus, 15 parts of magnesium hydroxide, 10 parts of melamine cyanurate, 7 parts of aluminum diethyl phosphinate, 6 parts of pentaerythritol, 5 parts of trimethylol phosphine oxide, 3 parts of silane coupling agent, 4 parts of titanate coupling agent, 2 parts of stearic acid, 2 parts of polyethylene glycol, 2 parts of 2,6 - di - tert - butyl - p - cresol, 2 parts of triphenyl phosphite, 2 parts of 2,4 - dihydroxybenzophenone, 2 parts of sebacic acid diester, 4 parts of polytetrafluoroethylene micropowder, 3 parts of modified polydimethylsiloxane leveling agent, 5 parts of organic montmorillonite, 2 parts of polyether - modified silicone defoamer, and 40 parts of solvent.

[0034] A further solution of the present invention is that, by mass parts, it consists of the following components: 40 parts of organosilicon-modified epoxy resin, 20 parts of bio-based castor oil derivative, 15 parts of hydroxyapatite, 8 parts of carbon nanofibers, 15 parts of expanded graphite, 20 parts of ammonium polyphosphate, 10 parts of zinc borate, 8 parts of nano-silica, 5 parts of molybdenum oxide, 10 parts of microencapsulated red phosphorus, 20 parts of magnesium hydroxide, 15 parts of melamine cyanurate, 10 parts of aluminum diethylphosphinate, 8 parts of pentaerythritol, 8 parts of trimethylolphosphine oxide, 5 parts of silane coupling agent, 5 parts of titanate coupling agent, 3 parts of stearic acid, 3 parts of polyethylene glycol, 3 parts of 2,6-di-tert-butyl-p-cresol, 3 parts of triphenyl phosphite, 3 parts of 2,4-dihydroxybenzophenone, 3 parts of sebacic acid diester, 5 parts of polytetrafluoroethylene micropowder, 5 parts of modified polydimethylsiloxane leveling agent, 8 parts of organic montmorillonite, 3 parts of polyether-modified silicone defoaming agent, and 50 parts of solvent.

[0035] A further solution of the present invention is that the solvent is toluene, xylene, ethyl acetate or water.

[0036] A further solution of the present invention is a preparation method of a coating-type polymer flame retardant material, which includes the following steps:

[0037] Step 1, predispersion treatment:

[0038] Add hydroxyapatite, carbon nanofibers, expanded graphite, ammonium polyphosphate, zinc borate, nano-silica, molybdenum oxide, microencapsulated red phosphorus, magnesium hydroxide, and organic montmorillonite into the solvent, stir evenly to form an inorganic dispersion liquid, with a stirring speed of 300 - 500 r / min and a stirring time of 1 - 2 h;

[0039] Step 2, resin mixing:

[0040] Add organosilicon-modified epoxy resin and bio-based castor oil derivative into the reaction kettle, heat up to 60 - 80 °C, stir evenly, with a stirring speed of 200 - 400 r / min and a stirring time of 0.5 - 1 h;

[0041] Step 3, additive addition:

[0042] Sequentially add melamine cyanurate, aluminum diethylphosphinate, pentaerythritol, trimethylolphosphine oxide, silane coupling agent, titanate coupling agent, stearic acid, polyethylene glycol, 2,6-di-tert-butyl-p-cresol, triphenyl phosphite, 2,4-dihydroxybenzophenone, sebacic acid diester, polytetrafluoroethylene micropowder, modified polydimethylsiloxane leveling agent, and polyether-modified silicone defoaming agent to the resin mixture obtained in Step 2, and continue to stir for 30 - 60 min, with a stirring speed of 200 - 400 r / min;

[0043] Step 4, mixing and dispersion:

[0044] Add the inorganic dispersion obtained in Step 1 to the system obtained in Step 3, and disperse it using a high-speed disperser at a dispersion speed of 1000 - 1500 r / min for 1 - 2 h to obtain a coated polymer flame retardant material.

[0045] A further solution of the present invention is that in the pre-dispersion treatment of Step 1, the stirring speed is 400 r / min and the stirring time is 1.5 h.

[0046] A further solution of the present invention is that in the resin mixing of Step 2, the stirring speed is 300 r / min and the stirring time is 0.8 h.

[0047] A further solution of the present invention is that in the additive addition of Step 3, continue to stir for 50 min at a stirring speed of 300 r / min.

[0048] A further solution of the present invention is that in the mixing and dispersion of Step 4, the dispersion speed is 1200 r / min and the dispersion time is 1.5 h.

[0049] Organosilicon-modified epoxy resin: Relying on the excellent adhesion of epoxy resin, it can form a firm and dense coating on the surface of polymer materials, providing good adhesion and mechanical strength. The introduction of organosilicon significantly improves the heat resistance, weather resistance and flexibility of the material, endowing the flame retardant coating with excellent comprehensive properties.

[0050] Bio-based castor oil derivative: As an environmentally friendly raw material, its source is renewable, which not only reduces the impact on the environment, but also can cooperate with organosilicon-modified epoxy resin to improve the flexibility and film-forming properties of the coating, and enhance the processing performance and stability of the material.

[0051] Hydroxyapatite: It has good biocompatibility and chemical stability. In the flame retardant material, it can not only enhance the mechanical properties of the material, but also absorb heat through its own decomposition at high temperature to play a flame retardant role. At the same time, it is environmentally friendly and helps to improve the safety of the material.

[0052] Carbon nanofibers: They have extremely high strength and modulus, and can significantly enhance the mechanical properties of materials, such as tensile strength, bending strength, etc. In addition, the high conductivity of carbon nanofibers can form a good heat conduction network, promoting the dispersion of heat during combustion and inhibiting the increase of local temperature, thereby improving the flame retardant performance of the material.

[0053] Expanded graphite: It expands rapidly at high temperature to form an expanded carbon layer, which has good heat insulation and oxygen isolation properties, effectively preventing the transfer of heat and oxygen into the material interior, thereby inhibiting combustion.

[0054] Ammonium polyphosphate: When heated, it decomposes to produce phosphoric acid and ammonia. Phosphoric acid can catalyze the dehydration and carbonization of organic substances to form a carbonaceous layer, and ammonia can dilute the concentration of combustible gases, playing a role in gas-phase flame retardancy. It synergistically enhances the flame retardant effect with expanded graphite.

[0055] Zinc borate: During combustion, it can form a glassy protective film that covers the material surface, preventing heat transfer and oxygen entry. At the same time, it can also promote the formation of a carbon layer and enhance the flame retardant effect. In addition, zinc borate has a smoke suppression effect and can reduce the generation of smoke during combustion.

[0056] Nano-silica: It has a high specific surface area and good dispersibility, can be evenly dispersed in the material, and enhance the mechanical properties of the material. In terms of flame retardancy, nano-silica can synergistically act with other flame retardants to improve the density and stability of the carbon layer and enhance the flame retardant effect.

[0057] Molybdenum oxide: During combustion, it can promote the formation of a dense carbon layer on the material surface. At the same time, it can act as a Lewis acid catalyst to accelerate the thermal decomposition of polymers, generate more carbonaceous materials, and improve the flame retardant performance.

[0058] Microencapsulated red phosphorus: Red phosphorus is an efficient flame retardant. Microencapsulation can effectively solve the problems of easy moisture absorption and flammability of red phosphorus, and improve its stability and safety. During combustion, the phosphorus radicals generated by the decomposition of microencapsulated red phosphorus can capture the radicals in the combustion reaction and interrupt the combustion chain reaction, playing a flame retardant role.

[0059] Magnesium hydroxide: When heated and decomposed, it absorbs a large amount of heat, reduces the surface temperature of the material. The water vapor generated by decomposition can dilute the concentration of combustible gases. At the same time, the generated magnesium oxide covers the material surface, playing a role in heat insulation and oxygen isolation.

[0060] Melamine cyanurate: It is composed of elements such as nitrogen, carbon, and hydrogen. It decomposes to produce non-combustible gases at high temperatures, diluting the concentration of combustible gases. At the same time, it can promote the formation of an expanded carbon layer on the material surface, playing a flame retardant role.

[0061] Aluminum diethylphosphinate: It contains phosphorus and aluminum elements. During combustion, the phosphorus element forms phosphoric acid or metaphosphoric acid to promote the carbonization of the material, and the aluminum element can form an aluminum oxide protective film to improve the stability of the carbon layer. The two act synergistically to enhance the flame retardant effect.

[0062] Pentaerythritol: As a carbon source in the intumescent flame retardant system, under the action of catalysts such as phosphoric acid, it can be dehydrated and carbonized to form an expanded carbon layer, and synergistically improve the flame retardant performance with other flame retardants.

[0063] Trimethylolphosphine oxide: It contains phosphorus and oxygen elements. During combustion, it can form a phosphorus-containing flame retardant substance to promote the carbonization of the material. At the same time, it can synergistically act with other flame retardants to improve the flame retardant effect.

[0064] Silane coupling agents and titanate coupling agents: They can form chemical bonds between inorganic fillers and organic resins, improve the compatibility and dispersibility between the two, enhance the interfacial bonding force of the materials, thereby enhancing the mechanical properties and processing properties of the materials. At the same time, it is beneficial to the uniform dispersion of flame retardants in the materials and gives full play to the flame retardant effect.

[0065] Stearic acid: As a lubricant, it can reduce the frictional resistance of the material during processing, improve the fluidity of the material, enhance the processing performance, and at the same time help prevent the material from sticking during processing.

[0066] Polyethylene glycol: It can adjust the viscosity of the material, improve the processing performance of the material, and can also act as a dispersant to promote the uniform dispersion of other components in the material.

[0067] 2,6-Di-tert-butyl-p-cresol and triphenyl phosphite: They can effectively inhibit the oxidation reaction of the material during processing and use, prevent the material from aging, extend the service life of the material, and ensure the stable performance of the flame retardant material during long-term use.

[0068] 2,4-Dihydroxybenzophenone and bis(decyl) sebacate: They can absorb ultraviolet rays, prevent the material from degrading due to ultraviolet irradiation, improve the weather resistance of the material, and ensure that the flame retardant material can still maintain good performance in outdoor environments.

[0069] Polytetrafluoroethylene micropowder: It can reduce the friction coefficient of the material surface, improve the wear resistance and scratch resistance of the material, and at the same time endow the material with good self-cleaning performance.

[0070] Modified polydimethylsiloxane leveling agent: It can improve the leveling property of the coating, make the coating surface more smooth and flat, improve the appearance quality of the coating, and at the same time help improve the adhesion and water resistance of the coating.

[0071] Organic montmorillonite: It has a nano-layered structure and can form nano-scale barrier layers in the material to prevent the transfer of gas and heat, improve the heat resistance and flame retardant performance of the material, and at the same time enhance the mechanical properties of the material.

[0072] Polyether-modified silicone defoamer: It can effectively eliminate the bubbles generated during the preparation of the material, improve the density and uniformity of the material, and ensure the quality and performance of the material.

[0073] Solvent: As a dispersion medium, it can uniformly disperse various components, facilitate the preparation and processing of the material, and at the same time can adjust the viscosity of the material to meet different construction requirements.

[0074] Advantages of the present invention:

[0075] 1. The flame retardancy efficiency of the present invention is high: Multiple flame retardants in the material cooperate synergistically. When exposed to fire, expandable graphite, ammonium polyphosphate, etc. will expand, forming a continuous and dense expanded carbon layer, just like putting a solid "fireproof coat" on the material, effectively isolating external heat and oxygen and inhibiting the combustion reaction. The phosphorus free radicals generated by the decomposition of microencapsulated red phosphorus and the water vapor generated by the decomposition of magnesium hydroxide can dilute the concentration of combustible gases and interrupt the combustion chain reaction. Multiple flame retardant mechanisms work simultaneously, significantly improving the flame retardant performance of the material. Compared with ordinary products, it can more efficiently prevent the spread of flames.

[0076] 2. The present invention is environmentally friendly: The present invention uses bio-based castor oil derivatives to replace some traditional raw materials, reducing the dependence on non-renewable resources such as petroleum and reducing the environmental impact of the material from the source. At the same time, halogen-containing flame retardants are abandoned, avoiding the generation of toxic and harmful gases such as dioxins during combustion and reducing the potential hazards of fires to the environment and human health, meeting the requirements of current environmental protection development.

[0077] 3. The present invention has excellent comprehensive performance: The combination of organosilicon-modified epoxy resin and bio-based castor oil derivatives significantly improves the film-forming performance and adhesion of the material, ensuring that the flame retardant coating is tightly combined with the substrate, not easily falling off or cracking, and extending the service life of the flame retardant material. The addition of inorganic reinforcing materials such as carbon nanofibers and hydroxyapatite enhances the mechanical strength of the material, making the material more durable. In addition, the nano-barrier effect of organic montmorillonite effectively blocks the transfer of heat and gas, further improving the heat resistance and chemical corrosion resistance of the material and broadening the application scenarios of the material.

[0078] 4. The present invention has excellent processing performance: By adding interfacial modifiers such as silane coupling agents and titanate coupling agents, the compatibility between inorganic fillers and organic resins is improved, the viscosity of the material during processing is reduced, the occurrence of agglomeration is reduced, the dispersion uniformity of the material is improved, the energy consumption and cost during the preparation process are reduced, which is conducive to large-scale industrial production. Detailed implementation mode

[0079] The technical solutions of the present invention will be described clearly and completely below. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all of them. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative work shall fall within the protection scope of the present invention.

[0080] Example 1

[0081] A coated polymer flame retardant material

[0082] Raw material preparation

[0083] 20 parts of silicone-modified epoxy resin, 10 parts of bio-based castor oil derivative, 5 parts of hydroxyapatite, 3 parts of carbon nanofiber, 8 parts of expanded graphite, 10 parts of ammonium polyphosphate, 5 parts of zinc borate, 3 parts of nano-silica, 2 parts of molybdenum oxide, 5 parts of microencapsulated red phosphorus, 10 parts of magnesium hydroxide, 8 parts of melamine cyanurate, 5 parts of aluminum diethyl phosphinate, 3 parts of pentaerythritol, 3 parts of trimethylolphosphine oxide, 2 parts of silane coupling agent, 2 parts of titanate coupling agent, 1 part of stearic acid, 1 part of polyethylene glycol, 1 part of 2,6-di-tert-butyl-p-cresol, 1 part of triphenyl phosphite, 1 part of 2,4-dihydroxybenzophenone, 1 part of sebacic acid diester, 2 parts of polytetrafluoroethylene micropowder, 2 parts of modified polydimethylsiloxane leveling agent, 3 parts of organic montmorillonite, 1 part of polyether-modified silicone defoamer, 30 parts of toluene.

[0084] Preparation steps

[0085] Step 1, pre-dispersion treatment: Add the weighed hydroxyapatite, carbon nanofiber, expanded graphite, ammonium polyphosphate, zinc borate, nano-silica, molybdenum oxide, microencapsulated red phosphorus, magnesium hydroxide, and organic montmorillonite into toluene, and stir at a speed of 300 r / min for 1 h to form an inorganic dispersion.

[0086] Step 2, resin mixing: Add the silicone-modified epoxy resin and bio-based castor oil derivative into the reaction kettle, heat up to 60 °C, and stir at a speed of 200 r / min for 0.5 h.

[0087] Step 3, additive addition: Add melamine cyanurate, aluminum diethyl phosphinate, pentaerythritol, trimethylolphosphine oxide, silane coupling agent, titanate coupling agent, stearic acid, polyethylene glycol, 2,6-di-tert-butyl-p-cresol, triphenyl phosphite, 2,4-dihydroxybenzophenone, sebacic acid diester, polytetrafluoroethylene micropowder, modified polydimethylsiloxane leveling agent, and polyether-modified silicone defoamer to the resin mixture obtained in Step 2 in sequence, and continue to stir at a speed of 200 r / min for 30 min.

[0088] Step 4, mixing and dispersion: Add the inorganic dispersion obtained in Step 1 to the system obtained in Step 3, and disperse at a speed of 1000 r / min for 1 h using a high-speed disperser to obtain a coated polymer flame retardant material.

[0089] Example 2

[0090] A coated polymer flame retardant material

[0091] Raw material preparation

[0092] 30 parts of silicone-modified epoxy resin, 15 parts of bio-based castor oil derivative, 10 parts of hydroxyapatite, 6 parts of carbon nanofibers, 12 parts of expanded graphite, 15 parts of ammonium polyphosphate, 8 parts of zinc borate, 6 parts of nano-silica, 3 parts of molybdenum oxide, 8 parts of microencapsulated red phosphorus, 15 parts of magnesium hydroxide, 10 parts of melamine cyanurate, 7 parts of aluminum diethylphosphinate, 6 parts of pentaerythritol, 5 parts of trimethylolphosphine oxide, 3 parts of silane coupling agent, 4 parts of titanate coupling agent, 2 parts of stearic acid, 2 parts of polyethylene glycol, 2 parts of 2,6-di-tert-butyl-p-cresol, 2 parts of triphenyl phosphite, 2 parts of 2,4-dihydroxybenzophenone, 2 parts of sebacic acid diester, 4 parts of polytetrafluoroethylene micropowder, 3 parts of modified polydimethylsiloxane leveling agent, 5 parts of organic montmorillonite, 2 parts of polyether-modified silicone defoamer, 40 parts of xylene.

[0093] Preparation steps

[0094] Step 1, predispersion treatment: Add the weighed hydroxyapatite, carbon nanofibers, expanded graphite, ammonium polyphosphate, zinc borate, nano-silica, molybdenum oxide, microencapsulated red phosphorus, magnesium hydroxide, and organic montmorillonite to xylene, and stir at a speed of 400 r / min for 1.5 h to form an inorganic dispersion.

[0095] Step 2, resin mixing: Add the silicone-modified epoxy resin and bio-based castor oil derivative to the reaction kettle, heat up to 70 °C, and stir at a speed of 300 r / min for 0.8 h.

[0096] Step 3, additive addition: Sequentially add melamine cyanurate, aluminum diethylphosphinate, pentaerythritol, trimethylolphosphine oxide, silane coupling agent, titanate coupling agent, stearic acid, polyethylene glycol, 2,6-di-tert-butyl-p-cresol, triphenyl phosphite, 2,4-dihydroxybenzophenone, sebacic acid diester, polytetrafluoroethylene micropowder, modified polydimethylsiloxane leveling agent, and polyether-modified silicone defoamer to the resin mixture obtained in Step 2, and continue to stir at a speed of 300 r / min for 50 min.

[0097] Step 4, mixing and dispersion: Add the inorganic dispersion obtained in Step 1 to the system obtained in Step 3, and disperse at a speed of 1200 r / min for 1.5 h using a high-speed disperser to obtain a coated polymer flame retardant material.

[0098] Example 3

[0099] A coated polymer flame retardant material

[0100] Raw material preparation

[0101] 40 parts of silicone-modified epoxy resin, 20 parts of bio-based castor oil derivative, 15 parts of hydroxyapatite, 8 parts of carbon nanofibers, 15 parts of expanded graphite, 20 parts of ammonium polyphosphate, 10 parts of zinc borate, 8 parts of nano-silica, 5 parts of molybdenum oxide, 10 parts of microencapsulated red phosphorus, 20 parts of magnesium hydroxide, 15 parts of melamine cyanurate, 10 parts of aluminum diethylphosphinate, 8 parts of pentaerythritol, 8 parts of trimethylolphosphine oxide, 5 parts of silane coupling agent, 5 parts of titanate coupling agent, 3 parts of stearic acid, 3 parts of polyethylene glycol, 3 parts of 2,6-di-tert-butyl-p-cresol, 3 parts of triphenyl phosphite, 3 parts of 2,4-dihydroxybenzophenone, 3 parts of sebacic acid diester, 5 parts of polytetrafluoroethylene micropowder, 5 parts of modified polydimethylsiloxane leveling agent, 8 parts of organic montmorillonite, 3 parts of polyether-modified silicone defoamer, 50 parts of ethyl acetate.

[0102] Preparation steps

[0103] Step 1, pre-dispersion treatment: Add the weighed hydroxyapatite, carbon nanofibers, expanded graphite, ammonium polyphosphate, zinc borate, nano-silica, molybdenum oxide, microencapsulated red phosphorus, magnesium hydroxide, and organic montmorillonite into ethyl acetate, and stir at a speed of 400 r / min for 1.5 h to form an inorganic dispersion.

[0104] Step 2, resin mixing: Add the silicone-modified epoxy resin and bio-based castor oil derivative into the reaction kettle, heat up to 80 °C, and stir at a speed of 300 r / min for 0.75 h.

[0105] Step 3, additive addition: Sequentially add melamine cyanurate, aluminum diethylphosphinate, pentaerythritol, trimethylolphosphine oxide, silane coupling agent, titanate coupling agent, stearic acid, polyethylene glycol, 2,6-di-tert-butyl-p-cresol, triphenyl phosphite, 2,4-dihydroxybenzophenone, sebacic acid diester, polytetrafluoroethylene micropowder, modified polydimethylsiloxane leveling agent, and polyether-modified silicone defoamer to the resin mixture obtained in Step 2, and continue to stir at a speed of 300 r / min for 45 min.

[0106] Step 4, mixing and dispersion: Add the inorganic dispersion obtained in Step 1 into the system obtained in Step 3, and disperse at a speed of 1200 r / min for 1.5 h using a high-speed disperser to obtain a coated polymer flame retardant material.

[0107] Comparative Example 1

[0108] Select a common ordinary halogen-containing coated polymer flame retardant material on the market as Comparative Example 1. It mainly uses halogen-containing epoxy resin as the matrix resin, and is formulated with conventional flame retardants such as antimony trioxide and brominated flame retardants, and a small amount of inorganic fillers and additives are added. In the formulation system of this comparative example material, the mass ratio of halogen-containing epoxy resin is about 50%, and the total mass ratio of antimony trioxide and brominated flame retardant reaches 30%. This enables a certain flame retardant effect to be achieved, but due to the extensive use of flame retardants, the mechanical properties of the material itself are weakened, and due to the presence of halogen-containing components, the environmental performance is poor. At the same time, this material does not use additives with nanostructures, nor does it have a composite formulation for systematically optimizing the comprehensive properties of the material, so there are deficiencies in terms of heat resistance, weather resistance, and coating adhesion.

[0109] Details of performance testing

[0110] 1. Vertical burning test

[0111] According to the UL94 vertical burning test standard, the flame retardant materials of Examples 1-3 and Comparative Example 1 were made into splines with dimensions of 127 mm × 12.7 mm × 3.2 mm. The splines were fixed on the test rack, and a Bunsen burner was used to apply a flame to the bottom of the splines for 10 seconds. After removing the flame, the burning behavior of the splines was recorded, including the flaming combustion time, non-flaming combustion time, and whether there were molten drops, etc.

[0112] After removing the flame, the splines of Examples 1-3 had short flaming and non-flaming combustion times, and no molten drops were produced, meeting the V-0 grade standard; after removing the flame, the splines of Comparative Example 1 had a relatively long flaming combustion time. Although it did not drip and ignite the absorbent cotton, the rating only reached V-1 grade.

[0113] 2. Adhesion test

[0114] The adhesion test was carried out in accordance with GB / T 9286-1998 "Cross-cut test for paints and varnishes". A cross-cut tool was used to draw 100 squares of 1 mm × 1 mm on the surface of the sample plate coated with the flame retardant material, and then a special tape was pasted on the cross-cut area and quickly pulled up in a direction perpendicular to the surface of the sample plate. Observe the peeling situation of the coating in the square area and rate it according to levels 0-5. Level 0 indicates the best adhesion and no coating peeling; level 5 indicates the worst adhesion and large-area coating peeling.

[0115] After the test, for the coatings of Examples 1-3, almost no coating peeled off in the square area, and the rating was 1 level; for the coating of Comparative Example 1, peeling occurred at the edges of some squares, and the rating was 2 levels.

[0116] 3. Heat distortion temperature test

[0117] According to ASTM D648 "Standard Test Method for Deflection Temperature of Plastics Under Load", the flame-retardant materials of Examples 1-3 and Comparative Example 1 were made into splines with dimensions of 127 mm × 12.7 mm × 3.2 mm. The splines were placed in a heat distortion temperature tester, a certain bending stress was applied, and they were heated at a certain heating rate. When the bending deformation of the splines reached the specified value, the temperature at this time was recorded, which was the heat distortion temperature.

[0118] The heat distortion temperature of Example 1 was 150 °C, that of Example 2 was increased to 160 °C, and that of Example 3 reached 170 °C; due to the limited heat resistance of the material in Comparative Example 1, the heat distortion temperature was only 120 °C.

[0119] 4. Smoke density test

[0120] The NBS smoke chamber method was used to test the smoke generated during the combustion of the materials of the examples and comparative examples. Splines of a certain size were placed in the smoke chamber, and after ignition, the light transmittance in the smoke chamber was measured to calculate the smoke density during the combustion of the material.

[0121] Due to the presence of halogen-based flame retardants in Comparative Example 1, a large amount of thick smoke was released during combustion, and the smoke density was much higher than that of Examples 1-3. However, since the examples did not use halogen-containing flame retardants and had a reasonable formulation, the amount of smoke generated during the combustion process was small, and the smoke density was at a low level, further demonstrating their environmental protection advantages.

[0122] The examples given in the present invention are illustrative rather than restrictive of the embodiments. For those of ordinary skill in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to enumerate all the embodiments here, and the obvious changes or modifications derived therefrom are still within the protection scope of the present invention.

Claims

1. A coated polymer flame retardant material, characterized in that: By mass, it is composed of the following components: Polymer matrix 20-40 parts of silicone modified epoxy resin, 10-20 parts of bio-based castor oil derivative; Inorganic non-metallic matrix 5-15 parts of hydroxyapatite, 3-8 parts of carbon nanofibers; Inorganic flame retardants 8-15 parts of expanded graphite, 10-20 parts of ammonium polyphosphate, 5-10 parts of zinc borate, 3-8 parts of nano silicon dioxide, 2-5 parts of molybdenum oxide, 5-10 parts of microencapsulated red phosphorus, and 10-20 parts of magnesium hydroxide; Organic flame retardants 8-15 parts of melamine cyanurate, 5-10 parts of aluminum diethylphosphinate, 3-8 parts of pentaerythritol, and 3-8 parts of trishydroxymethylphosphine oxide; Adhesion promoter 2-5 parts of silane coupling agent, 2-5 parts of titanate coupling agent; Dispersants 1-3 parts of stearic acid, 1-3 parts of polyethylene glycol; Antioxidants 1-3 parts of 2,6-di-tert-butyl-p-cresol, 1-3 parts of triphenyl phosphite; Light Stabilizer 1-3 parts of 2,4-dihydroxybenzophenone, 1-3 parts of sebacate; Leveling agent 2-5 parts of polytetrafluoroethylene micropowder and 2-5 parts of modified polydimethylsiloxane leveling agent; Rheology additives 3-8 parts of organic montmorillonite; Defoaming agent 1-3 parts of polyether modified silicon defoamer; 30-50 parts of solvent.

2. A coated polymer flame retardant material according to claim 1, characterized in that: The invention is composed of the following components by mass: 20 parts of organosilicon-modified epoxy resin, 10 parts of bio-based castor oil derivatives, 5 parts of hydroxyapatite, 3 parts of carbon nanofibers, 8 parts of expanded graphite, 10 parts of ammonium polyphosphate, 5 parts of zinc borate, 3 parts of nano-silicon dioxide, 2 parts of molybdenum oxide, 5 parts of microencapsulated red phosphorus, 10 parts of magnesium hydroxide, 8 parts of melamine cyanurate, 5 parts of diethyl aluminum phosphinate, 3 parts of pentaerythritol, 3 parts of trimethylol phosphine oxide, 2 parts of silane coupling agent, 2 parts of titanate coupling agent, 1 part of stearic acid, 1 part of polyethylene glycol, 1 part of 2,6-di-tert-butyl-p-cresol, 1 part of triphenyl phosphite, 1 part of 2,4-dihydroxybenzophenone, 1 part of sebacate, 2 parts of polytetrafluoroethylene micropowder, 2 parts of modified polydimethylsiloxane leveling agent, 3 parts of organic montmorillonite, 1 part of polyether-modified silicon defoamer, and 30 parts of solvent.

3. A coated polymer flame retardant material according to claim 1, characterized in that: The invention is composed of the following components by mass: 30 parts of organosilicon-modified epoxy resin, 15 parts of bio-based castor oil derivatives, 10 parts of hydroxyapatite, 6 parts of carbon nanofibers, 12 parts of expanded graphite, 15 parts of ammonium polyphosphate, 8 parts of zinc borate, 6 parts of nano-silicon dioxide, 3 parts of molybdenum oxide, 8 parts of microencapsulated red phosphorus, 15 parts of magnesium hydroxide, 10 parts of melamine cyanurate, 7 parts of aluminum diethylphosphinate, 6 parts of pentaerythritol, 5 parts of trihydroxymethylphosphine oxide, 3 parts of silane coupling agent, 4 parts of titanate coupling agent, 2 parts of stearic acid, 2 parts of polyethylene glycol, 2 parts of 2,6-di-tert-butyl-p-cresol, 2 parts of triphenyl phosphite, 2 parts of 2,4-dihydroxybenzophenone, 2 parts of sebacate, 4 parts of polytetrafluoroethylene micropowder, 3 parts of modified polydimethylsiloxane leveling agent, 5 parts of organic montmorillonite, 2 parts of polyether-modified silicon defoamer, and 40 parts of solvent.

4. The coated polymer flame retardant material according to claim 1, characterized in that: The invention is composed of the following components by mass: 40 parts of organosilicon-modified epoxy resin, 20 parts of bio-based castor oil derivative, 15 parts of hydroxyapatite, 8 parts of carbon nanofiber, 15 parts of expanded graphite, 20 parts of ammonium polyphosphate, 10 parts of zinc borate, 8 parts of nano-silicon dioxide, 5 parts of molybdenum oxide, 10 parts of microencapsulated red phosphorus, 20 parts of magnesium hydroxide, 15 parts of melamine cyanurate, 10 parts of diethyl aluminum phosphinate, 10 parts of ammonium quaternary ammonium sulfate, 10 parts of tert-butyl cyanamide, 10 parts of quaternary ammonium ... 8 parts of tetraol, 8 parts of trihydroxymethylphosphine oxide, 5 parts of silane coupling agent, 5 parts of titanate coupling agent, 3 parts of stearic acid, 3 parts of polyethylene glycol, 3 parts of 2,6-di-tert-butyl-p-cresol, 3 parts of triphenyl phosphite, 3 parts of 2,4-dihydroxybenzophenone, 3 parts of sebacate, 5 parts of polytetrafluoroethylene micropowder, 5 parts of modified polydimethylsiloxane leveling agent, 8 parts of organic montmorillonite, 3 parts of polyether modified silicon defoamer, and 50 parts of solvent.

5. The coated polymer flame retardant material according to claim 1, characterized in that: The solvent is toluene, xylene, ethyl acetate or water.

6. The coated polymer flame retardant material according to claim 1, characterized in that: The method for preparing a coated polymer flame retardant material comprises the following steps: Step 1: Pre-dispersion treatment: Add hydroxyapatite, carbon nanofiber, expanded graphite, ammonium polyphosphate, zinc borate, nano-silicon dioxide, molybdenum oxide, microencapsulated red phosphorus, magnesium hydroxide, and organic montmorillonite to the solvent, stir evenly to form an inorganic dispersion, the stirring speed is 300-500 r / min, and the stirring time is 1-2 h; Step 2: Resin mixing: Add silicone-modified epoxy resin and bio-based castor oil derivative into the reactor, heat to 60-80°C, stir evenly, stir at a speed of 200-400 r / min, and stir for 0.5-1h; Step 3: Add additives: To the resin mixture obtained in step 2, add melamine cyanurate, diethyl aluminum phosphinate, pentaerythritol, trihydroxymethyl phosphine oxide, silane coupling agent, titanate coupling agent, stearic acid, polyethylene glycol, 2,6-di-tert-butyl-p-cresol, triphenyl phosphite, 2,4-dihydroxybenzophenone, sebacate, polytetrafluoroethylene powder, modified polydimethylsiloxane leveling agent, polyether modified silicon defoamer in sequence, and continue stirring for 30-60 minutes at a stirring speed of 200-400 r / min; Step 4: Mixing and dispersion: The inorganic dispersion obtained in step 1 is added to the system obtained in step 3, and dispersed by a high-speed disperser at a dispersion speed of 1000-1500 r / min and a dispersion time of 1-2 h to obtain a coated polymer flame retardant material.

7. A coated polymer flame retardant material according to claim 6, characterized in that: In the pre-dispersion treatment of step 1, the stirring speed is 400 r / min and the stirring time is 1.5 h.

8. The coated polymer flame retardant material according to claim 6, characterized in that: In the resin mixing of step 2, the stirring speed is 300 r / min and the stirring time is 0.8 h.

9. The coated polymer flame retardant material according to claim 6, characterized in that: During the addition of the additives in step 3, stirring was continued for 50 minutes at a stirring speed of 300 r / min.

10. The coated polymer flame retardant material according to claim 6, characterized in that: In the mixing and dispersing of step 4, the dispersing speed is 1200 r / min and the dispersing time is 1.5 h.