CN117467193A - Amorphous flame-retardant ceramic carbonizing agent material, preparation method thereof and flame-retardant material - Google Patents

Amorphous flame-retardant ceramic carbonizing agent material, preparation method thereof and flame-retardant material Download PDF

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CN117467193A
CN117467193A CN202311509434.XA CN202311509434A CN117467193A CN 117467193 A CN117467193 A CN 117467193A CN 202311509434 A CN202311509434 A CN 202311509434A CN 117467193 A CN117467193 A CN 117467193A
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flame
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陈建青
汪家克
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Suzhou Baiyan Flame Retardant Materials Co ltd
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    • 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
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/26—Silicon- containing compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • 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
    • C08K2003/222—Magnesia, i.e. magnesium oxide
    • 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
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • 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
    • C08L2201/00—Properties
    • C08L2201/14—Gas barrier composition
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel

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Abstract

The invention belongs to the technical field of flame-retardant materials, and particularly relates to an amorphous flame-retardant ceramic carbonizing agent material, a preparation method thereof and a flame-retardant material. The char-forming agent material comprises 100 parts by mass of organic silicon resin; 70-80 parts by mass of ceramic-based treated porcelain powder; 20-30 parts by mass of a high-temperature-resistant nano stabilizer; 5-15 parts by mass of a structural modifier; 20-30 parts by mass of gas phase nano silicon dioxide; 50-60 parts by mass of magnesium oxide; 50-60 parts of aluminum oxide. The char-forming agent material has excellent flame retardant property and environmental protection property. When the material is heated by combustion, the material forms a molten liquid phase component, so that the crusting property is improved, the bridge effect of an inorganic state and an organic state is achieved, in addition, a viscous melt generated by the melting of the material bonds the polymer carbon layer, the compactness and the thermal stability of the carbon layer are improved, the generation of combustible gas is reduced, the barrier property of a barrier layer is improved, and the flame retardant efficiency is improved.

Description

Amorphous flame-retardant ceramic carbonizing agent material, preparation method thereof and flame-retardant material
Technical Field
The invention belongs to the technical field of flame-retardant materials, and particularly relates to an amorphous flame-retardant ceramic carbonizing agent material, a preparation method thereof and a flame-retardant material.
Background
With the rapid development of economy, the amount of plastic used has increased dramatically. In order to more scientifically, comprehensively and objectively reflect the fire hazard of plastic products under the actual fire condition, better distinguish the combustion performance of different materials, and meet the requirements of international standards such as American insurance laboratory (UL), international electrotechnical Association (IEC), european Union building product regulations (CPR) and the like, a series of mandatory national standards are formulated in China. Including the classification of the combustion performance of electric cables and optical cables (GB 31247-214) and the mandatory standards for civil architecture design GB 51348.
From the development trend of the whole standard, not only needs to reduce the hazard of plastic fire by improving the requirement of flame retardance, but also needs to propose more humanized standard requirement in the aspect of environmental protection. Therefore, improving the environmental protection and flame retardance of plastics has become one of the important tasks of research and development material workers.
Key factors of fire hazard include rate of heat release, rate of smoke generation, and rate of toxic gas release. Other factors also include ignitability, resistance to extinguishment, flammability of the volatiles produced, and smoke shielding. High and early heat release rates can lead to rapid fire spread and fast flame propagation rates. Thus, in the case of fire, the escape time of a person is mainly dependent on the rate of heat release. The amorphous flame-retardant ceramic carbonizing agent is developed aiming at controlling the three speeds and four characteristics.
However, the traditional flame-retardant char forming agent has the defects of poor dispersibility processing technology, poor flame-retardant char forming performance, falling during combustion, high heat release speed, high smoke density, high material cost and the like. The amorphous flame-retardant ceramic carbonizing agent is a functional flame-retardant ceramic carbonizing agent synthesized by a high-molecular organic material, a ceramic inorganic material, a nano material and the like, and has the advantages of small product addition amount, low cost, low toxicity index conductivity, no halogen, environment friendliness and the like, and the synergistic flame retardance, low heat release, controlled combustion dripping, small smoke peak value and the like of the flame-retardant polymer are realized by matching the amorphous flame-retardant ceramic carbonizing agent with the inorganic flame retardant.
Amorphous flame retardant ceramic char forming agents have many advantages in the flame retardant field. However, due to the complexity of the compound formulation, the coordination among the compound formulation and the like, the problems of low flame retardant efficiency, poor heat release stability, poor char formation performance and the like exist. It is difficult to generate a carbon layer of good morphology in a short time, resulting in failure to efficiently achieve the intended effect. Therefore, improving the char formation performance and synergistic flame retarding ability of char-forming agents is an important research direction for improving overall performance.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention adopts a melting modification synthesis method, the organic silicon resin is added into the ceramic powder with different temperature resistance grades after treatment to be fully dispersed, then nano silicon dioxide, a structural modifier, a high temperature resistant nano stabilizer, magnesium hydride and aluminum oxide are added again to carry out organic modification synthesis, and the material proportion and the manufacturing process parameters are coordinated to prepare the amorphous flame retardant ceramic carbon forming agent material. The product can exert the synergistic flame-retardant effect of the halogen-free flame-retardant polyolefin material under the flame condition, thereby promoting the formation of a carbon layer for isolating heat and combustible gas transfer on the surface of the polymer by the char formation reaction, and simultaneously, the liquid phase melt generated by the interaction of the thermal decomposition product and the porcelain can bond the carbon layer of the polymer to form a compact carbon layer, thereby not only reducing heat release, but also reducing smoke yield and reducing smoke toxicity, and further, the flame-retardant performance and the combustion heat release, flame propagation speed, combustion falling objects, smoke toxicity and other standards of the halogen-free flame-retardant polyolefin material are obviously improved.
The invention provides an amorphous flame-retardant ceramic carbonizing agent material, which comprises the following components in percentage by weight:
100 parts by mass of organic silicon resin;
70-80 parts by mass of ceramic-based treated porcelain powder;
20-30 parts by mass of a high-temperature-resistant nano stabilizer;
5-15 parts by mass of a structural modifier;
20-30 parts by mass of gas phase nano silicon dioxide;
50-60 parts by mass of magnesium oxide;
50-60 parts of aluminum oxide.
The second aspect of the invention provides a preparation method of an amorphous flame-retardant ceramic carbon forming agent material, which comprises the following steps:
step 1: drying the organic silicon resin;
step 2: adding the organic silicon resin into an internal mixer according to the formula amount, heating and melting;
step 3: adding ceramic powder treated by a ceramic matrix in advance according to the formula amount for banburying;
step 4: adding high temperature resistant nano whisker and a structural modifier according to the formula amount, and carrying out heat preservation banburying;
step 5: according to the formula amount, adding gas phase nano silicon dioxide, magnesium oxide and aluminum oxide, banburying, extruding and crushing to prepare the amorphous flame-retardant ceramic carbonizing agent material.
Further, in the step 1 of the preparation method of the amorphous flame-retardant ceramic carbonizing agent material, the organic silicon resin is placed in an oven at 80+/-3 ℃ to be dried for 4 hours, and then the organic silicon resin is weighed according to a research formula.
Further, in the step 2 of the preparation method of the amorphous flame-retardant ceramic carbonizing agent material, the temperature and the rotating speed of the internal mixer are respectively set to be 100-110 ℃ and 30-40 Hz, and the heating and melting time is 10-20 min.
Further, in the step 3 of the preparation method of the amorphous flame-retardant ceramic carbonizing agent material, the banburying time is 60-70 min.
Further, in the step 4 of the preparation method of the amorphous flame-retardant ceramic carbonizing agent material, the time of heat preservation banburying is 40-50 min.
Further, in the step 5 of the preparation method of the amorphous flame-retardant ceramic carbonizing agent material, the banburying time is 50-60 min.
The third aspect of the invention also provides a flame retardant material comprising a thermoplastic polyolefin, aluminum hydroxide and the amorphous flame retardant ceramic char-forming agent material described above.
Further, 100 parts by mass of thermoplastic polyolefin material, 150 parts by mass of aluminum hydroxide and 10 parts by mass of amorphous flame-retardant ceramic carbonizing agent are added into a scouring machine, sheet is discharged at 120 ℃ on the scouring machine, and the sheet is placed into a flat vulcanizing machine with the set temperature of 160 ℃ to be preheated for 2min and maintained for 5min to obtain the flame-retardant ceramic carbonizing agent.
Advantageous effects
The material is prepared by reacting SiO at different temperatures and times 2 、Al 2 O 3 、MgO、Na 2 O、K 2 O、TiO 2 By melting CaO, B, or the likeCompared with the conventional inorganic carbonizing agent, the amorphous flame-retardant ceramic carbonizing agent material prepared by the blending method can generate molten liquid phase components during combustion, improves the crusting property of the material, and plays a role in bridging inorganic and organic states.
Amorphous polymers exist in three states which differ in the nature of thermal movement depending on temperature-glass, superelastic and liquid phases, molecular chains are not mobile at low temperatures, in which case the polymer behaves as a solid in the amorphous state, the energy of thermal movement becomes large enough to produce a displacement of the molecular chains into the superelastic state at sufficiently high temperatures, characterized by the ability of the polymer to easily stretch or compress, the transition from the superelastic state to the glassy state being ceramified, not only the molecular fragments but also the whole macromolecules being displaced in the viscous fluid state, the polymer then becoming fluid, the char forming reaction forming a char layer at the polymer which can insulate heat and combustible gas transfer. Simultaneously, the generated viscous melt can bond the polymer carbon layer, so that the compactness and the thermal stability of the carbon layer can be improved. Not only reduces the generation of combustible gas, but also improves the barrier property of the barrier layer and the flame retardant efficiency. The amorphous ceramic is cooled to form a compact barrier layer with good thermal stability, which has an inhibiting effect on mass transfer and heat transfer between a coacervate phase and a gas phase, and greatly improves the char forming performance of the char forming agent, so that the flame retardant performance of the flame retardant polyolefin material is obviously improved, and meanwhile, compared with the traditional inorganic char forming agent, the carbon emission can be reduced.
Detailed Description
The invention is further illustrated by the following specific examples, which are intended to illustrate the problem and to explain the invention, without limiting it.
The invention provides an amorphous flame-retardant ceramic carbonizing agent material and a preparation method thereof, wherein the material comprises the following components: 100 parts of organic silicon resin, 70-80 parts of ceramic-based treated porcelain powder, 20-30 parts of high-temperature-resistant nano stabilizer, 5-15 parts of structural modifier, 20-30 parts of gas-phase nano silicon dioxide, 50-60 parts of magnesium oxide and 50-60 parts of aluminum oxide.
Example 1
(1) Before the organic silicon resin is used, the organic silicon resin is placed in an oven at 80 ℃ for drying for 4 hours, and then the ceramic powder is treated by a ceramic base according to 100 parts by mass of the organic silicon resin, 20 parts by mass of a high-temperature-resistant nano stabilizer, 5 parts by mass of a structure modifier, 20 parts by mass of fumed silica, 50 parts by mass of magnesium oxide and 50 parts by mass of aluminum oxide are respectively measured.
(2) Adding the organic silicon resin into an internal mixer (the set temperature and the rotating speed are 100 ℃ and 30Hz respectively), heating and melting for 10min, and then adding ceramic base treated porcelain powder for banburying for 60min. Adding the high temperature resistant nano whisker again, carrying out heat preservation and honey refining on the structural modifier for 40min, then adding the gas phase nano silicon dioxide, magnesium oxide and aluminum oxide, carrying out banburying for 50min, and then extruding and crushing to obtain the amorphous flame retardant ceramic carbonizing agent.
(3) 100 parts by mass of thermoplastic polyolefin material is added with 150 parts by mass of aluminum hydroxide, 10 parts by mass of amorphous flame-retardant ceramic carbonizing agent is added, a sheet is discharged at 120 ℃ on a start-up machine, the sheet is placed in a flat vulcanizing machine with the set temperature of 160 ℃ for preheating for 2min, the pressure is maintained for 5min, and then the sheet is naturally cooled to a room temperature section to prepare a test sample.
Example 2
(1) Before the organic silicon resin is used, the organic silicon resin is placed in an oven at 80 ℃ for drying for 4 hours, and then the ceramic powder is treated by a ceramic base according to 100 parts by mass of the organic silicon resin, 21 parts by mass of a high-temperature-resistant nano stabilizer, 6 parts by mass of a structure modifier, 21 parts by mass of fumed silica, 51 parts by mass of magnesium oxide and 51 parts by mass of aluminum oxide are respectively measured.
(2) The organic silicon resin is added into an internal mixer (the set temperature and the rotating speed are 101 ℃ and 31Hz respectively) to be heated and melted for 11min, and then ceramic base treatment porcelain powder is added for banburying for 61min. Adding the high temperature resistant nano whisker again, carrying out heat preservation and refining for 41min by the structural modifier, then adding the gas phase nano silicon dioxide, magnesium oxide and aluminum oxide, carrying out banburying for 51min, and then extruding and crushing to obtain the amorphous flame retardant ceramic carbonizing agent.
(3) 100 parts by mass of thermoplastic polyolefin material is added with 150 parts by mass of aluminum hydroxide, 10 parts by mass of amorphous flame-retardant ceramic carbonizing agent is added, a sheet is discharged at 120 ℃ on a start-up machine, the sheet is placed in a flat vulcanizing machine with the set temperature of 160 ℃ for preheating for 2min, the pressure is maintained for 5min, and then the sheet is naturally cooled to a room temperature section to prepare a test sample.
Example 3
(1) Before the organic silicon resin is used, the organic silicon resin is placed in an oven at 80 ℃ for drying for 4 hours, and then 100 parts by weight of the organic silicon resin, 72 parts by weight of ceramic powder treated by a ceramic base, 22 parts by weight of high-temperature resistant nano stabilizer, 7 parts by weight of structure modifier, 22 parts by weight of fumed silica, 52 parts by weight of magnesia and 52 parts by weight of alumina are respectively measured.
(2) The organic silicon resin is added into an internal mixer (the set temperature and the rotating speed are 102 ℃ and 32Hz respectively) to be heated and melted for 12min, and then ceramic base treatment porcelain powder is added for banburying for 62min. Adding the high temperature resistant nano whisker again, carrying out heat preservation and refining on the structural modifier for 42min, then adding the gas phase nano silicon dioxide, magnesium oxide and aluminum oxide, carrying out banburying for 52min, and then extruding and crushing to obtain the amorphous flame retardant ceramic carbonizing agent.
(3) 100 parts by mass of thermoplastic polyolefin material is added with 150 parts by mass of aluminum hydroxide, 10 parts by mass of amorphous flame-retardant ceramic carbonizing agent is added, a sheet is discharged at 120 ℃ on a start-up machine, the sheet is placed in a flat vulcanizing machine with the set temperature of 160 ℃ for preheating for 2min, the pressure is maintained for 5min, and then the sheet is naturally cooled to a room temperature section to prepare a test sample.
Example 4
(1) Before the organic silicon resin is used, the organic silicon resin is placed in an oven at 80 ℃ for drying for 4 hours, and then the organic silicon resin is subjected to ceramic base treatment according to 100 parts by weight of the organic silicon resin, 73 parts by weight of ceramic powder, 23 parts by weight of high-temperature-resistant nano stabilizer, 8 parts by weight of structural modifier, 23 parts by weight of fumed silica, 53 parts by weight of magnesia and 53 parts by weight of alumina are respectively measured.
(2) The organic silicon resin is added into an internal mixer (the set temperature and the rotating speed are 103 ℃ and 33Hz respectively) to be heated and melted for 13min, and then ceramic base treatment porcelain powder is added for internal mixing for 63min. Adding the high temperature resistant nano whisker again, carrying out heat preservation and refining for 43min by the structural modifier, then adding the gas phase nano silicon dioxide, magnesium oxide and aluminum oxide, carrying out banburying for 53min, and then extruding and crushing to obtain the amorphous flame retardant ceramic carbonizing agent.
(3) 100 parts by mass of thermoplastic polyolefin material is added with 150 parts by mass of aluminum hydroxide, 10 parts by mass of amorphous flame-retardant ceramic carbonizing agent is added, a sheet is discharged at 120 ℃ on a start-up machine, the sheet is placed in a flat vulcanizing machine with the set temperature of 160 ℃ for preheating for 2min, the pressure is maintained for 5min, and then the sheet is naturally cooled to a room temperature section to prepare a test sample.
Example 5
(1) Before the organic silicon resin is used, the organic silicon resin is placed in an oven at 80 ℃ for drying for 4 hours, and then the ceramic powder is treated by ceramic base according to 100 parts by mass of the organic silicon resin, 24 parts by mass of high-temperature resistant nano stabilizer, 9 parts by mass of structure modifier, 24 parts by mass of fumed silica, 54 parts by mass of magnesia and 54 parts by mass of alumina are respectively measured.
(2) The organic silicon resin is added into an internal mixer (the set temperature and the rotating speed are 104 ℃ and 34Hz respectively) to be heated and melted for 14min, and then ceramic base treatment porcelain powder is added for banburying for 64min. Adding the high temperature resistant nano whisker again, carrying out heat preservation and refining on the structural modifier for 44min, then adding the gas phase nano silicon dioxide, magnesium oxide and aluminum oxide, carrying out banburying for 54min, and then extruding and crushing to obtain the amorphous flame retardant ceramic carbonizing agent.
(3) 100 parts by mass of thermoplastic polyolefin material is added with 150 parts by mass of aluminum hydroxide, 10 parts by mass of amorphous flame-retardant ceramic carbonizing agent is added, a sheet is discharged at 120 ℃ on a start-up machine, the sheet is placed in a flat vulcanizing machine with the set temperature of 160 ℃ for preheating for 2min, the pressure is maintained for 5min, and then the sheet is naturally cooled to a room temperature section to prepare a test sample.
Example 6
(1) Before the organic silicon resin is used, the organic silicon resin is placed in an oven at 80 ℃ for drying for 4 hours, and then the ceramic powder is treated by a ceramic base according to 100 parts by weight of the organic silicon resin, 25 parts by weight of a high-temperature-resistant nano stabilizer, 10 parts by weight of a structure modifier, 25 parts by weight of fumed silica, 55 parts by weight of magnesium oxide and 55 parts by weight of aluminum oxide are respectively measured.
(2) The organic silicon resin is added into an internal mixer (the set temperature and the rotating speed are 105 ℃ and 35Hz respectively) to be heated and melted for 15min, and then ceramic base treatment porcelain powder is added for banburying for 65min. Adding the high temperature resistant nano whisker again, carrying out heat preservation and refining on the structural modifier for 45min, then adding the gas phase nano silicon dioxide, magnesium oxide and aluminum oxide, carrying out banburying for 55min, and then extruding and crushing to obtain the amorphous flame retardant ceramic carbonizing agent.
(3) 100 parts by mass of thermoplastic polyolefin material is added with 150 parts by mass of aluminum hydroxide, 10 parts by mass of amorphous flame-retardant ceramic carbonizing agent is added, a sheet is discharged at 120 ℃ on a start-up machine, the sheet is placed in a flat vulcanizing machine with the set temperature of 160 ℃ for preheating for 2min, the pressure is maintained for 5min, and then the sheet is naturally cooled to a room temperature section to prepare a test sample.
Example 7
(1) Before the organic silicon resin is used, the organic silicon resin is placed in an oven at 80 ℃ for drying for 4 hours, and then the ceramic powder is treated by ceramic base according to 100 parts by mass of the organic silicon resin, 26 parts by mass of high-temperature resistant nano stabilizer, 11 parts by mass of structural modifier, 26 parts by mass of fumed silica, 56 parts by mass of magnesia and 56 parts by mass of alumina are respectively measured.
(2) The organic silicon resin is added into an internal mixer (the set temperature and the rotating speed are 106 ℃ and 36Hz respectively) to be heated and melted for 16min, and then ceramic base treatment porcelain powder is added for banburying for 66min. Adding the high temperature resistant nano whisker again, carrying out heat preservation and refining for 46min by the structural modifier, then adding the gas phase nano silicon dioxide, magnesium oxide and aluminum oxide, carrying out banburying for 56min, and then extruding and crushing to obtain the amorphous flame retardant ceramic carbonizing agent.
(3) 100 parts by mass of thermoplastic polyolefin material is added with 150 parts by mass of aluminum hydroxide, 10 parts by mass of amorphous flame-retardant ceramic carbonizing agent is added, a sheet is discharged at 120 ℃ on a start-up machine, the sheet is placed in a flat vulcanizing machine with the set temperature of 160 ℃ for preheating for 2min, the pressure is maintained for 5min, and then the sheet is naturally cooled to a room temperature section to prepare a test sample.
Example 8
(1) Before the organic silicon resin is used, the organic silicon resin is placed in an oven at 80 ℃ for drying for 4 hours, and then the ceramic powder is treated by ceramic base 77 parts by weight of ceramic powder, 27 parts by weight of high-temperature resistant nano stabilizer, 12 parts by weight of structural modifier, 27 parts by weight of fumed silica, 57 parts by weight of magnesium oxide and 57 parts by weight of aluminum oxide are respectively measured.
(2) The organic silicon resin is added into an internal mixer (the set temperature and the rotating speed are respectively 107 ℃ and 37 Hz) to be heated and melted for 17min, and then ceramic base treatment porcelain powder is added to be internally mixed for 67min. Adding the high temperature resistant nano whisker again, carrying out heat preservation and refining for 47min by the structural modifier, then adding the gas phase nano silicon dioxide, magnesium oxide and aluminum oxide, carrying out banburying for 57min, and then extruding and crushing to obtain the amorphous flame retardant ceramic carbonizing agent.
(3) 100 parts by mass of thermoplastic polyolefin material is added with 150 parts by mass of aluminum hydroxide, 10 parts by mass of amorphous flame-retardant ceramic carbonizing agent is added, a sheet is discharged at 120 ℃ on a start-up machine, the sheet is placed in a flat vulcanizing machine with the set temperature of 160 ℃ for preheating for 2min, the pressure is maintained for 5min, and then the sheet is naturally cooled to a room temperature section to prepare a test sample.
Example 9
(1) Before the organic silicon resin is used, the organic silicon resin is placed in an oven at 80 ℃ for drying for 4 hours, and then the ceramic powder is treated by ceramic base 78 parts by weight, the high temperature resistant nano stabilizer 28 parts by weight, the structure modifier 13 parts by weight, the fumed silica 28 parts by weight, the magnesium oxide 58 parts by weight and the aluminum oxide 58 parts by weight are respectively measured.
(2) The organic silicon resin is added into an internal mixer (the set temperature and the rotating speed are respectively 108 ℃ and 38 Hz) to be heated and melted for 18min, and then ceramic base treatment porcelain powder is added for internal mixing for 68min. Adding the high temperature resistant nano whisker again, carrying out heat preservation and honey refining on the structural modifier for 48min, then adding the gas phase nano silicon dioxide, magnesium oxide and aluminum oxide, carrying out banburying for 58min, and then extruding and crushing to obtain the amorphous flame retardant ceramic carbonizing agent.
(3) 100 parts by mass of thermoplastic polyolefin material is added with 150 parts by mass of aluminum hydroxide, 10 parts by mass of amorphous flame-retardant ceramic carbonizing agent is added, a sheet is discharged at 120 ℃ on a start-up machine, the sheet is placed in a flat vulcanizing machine with the set temperature of 160 ℃ for preheating for 2min, the pressure is maintained for 5min, and then the sheet is naturally cooled to a room temperature section to prepare a test sample.
Example 10
(1) Before the organic silicon resin is used, the organic silicon resin is placed in an oven at 80 ℃ for drying for 4 hours, and then the ceramic powder is treated by ceramic base according to 100 parts by mass of the organic silicon resin, 29 parts by mass of high-temperature-resistant nano stabilizer, 14 parts by mass of structure modifier, 29 parts by mass of fumed silica, 59 parts by mass of magnesia and 59 parts by mass of alumina are respectively measured.
(2) The organic silicon resin is added into an internal mixer (the set temperature and the rotating speed are 109 ℃ and 39Hz respectively) to be heated and melted for 19min, and then ceramic base treatment porcelain powder is added for internal mixing for 69min. Adding the high temperature resistant nano whisker again, carrying out heat preservation and refining on the structural modifier for 49min, then adding the gas phase nano silicon dioxide, magnesium oxide and aluminum oxide, carrying out banburying for 59min, and then extruding and crushing to obtain the amorphous flame retardant ceramic carbonizing agent.
(3) 100 parts by mass of thermoplastic polyolefin material is added with 150 parts by mass of aluminum hydroxide, 10 parts by mass of amorphous flame-retardant ceramic carbonizing agent is added, a sheet is discharged at 120 ℃ on a start-up machine, the sheet is placed in a flat vulcanizing machine with the set temperature of 160 ℃ for preheating for 2min, the pressure is maintained for 5min, and then the sheet is naturally cooled to a room temperature section to prepare a test sample.
Example 11
(1) Before the organic silicon resin is used, the organic silicon resin is placed in an oven at 80 ℃ for drying for 4 hours, and then 80 parts by weight of ceramic powder is treated by a ceramic base according to 100 parts by weight of the organic silicon resin, 30 parts by weight of high-temperature resistant nano stabilizer, 15 parts by weight of structure modifier, 30 parts by weight of fumed silica, 60 parts by weight of magnesium oxide and 60 parts by weight of aluminum oxide are respectively measured.
(2) Adding the organic silicon resin into an internal mixer (the set temperature and the rotating speed are 110 ℃ and 40Hz respectively), heating and melting for 20min, and then adding ceramic base treated porcelain powder for banburying for 70min. Adding the high temperature resistant nano whisker again, carrying out heat preservation and honey refining on the structural modifier for 50min, then adding the gas phase nano silicon dioxide, magnesium oxide and aluminum oxide, carrying out banburying for 60min, and then extruding and crushing to obtain the amorphous flame retardant ceramic carbonizing agent.
(3) 100 parts by mass of thermoplastic polyolefin material is added with 150 parts by mass of aluminum hydroxide, 10 parts by mass of amorphous flame-retardant ceramic carbonizing agent is added, a sheet is discharged at 120 ℃ on a start-up machine, the sheet is placed in a flat vulcanizing machine with the set temperature of 160 ℃ for preheating for 2min, the pressure is maintained for 5min, and then the sheet is naturally cooled to a room temperature section to prepare a test sample.
Comparative example 1
Adding 150 parts of aluminum hydroxide into 100 parts of thermoplastic polyolefin material, preheating for 2min in a plate vulcanizing machine with the temperature of 160 ℃ at 120 ℃ on a driving machine, maintaining the pressure for 5min, and naturally cooling to a room temperature section to obtain a test sample.
Comparative example 2
100 parts of thermoplastic polyolefin material is added with 150 parts of aluminum hydroxide and 10 parts of magnesium hydroxide by mass, a piece is discharged from a 120-DEG C sheet mill on an open mill and is placed in a flat vulcanizing machine with a set temperature of 160 ℃ for preheating for 2min, the pressure is maintained for 5min, and then the test sample can be obtained after natural cooling to a room temperature section.
Comparative example 3
100 parts of thermoplastic polyolefin material is added with 150 parts of aluminum hydroxide and 10 parts by mass of organic montmorillonite, a piece is taken out on a driving machine at 120 ℃ and placed in a flat vulcanizing machine with the set temperature of 160 ℃ to be preheated for 2min, the pressure is maintained for 5min, and then the test sample can be obtained after natural cooling to the room temperature.
Comparative example 4
100 parts of thermoplastic polyolefin material is added with 150 parts of aluminum hydroxide and 10 parts of ammonium polyphosphate by mass, a piece is discharged from a piece at 120 ℃ on a driving machine and placed in a flat vulcanizing machine with the set temperature of 160 ℃ to be preheated for 2min, the pressure is maintained for 5min, and then the sample is naturally cooled to a room temperature section to prepare a test sample.
Comparative example 5
100 parts of thermoplastic polyolefin material is added with 150 parts of aluminum hydroxide and 10 parts by mass of aluminum hypophosphite, a piece is discharged at 120 ℃ on a driving machine and placed in a flat vulcanizing machine with the set temperature of 160 ℃ to be preheated for 2 minutes, the pressure is maintained for 5 minutes, and then the test sample can be obtained after natural cooling to a room temperature section.
Comparative example 6
100 parts of thermoplastic polyolefin material is added with 150 parts of aluminum hydroxide and 10 parts by mass of red phosphorus, a piece is discharged at 120 ℃ on a driving machine and placed in a flat vulcanizing machine with the set temperature of 160 ℃ to be preheated for 2 minutes, the pressure is maintained for 5 minutes, and then the test sample can be obtained after natural cooling to a room temperature section.
Effect verification
The sample specifications of each example and comparative example are as follows: 130mm by 6mm by 3mm limiting oxygen index test bars, 130mm by 13mm by 1.6mm vertical burn test bars, 100mm by 4mm cone calorimeter sample pieces, 4mm by 1mm tensile bars.
The standard samples obtained in examples 1 to 11 and comparative examples 1 to 6 were subjected to a vertical combustion test in accordance with GB/T2408-2008 (1.6 mm); limiting oxygen index test was performed according to GB/T2406.2-2009; testing according to GB/T16172 ISO5660-1 cone calorimeter to obtain peak heat release value, total heat release amount and smoke production rate; tensile testing was performed according to GB/T1040.3-2006; the test results are as follows.
The above embodiments are illustrative for the purpose of illustrating the technical concept and features of the present invention so that those skilled in the art can understand the content of the present invention and implement it accordingly, and thus do not limit the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.

Claims (9)

1. An amorphous flame-retardant ceramic carbonizing material is characterized in that: the composition comprises the following components:
100 parts by mass of organic silicon resin;
70-80 parts by mass of ceramic-based treated porcelain powder;
20-30 parts by mass of a high-temperature-resistant nano stabilizer;
5-15 parts by mass of a structural modifier;
20-30 parts by mass of gas phase nano silicon dioxide;
50-60 parts by mass of magnesium oxide;
50-60 parts of aluminum oxide.
2. The method for preparing the amorphous flame-retardant ceramic char-forming agent material according to claim 1, wherein the method comprises the following steps: the method comprises the following steps:
step 1: drying the organic silicon resin;
step 2: adding the organic silicon resin into an internal mixer according to the formula amount, heating and melting;
step 3: adding ceramic powder treated by a ceramic matrix in advance according to the formula amount for banburying;
step 4: adding high temperature resistant nano whisker and a structural modifier according to the formula amount, and carrying out heat preservation banburying;
step 5: according to the formula amount, adding gas phase nano silicon dioxide, magnesium oxide and aluminum oxide, banburying, extruding and crushing to prepare the amorphous flame-retardant ceramic carbonizing agent material.
3. The method for preparing the amorphous flame-retardant ceramic char-forming agent material according to claim 2, wherein: in the step 1, the organic silicon resin is placed in an oven at 80+/-3 ℃ to be dried for 4 hours, and then is weighed according to a research formula.
4. The method for preparing the amorphous flame-retardant ceramic char-forming agent material according to claim 2, wherein: in the step 2, the temperature and the rotating speed of the internal mixer are respectively set to be 100-110 ℃ and 30-40 Hz, and the heating and melting time is set to be 10-20 min.
5. The method for preparing the amorphous flame-retardant ceramic char-forming agent material according to claim 2, wherein: in the step 3, the banburying time is 60-70 min.
6. The method for preparing the amorphous flame-retardant ceramic char-forming agent material according to claim 2, wherein: in the step 4, the time of heat preservation banburying is 40-50 min.
7. The method for preparing the amorphous flame-retardant ceramic char-forming agent material according to claim 2, wherein: in the step 5, banburying time is 50-60 min.
8. A flame retardant material, characterized by: comprising a thermoplastic polyolefin, aluminum hydroxide and the amorphous flame retardant ceramic char-forming agent material of claim 1.
9. The flame retardant material of claim 8, wherein: 100 parts by mass of thermoplastic polyolefin material, 150 parts by mass of aluminum hydroxide and 10 parts by mass of amorphous flame-retardant ceramic carbonizing agent are added into a scouring machine, sheet is discharged at 120 ℃ on the scouring machine, and the sheet is placed into a flat vulcanizing machine with the set temperature of 160 ℃ to be preheated for 2min and maintained for 5min to obtain the flame-retardant ceramic carbonizing agent.
CN202311509434.XA 2023-11-14 2023-11-14 Amorphous flame-retardant ceramic carbonizing agent material, preparation method thereof and flame-retardant material Pending CN117467193A (en)

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Publication number Priority date Publication date Assignee Title
CN105694471A (en) * 2016-04-17 2016-06-22 北京化工大学 Preparation method of ceramizing fire-resistant silicon rubber
CN105860536A (en) * 2016-04-13 2016-08-17 山东兆圭高分子材料科技有限公司 Flame-retardant and fire-resistant ceramic silicone rubber and preparation method thereof
CN109776934A (en) * 2018-12-29 2019-05-21 惠州市安品新材料有限公司 Fire-resisting cable composite polyolefine material
WO2022135250A1 (en) * 2020-12-21 2022-06-30 金发科技股份有限公司 Alloy material having ceramicized surface, preparation method therefor and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105860536A (en) * 2016-04-13 2016-08-17 山东兆圭高分子材料科技有限公司 Flame-retardant and fire-resistant ceramic silicone rubber and preparation method thereof
CN105694471A (en) * 2016-04-17 2016-06-22 北京化工大学 Preparation method of ceramizing fire-resistant silicon rubber
CN109776934A (en) * 2018-12-29 2019-05-21 惠州市安品新材料有限公司 Fire-resisting cable composite polyolefine material
WO2022135250A1 (en) * 2020-12-21 2022-06-30 金发科技股份有限公司 Alloy material having ceramicized surface, preparation method therefor and application thereof

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