CN110982193A - High-performance electric power meter shell material and preparation method thereof - Google Patents
High-performance electric power meter shell material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-performance electric power meter shell material, which belongs to the technical field of electric meter shell material preparation and comprises the following raw materials: polyvinyl chloride, polyethylene, a modified flame retardant, nano silicon dioxide, glass fiber, methyl methacrylate, polylactic acid, decabromodiphenylethane, chitin, di (2, 3-dichloropropyl) octyl phosphate, tri (neopentyl glycol phosphate) methylamine, an insulating assistant, vinyl triethoxysilane and hexachlorocyclotriphosphazene; the high-performance electric meter shell material is prepared by preparing a base material, preparing a modified material and mixing a main material and the modified material. The shell material of the electric power meter prepared by the invention has excellent fire resistance.
Description
Technical Field
The invention belongs to the technical field of electric meter shell material preparation, and particularly relates to a high-performance electric power electric meter shell material and a preparation method thereof.
Background
The electric meter is an electric energy meter for short, is an instrument for measuring electric energy, is also called an electric meter, a fire meter, an electric energy meter and a kilowatt-hour meter, and is an instrument for measuring various electric quantities. The electric meter case mainly functions to protect the internal parts of the electric meter, and requires good mechanical properties, good thermal stability and flame retardancy. At present, the shell material of the domestic electric meter is mostly made of flame-retardant ABS. Although flame-retardant ABS is inexpensive, its rigidity is not very good. Reinforced Polycarbonate (PC) is mostly adopted at present abroad, and along with the development of economy in China, a large amount of reinforced PC is also adopted as the material of the shell of the electric meter at home. Polycarbonate is a colorless and transparent amorphous thermoplastic material, has chemical properties of weak acid resistance, weak base resistance, neutral oil resistance, ultraviolet light resistance and strong base resistance, and has physical properties of linear expansion coefficient: 38 multiplied by 10cm/cm < 2 >, the thermal deformation temperature is 135 ℃, and the defects of poor stability, easy stress crack, low impact resistance to a notch, poor wear resistance, low adhesive force to a metal piece, high viscosity, poor fluidity, influence on processing injection molding and the like exist.
Chinese patent application document "a power electric meter shell material (publication number: CN 104479255A)" discloses a power electric meter shell material, which is prepared from the following raw materials in parts by weight: 90-100 parts of polyvinyl chloride, 60-70 parts of polyethylene, 40-50 parts of methyl methacrylate, 38-42 parts of glass fiber, 30-36 parts of polyvinyl chloride, 25-28 parts of polylactic acid, 20-22 parts of decabromodiphenylethane, 18-20 parts of an insulating additive, 12-15 parts of chitin, 10-12 parts of pine oil powder, 7-8 parts of silicon carbide powder, 4-5 parts of sodium succinate, 2-4 parts of talcum powder, 2-3 parts of barium sulfate and 1-2 parts of graphite powder. The material of the invention has higher mechanical property, thermal stability and flame retardant property. Although the flame retardant performance is improved by adding the flame retardant, the flame retardant performance of the electricity meter shell material is obviously not enough by only adding the flame retardant into the electricity meter shell material, and the engineering electricity meter shell material has high requirement on the flame retardant performance, so that the problem of insufficient flame retardant performance of the electricity meter shell material needs to be solved by developing a higher flame retardant electricity meter shell material.
Disclosure of Invention
The invention aims to provide a high-performance electric power meter shell material and a preparation method thereof, and aims to solve the problem of how to optimize components, dosage, methods and the like and improve the fire resistance of the electric power meter shell material on the basis of a fireproof electric power meter shell material disclosed in the patent application document 'an electric power meter shell material (publication number: CN 104479255A').
In order to solve the technical problems, the invention adopts the following technical scheme:
a high-performance electric meter shell material comprises the following raw materials: polyvinyl chloride, polyethylene, a modified flame retardant, nano silicon dioxide, glass fiber, methyl methacrylate, polylactic acid, decabromodiphenylethane, chitin, di (2, 3-dichloropropyl) octyl phosphate, tri (neopentyl glycol phosphate) methylamine, an insulating assistant, vinyl triethoxysilane and hexachlorocyclotriphosphazene;
the modified flame retardant comprises the following raw materials in parts by weight: 8-12 parts of asphalt, 1-5 parts of potassium persulfate, 2-5 parts of polyaryl phosphate, 3-6 parts of polypropylene, 4-8 parts of silane coupling agent KH-550, 3-9 parts of kieselguhr, 2-6 parts of aluminum polyphosphate, 4-8 parts of sepiolite powder, 3-9 parts of nano aluminum hydroxide, 2-5 parts of antimony trioxide and 4-8 parts of zinc borate;
the insulating auxiliary agent comprises the following raw materials in parts by weight: 4-7 parts of pine oil, 3-6 parts of boron carbide, 2-5 parts of kapok, 1-4 parts of potassium acetate, 3-6 parts of hydrogen-containing silicone oil, 1-5 parts of bismaleimide, 2-6 parts of polyvinyl sulfonic acid, 1-4 parts of epoxy resin, 3-5 parts of methyl tetrahydrophthalic anhydride and 4-8 parts of methyl silicone oil;
the weight ratio of the polyvinyl chloride, the chitin, the polyethylene, the modified flame retardant and the insulating auxiliary agent is (15-25): (6-9): (4-8): (9-12): (1-3).
Further, the weight ratio of the polyvinyl chloride, the chitin, the polyethylene, the modified flame retardant and the insulating auxiliary agent is 21.3: 7.2: 5.8: 10.8: 2.3.
further, the feed comprises the following raw materials in parts by weight: 15-25 parts of polyvinyl chloride, 4-8 parts of polyethylene, 9-12 parts of modified flame retardant, 3-6 parts of nano silicon dioxide, 1-5 parts of glass fiber, 1-3 parts of methyl methacrylate, 2-5 parts of polylactic acid, 4-8 parts of decabromodiphenylethane, 6-9 parts of chitin, 3-9 parts of di (2, 3-dichloropropyl) octyl phosphate, 2-5 parts of tri (neopentyl glycol phosphate) methylamine, 1-3 parts of insulating assistant, 4-8 parts of vinyl triethoxysilane and 8-12 parts of hexachlorocyclotriphosphazene.
Further, the modified flame retardant is prepared by the following process: uniformly mixing the asphalt, the polypropylene, the potassium persulfate and the polyaryl phosphate, heating to 60-80 ℃, keeping the temperature for 2-4h to obtain a core, adding a silane coupling agent KH-550, the kieselguhr, the sepiolite powder, the nano aluminum hydroxide, the antimony trioxide, the zinc borate and the aluminum polyphosphate into the core, uniformly mixing, stirring at the rotation speed of 650 plus 850r/min for 10-30min, adjusting the pH to 3.5-5.0, heating to 65-75 ℃, keeping the temperature for 0.5-1.5h to form a shell layer on the periphery of the core, washing, drying in vacuum at 65-75 ℃ to constant weight, and cooling to room temperature to obtain the modified flame retardant.
Further, the insulating auxiliary agent is prepared by the following process: mixing oleum Pini, boron carbide, kapok and potassium acetate uniformly, heating to 100-, then adding hydrogen-containing silicone oil and bismaleimide, mixing uniformly, heating to 135 ℃ at 125-, then adding methyl tetrahydrophthalic anhydride, mixing uniformly, heating to 80-120 ℃, preserving heat for 1-3h, cooling to room temperature, adding methyl silicone oil, mixing uniformly, stirring at the rotating speed of 650 plus 850r/min for 20-40min, evacuating, removing bubbles, and cooling to room temperature to obtain the insulating assistant.
The invention provides a preparation method of a high-performance electric power meter shell material, which comprises the following steps:
s1, uniformly mixing ethylene propylene rubber, styrene butadiene rubber and ammonium polyphosphate, heating to 120-;
s2, uniformly mixing polyvinyl chloride and fluorocarbon resin, heating to 110-130 ℃, preserving heat for 20-40min, adding chitin, polyethylene, silicon-hydrogen-containing group, cellulose ether, carbon black N330, glass fiber, sodium silicate, chlorinated paraffin, dimethyl silicone oil, expanded vermiculite, a promoter TMDT, zinc oxide, stearic acid and an anti-aging agent RD, uniformly mixing, stirring at the rotating speed of 850-1050r/min for 1-2h, continuously heating to 80-90 ℃, preserving heat for 5-15min, adding a modified flame retardant and an insulating assistant, uniformly mixing, stirring at the rotating speed of 2500-3500r/min for 5-15min, and cooling to room temperature to obtain a modified material;
s3, heating the base material obtained in the step S1 to 110-.
The invention has the following beneficial effects:
(1) as can be seen from the data of examples 1 to 3 and comparative example 7, the fire resistance of the high performance electricity meter case material prepared in examples 1 to 3 is significantly higher than that of the electricity meter case material prepared in comparative example 7; meanwhile, as can be seen from the data of examples 1 to 3, example 1 is the most preferred example.
(2) As can be seen from the data of the example 1 and the comparative examples 1 to 6, the polyvinyl chloride, the chitin, the polyethylene, the modified flame retardant and the insulating assistant play a synergistic role in preparing the high-performance electric power meter shell material, and the fire resistance of the high-performance electric power meter shell material is synergistically improved; this is:
polyvinyl chloride, chitin, polyethylene, a modified flame retardant and an insulating auxiliary agent are used as a reinforcing system, polyvinyl chloride is used as a basic electric meter shell material, chitin and polyethylene are used as fire-resistant fillers, the surfaces of the chitin and the polyethylene contain a large number of hydroxyl groups, and the hydroxyl groups can be connected with unsaturated bonds on the surface of the polyvinyl chloride under the connecting action of the insulating auxiliary agent, so that the chitin and the polyethylene surround the polyvinyl chloride, the surface area of the polyvinyl chloride is increased, more contact areas are obtained when the basic electric meter shell material is used, the fire resistance of the polyvinyl chloride is reinforced by the fire-resistant fillers wrapped outside the polyvinyl chloride, and the fire resistance of the polyvinyl chloride is effectively improved, wherein the organic modified montmorillonite has a good barrier effect, and alkyl ammonium salts contained in the organic modified montmorillonite are subjected to Hofmann degradation when being heated, the acidic points with catalytic activity are formed, the formation of the carbon layer is promoted, the formation of the carbon layer can provide more cross-linked spaces for polyethylene, the polyethylene is connected to polyvinyl chloride in a cross-linked mode, after more polyethylene is obtained from unsaturated bonds on the periphery of the polyvinyl chloride, the polyethylene can well play a role in isolating oxygen, the fire resistance of the polyvinyl chloride is further effectively improved, chitin and a modified fire retardant which have fire resistance are matched, and the chitin and the modified fire retardant are distributed on all parts on the periphery of the polyvinyl chloride under the connecting effect of an insulating assistant, so that all positions on the surface of the polyvinyl chloride have strong fire resistance.
The added modified flame retardant takes the asphalt and the polyaryl phosphate as raw materials, takes potassium persulfate as an initiator to prepare a core, and then takes a silane coupling agent KH-550 as a connecting intermediate between the core and a shell layer to realize that the diatomite, the sepiolite powder, the nano aluminum hydroxide, the antimony trioxide, the zinc borate and the aluminum polyphosphate are connected to the periphery of the core through the silane coupling agent KH-550 to form the shell layer, because the diatomite, the sepiolite powder, the nano aluminum hydroxide, the antimony trioxide, the zinc borate and the aluminum polyphosphate are all refractory fillers, on one hand, the modified granulated flame retardant is endowed with good flame retardant effect on the periphery of the core, and simultaneously, the prepared modified granulated flame retardant is formed due to the formation of the core shell, the surface area of the granulated modified flame retardant is smaller, in a reinforcing system, the insulating assistant can further connect the modified flame retardant to the periphery of polyvinyl chloride, the granulation modified flame retardant with smaller surface area can be more uniformly distributed on the outer surface of the polyvinyl chloride, so that the polyvinyl chloride forms a grid structure, the chitin and the polyethylene can be connected to the polyvinyl chloride by the insulating auxiliary agent in the grid structure, and the reinforcement of the flame retardant property of the polyvinyl chloride is effectively realized under the combined action of the modified flame retardant, the chitin and the polyethylene.
Meanwhile, the silane coupling agent KH-550 is migrated to the surface of the fire-resistant monomer main material after being heated to form a high molecular gradient material, so that an inorganic heat insulation protective layer with Si-C and Si-O bonds is generated, and KH-550 can be connected between hydroxyl on the surface of the fire-resistant filler and the fire-resistant monomer main material, so that the diatomite, the aluminum polyphosphate, the sepiolite powder, the nano aluminum hydroxide, the antimony trioxide and the zinc borate are wrapped on the periphery of the fire-resistant monomer main material, and the fire resistance of the monomer main material is further improved by the fire resistance of the fire-resistant filler.
In addition, the added insulating auxiliary agent is obtained by uniformly mixing pine oil, boron carbide, kapok and potassium acetate, heating, preserving heat and continuously stirring in the heat preservation process, then adding hydrogen-containing silicone oil and bismaleimide to be uniformly mixed, heating, preserving heat, vacuumizing, cooling, adding polyvinyl sulfonic acid and epoxy resin to be uniformly mixed, heating, preserving heat, stirring, cooling to room temperature, then adding methyl tetrahydrophthalic anhydride to be uniformly mixed, heating, preserving heat, cooling to room temperature, adding methyl silicone oil to be uniformly mixed, stirring, evacuating, defoaming and cooling to room temperature, wherein the epoxy resin is used as a base resin, polyvinyl sulfonic acid, hydrogen-containing silicone oil and bismaleimide are used as organic modifying auxiliary agents, pine oil, boron carbide, kapok and potassium acetate are used as insulating fillers, the surface of the insulating fillers is modified by the organic modifying auxiliary agents, and the combination of hydroxyl on the surface of the insulating fillers and unsaturated bonds of the organic modifying auxiliary agents is realized, and the curing effect of the methyl tetrahydrophthalic anhydride is applied to the preparation of the insulating electricity meter shell material, so that the excellent insulating property of the pine oil, the boron carbide, the kapok and the potassium acetate insulating filler is reinforced in the electricity meter shell material, and the reinforcing effect on the insulating property of the electricity meter shell material is realized.
(3) As can be seen from the data of comparative examples 8-10, the weight ratio of polyvinyl chloride, chitin, polyethylene, modified flame retardant, and insulating aid is not (15-25): (6-9): (4-8): (9-12): (1-3), the fire resistance value of the obtained electricity meter case material is very different from that of examples 1-3, much smaller than that of examples 1-3, and not much different from that of the prior art (comparative example 7). In the embodiments 1 to 3 of the invention, when the high-performance electric power meter shell material is prepared, the weight ratio of polyvinyl chloride, chitin, polyethylene, modified flame retardant and insulating auxiliary agent is controlled to be (15-25): (6-9): (4-8): (9-12): and (1-3) the polyvinyl chloride is used as the main raw material of a reinforcing system, the chitin, the polyethylene and the modified flame retardant are used as the fire-resistant reinforcing auxiliary agent, and under the connection action of the insulating auxiliary agent, the hydroxyl on the surface of the fire-resistant reinforcing auxiliary agent is combined with the unsaturated bond on the surface of the main material polyvinyl chloride, so that the fire resistance of the chitin, the polyethylene and the modified flame retardant is fully utilized, and the fire resistance reinforcement of the polyvinyl chloride is realized.
(4) By adding vinyl triethoxysilane and hexachlorocyclotriphosphazene into the base material, the vinyl triethoxysilane contains organic silicon functional groups, and the organic silicon functional groups on the vinyl triethoxysilane replace chlorine atoms in the vinyl triethoxysilane, the abundant silicon elements can be utilized to reduce the amount of phosphorus and nitrogen in the flame retardant in the process of preparing the base material, so that the fire resistance of the shell material of the electric meter is improved.
Detailed Description
In order to facilitate a better understanding of the invention, the following examples are given to illustrate, but not to limit the scope of the invention.
In an embodiment, the high-performance electric power meter shell material comprises the following raw materials in parts by weight: 15-25 parts of polyvinyl chloride, 4-8 parts of polyethylene, 9-12 parts of modified flame retardant, 3-6 parts of nano silicon dioxide, 1-5 parts of glass fiber, 1-3 parts of methyl methacrylate, 2-5 parts of polylactic acid, 4-8 parts of decabromodiphenylethane, 6-9 parts of chitin, 3-9 parts of di (2, 3-dichloropropyl) octyl phosphate, 2-5 parts of tri (neopentyl glycol phosphate) methylamine, 1-3 parts of insulating assistant, 4-8 parts of vinyl triethoxysilane and 8-12 parts of hexachlorocyclotriphosphazene.
The modified flame retardant is prepared by the following process: uniformly mixing 8-12 parts of asphalt, 3-6 parts of polypropylene, 1-5 parts of potassium persulfate and 2-5 parts of polyaryl phosphate according to parts by weight, heating to 60-80 ℃, preserving heat for 2-4 hours to obtain a core, adding 4-8 parts of silane coupling agent KH-550, 3-9 parts of diatomite, 4-8 parts of sepiolite powder, 3-9 parts of nano aluminum hydroxide, 2-5 parts of antimony trioxide, 4-8 parts of zinc borate and 2-6 parts of aluminum polyphosphate into the core, uniformly mixing, stirring at the rotation speed of 650 plus 850r/min for 10-30 minutes, adjusting the pH value to 3.5-5.0, heating to 65-75 ℃, preserving heat for 0.5-1.5 hours to form a shell layer on the periphery of the core, washing, drying in vacuum at 65-75 ℃ to constant weight, and cooling to room temperature to obtain the modified flame retardant.
The insulating assistant is prepared by the following process: mixing oleum Pini, boron carbide, kapok and potassium acetate uniformly, heating to 100-, then adding hydrogen-containing silicone oil and bismaleimide, mixing uniformly, heating to 135 ℃ at 125-, then adding methyl tetrahydrophthalic anhydride, mixing uniformly, heating to 80-120 ℃, preserving heat for 1-3h, cooling to room temperature, adding methyl silicone oil, mixing uniformly, stirring at the rotating speed of 650 plus 850r/min for 20-40min, evacuating, removing bubbles, and cooling to room temperature to obtain the insulating assistant.
The preparation method of the high-performance electric meter shell material comprises the following steps:
s1, uniformly mixing ethylene propylene rubber, styrene butadiene rubber and ammonium polyphosphate, heating to 120-;
s2, uniformly mixing polyvinyl chloride and fluorocarbon resin, heating to 110-130 ℃, preserving heat for 20-40min, adding chitin, polyethylene, silicon-hydrogen-containing group, cellulose ether, carbon black N330, glass fiber, sodium silicate, chlorinated paraffin, dimethyl silicone oil, expanded vermiculite, a promoter TMDT, zinc oxide, stearic acid and an anti-aging agent RD, uniformly mixing, stirring at the rotating speed of 850-1050r/min for 1-2h, continuously heating to 80-90 ℃, preserving heat for 5-15min, adding a modified flame retardant and an insulating assistant, uniformly mixing, stirring at the rotating speed of 2500-3500r/min for 5-15min, and cooling to room temperature to obtain a modified material;
s3, heating the modified base material obtained in the step S1 to 110-130 ℃, preserving heat for 20-30min, adding the modified material obtained in the step S2, cooling to 70-80 ℃, preserving heat for 1-2h, stirring at the rotating speed of 850r/min for 1-2h, and cooling to room temperature to obtain the high-performance electric meter shell material.
Example 1
The high-performance electric meter shell material comprises the following raw materials in parts by weight: 20 parts of polyvinyl chloride, 6 parts of polyethylene, 10 parts of modified flame retardant, 4.5 parts of nano silicon dioxide, 3 parts of glass fiber, 2 parts of methyl methacrylate, 3.5 parts of polylactic acid, 6 parts of decabromodiphenylethane, 7.5 parts of chitin, 6 parts of di (2, 3-dichloropropyl) octyl phosphate, 3.5 parts of tri (neopentyl glycol phosphate) methylamine, 2 parts of insulating assistant, 6 parts of vinyl triethoxysilane and 10 parts of hexachlorocyclotriphosphazene.
The modified flame retardant is prepared by the following process: uniformly mixing 10 parts of asphalt, 4.5 parts of polypropylene, 3 parts of potassium persulfate and 3.5 parts of polyaryl phosphate according to parts by weight, heating to 70 ℃, preserving heat for 3 hours to obtain a core, adding 6 parts of silane coupling agent KH-550, 6 parts of kieselguhr, 6 parts of sepiolite powder, 6 parts of nano aluminum hydroxide, 3.5 parts of antimony trioxide, 6 parts of zinc borate and 4 parts of aluminium polyphosphate into the core, uniformly mixing, stirring at the rotating speed of 750r/min for 20 minutes, adjusting the pH value to 4, heating to 70 ℃, preserving heat for 1 hour to form a shell layer on the periphery of the core, washing, drying at 70 ℃ in vacuum to constant weight, and cooling to room temperature to obtain the modified flame retardant.
The insulating assistant is prepared by the following process: 6.3 parts of pine oil, 4.7 parts of boron carbide, 3.3 parts of kapok and 2.4 parts of potassium acetate are uniformly mixed according to the parts by weight, the temperature is raised to 106 ℃, the temperature is kept for 37min, stirring is carried out continuously in the heat preservation process, then 4.7 parts of hydrogen-containing silicone oil and 3.2 parts of bismaleimide are added and uniformly mixed, the temperature is raised to 128 ℃, the temperature is kept for 34min, vacuumizing is carried out for 12min, the temperature is lowered to 82 ℃, 4.6 parts of polyvinyl sulfonic acid and 2.7 parts of epoxy resin are added and uniformly mixed, the temperature is raised to 134 ℃, the temperature is kept for 38min, stirring is carried out at the rotating speed of 745r/min for 2.2h, cooling is carried out to the room temperature, then 4.3 parts of methyl tetrahydrophthalic anhydride is added and uniformly mixed, the temperature is raised to 102 ℃, the temperature is kept for 2.2h, cooling is carried out to the room temperature, 6.3 parts of methyl silicone oil is.
The preparation method of the high-performance electric meter shell material comprises the following steps:
s1, uniformly mixing ethylene propylene rubber, styrene butadiene rubber and ammonium polyphosphate, heating to 125 ℃, preserving heat for 50min, stirring at a rotating speed of 2000r/min for 20min, cooling to room temperature to obtain a base material, adding vinyltriethoxysilane and hexachlorocyclotriphosphazene into the base material, uniformly mixing, heating to 120 ℃, and preserving heat for 15min to obtain a modified base material;
s2, uniformly mixing polyvinyl chloride and fluorocarbon resin, heating to 120 ℃, preserving heat for 30min, then adding chitin, polyethylene, silicon-hydrogen-containing groups, cellulose ether, carbon black N330, glass fiber, sodium silicate, chlorinated paraffin, dimethyl silicone oil, expanded vermiculite, a promoter TMDT, zinc oxide, stearic acid and an anti-aging agent RD, uniformly mixing, stirring at a rotation speed of 950r/min for 1.5h, then continuously heating to 85 ℃, preserving heat for 10min, then adding a modified flame retardant and an insulating auxiliary agent, uniformly mixing, stirring at a rotation speed of 3000r/min for 10min, and cooling to room temperature to obtain a modified material;
s3, heating the modified base material obtained in the step S1 to 120 ℃, preserving heat for 25min, then adding the modified material obtained in the step S2, cooling to 75 ℃, preserving heat for 1.5h, stirring at the rotating speed of 750r/min for 1.5h, and cooling to room temperature to obtain the high-performance electric power meter shell material.
Example 2
The high-performance electric meter shell material comprises the following raw materials in parts by weight: 15 parts of polyvinyl chloride, 8 parts of polyethylene, 9 parts of modified flame retardant, 6 parts of nano silicon dioxide, 1 part of glass fiber, 3 parts of methyl methacrylate, 2 parts of polylactic acid, 8 parts of decabromodiphenylethane, 6 parts of chitin, 9 parts of di (2, 3-dichloropropyl) octyl phosphate, 2 parts of tri (neopentyl glycol phosphate) methylamine, 3 parts of insulating assistant, 4 parts of vinyl triethoxysilane and 12 parts of hexachlorocyclotriphosphazene.
The modified flame retardant is prepared by the following process: uniformly mixing 8-12 parts of asphalt, 3-6 parts of polypropylene, 1-5 parts of potassium persulfate and 2-5 parts of polyaryl phosphate according to parts by weight, heating to 60-80 ℃, preserving heat for 2-4 hours to obtain a core, adding 4-8 parts of silane coupling agent KH-550, 3-9 parts of diatomite, 4-8 parts of sepiolite powder, 3-9 parts of nano aluminum hydroxide, 2-5 parts of antimony trioxide, 4-8 parts of zinc borate and 2-6 parts of aluminum polyphosphate into the core, uniformly mixing, stirring at the rotation speed of 650 plus 850r/min for 10-30 minutes, adjusting the pH value to 3.5-5.0, heating to 65-75 ℃, preserving heat for 0.5-1.5 hours to form a shell layer on the periphery of the core, washing, drying in vacuum at 65-75 ℃ to constant weight, and cooling to room temperature to obtain the modified flame retardant.
The insulating assistant is prepared by the following process: uniformly mixing 4 parts of pine oil, 6 parts of boron carbide, 2 parts of kapok and 4 parts of potassium acetate according to parts by weight, heating to 100 ℃, keeping the temperature for 50min, continuously stirring in the heat preservation process, then adding 3 parts of hydrogen-containing silicone oil and 5 parts of bismaleimide, uniformly mixing, heating to 125 ℃, keeping the temperature for 40min, vacuumizing for 5min, cooling to 90 ℃, adding 2 parts of polyvinyl sulfonic acid and 4 parts of epoxy resin, uniformly mixing, heating to 130 ℃, keeping the temperature for 45min, stirring at the rotation speed of 650r/min for 3h, cooling to room temperature, then adding 3 parts of methyl tetrahydrophthalic anhydride, uniformly mixing, heating to 120 ℃, keeping the temperature for 1h, cooling to room temperature, adding 8 parts of methyl silicone oil, uniformly mixing, stirring at the rotation speed of 650r/min for 40min, evacuating, removing bubbles, and cooling to room temperature to obtain the insulating assistant.
The preparation method of the high-performance electric meter shell material comprises the following steps:
s1, uniformly mixing ethylene propylene rubber, styrene butadiene rubber and ammonium polyphosphate, heating to 120 ℃, preserving heat for 30min, stirring at a rotating speed of 1500r/min for 30min, cooling to room temperature to obtain a base material, adding vinyltriethoxysilane and hexachlorocyclotriphosphazene into the base material, uniformly mixing, heating to 110 ℃, and preserving heat for 20min to obtain a modified base material;
s2, uniformly mixing polyvinyl chloride and fluorocarbon resin, heating to 110 ℃, preserving heat for 40min, then adding chitin, polyethylene, silicon-hydrogen-containing groups, cellulose ether, carbon black N330, glass fiber, sodium silicate, chlorinated paraffin, dimethyl silicone oil, expanded vermiculite, a promoter TMDT, zinc oxide, stearic acid and an anti-aging agent RD, uniformly mixing, stirring at a rotating speed of 850r/min for 2h, then continuously heating to 80 ℃, preserving heat for 15min, then adding a modified flame retardant and an insulating auxiliary agent, uniformly mixing, stirring at a rotating speed of 2500r/min for 15min, and cooling to room temperature to obtain a modified material;
s3, heating the modified base material obtained in the step S1 to 110 ℃, preserving heat for 30min, then adding the modified material obtained in the step S2, cooling to 70 ℃, preserving heat for 2h, stirring at the rotating speed of 650r/min for 2h, and cooling to room temperature to obtain the high-performance electric power meter shell material.
Example 3
The high-performance electric meter shell material comprises the following raw materials in parts by weight: 25 parts of polyvinyl chloride, 4 parts of polyethylene, 12 parts of modified flame retardant, 3 parts of nano silicon dioxide, 5 parts of glass fiber, 1 part of methyl methacrylate, 5 parts of polylactic acid, 4 parts of decabromodiphenylethane, 9 parts of chitin, 3 parts of di (2, 3-dichloropropyl) octyl phosphate, 5 parts of tri (neopentyl glycol phosphate) methylamine, 1 part of insulating assistant, 8 parts of vinyl triethoxysilane and 8 parts of hexachlorocyclotriphosphazene.
The modified flame retardant is prepared by the following process: uniformly mixing 12 parts of asphalt, 3 parts of polypropylene, 5 parts of potassium persulfate and 2 parts of polyaryl phosphate according to parts by weight, heating to 80 ℃, preserving heat for 2 hours to obtain a core, adding 8 parts of silane coupling agent KH-550, 3 parts of kieselguhr, 8 parts of sepiolite powder, 3 parts of nano aluminum hydroxide, 5 parts of antimony trioxide, 4 parts of zinc borate and 6 parts of aluminum polyphosphate into the core, uniformly mixing, stirring at the rotating speed of 650r/min for 30 minutes, adjusting the pH value to 3.5, heating to 75 ℃, preserving heat for 0.5 hour to form a shell layer on the periphery of the core, washing, drying at 75 ℃ in vacuum to constant weight, and cooling to room temperature to obtain the modified flame retardant.
The insulating assistant is prepared by the following process: uniformly mixing 7 parts of pine oil, 3 parts of boron carbide, 5 parts of kapok and 1 part of potassium acetate according to parts by weight, heating to 110 ℃, preserving heat for 20min, continuously stirring in the heat preservation process, then adding 6 parts of hydrogen-containing silicone oil and 1 part of bismaleimide, uniformly mixing, heating to 135 ℃, preserving heat for 20min, vacuumizing for 15min, cooling to 70 ℃, adding 6 parts of polyvinyl sulfonic acid and 1 part of epoxy resin, uniformly mixing, heating to 140 ℃, preserving heat for 25min, stirring at the rotating speed of 850r/min for 1h, cooling to room temperature, then adding 5 parts of methyl tetrahydrophthalic anhydride, uniformly mixing, heating to 80 ℃, preserving heat for 3h, cooling to room temperature, adding 4 parts of methyl silicone oil, uniformly mixing, stirring at the rotating speed of 850r/min for 20min, evacuating, removing bubbles, and cooling to room temperature to obtain the insulating assistant.
The preparation method of the high-performance electric meter shell material comprises the following steps:
s1, uniformly mixing ethylene propylene rubber, styrene butadiene rubber and ammonium polyphosphate, heating to 130 ℃, preserving heat for 10min, stirring at the rotating speed of 2500r/min for 10min, cooling to room temperature to obtain a base material, adding vinyltriethoxysilane and hexachlorocyclotriphosphazene into the base material, uniformly mixing, heating to 130 ℃, and preserving heat for 10min to obtain a modified base material;
s2, uniformly mixing polyvinyl chloride and fluorocarbon resin, heating to 130 ℃, preserving heat for 20min, then adding chitin, polyethylene, silicon-hydrogen-containing groups, cellulose ether, carbon black N330, glass fiber, sodium silicate, chlorinated paraffin, dimethyl silicone oil, expanded vermiculite, a promoter TMDT, zinc oxide, stearic acid and an anti-aging agent RD, uniformly mixing, stirring at the rotating speed of 1050r/min for 1h, then continuously heating to 90 ℃, preserving heat for 5min, then adding a modified flame retardant and an insulating auxiliary agent, uniformly mixing, stirring at the rotating speed of 3500r/min for 5min, and cooling to room temperature to obtain a modified material;
s3, heating the modified base material obtained in the step S1 to 130 ℃, preserving heat for 20min, then adding the modified material obtained in the step S2, cooling to 80 ℃, preserving heat for 1h, stirring at the rotating speed of 850r/min for 1h, and cooling to room temperature to obtain the high-performance electric power meter shell material.
Comparative example 1
The preparation process is basically the same as that of example 1, except that the raw materials for preparing the high-performance electric power meter shell material lack polyvinyl chloride, chitin, polyethylene, modified flame retardant and insulating auxiliary agent.
Comparative example 2
The same procedure as in example 1 was followed, except that polyvinyl chloride was absent from the raw materials for preparing the high-performance electricity meter case material.
Comparative example 3
The preparation process is basically the same as that of example 1, except that chitin is absent in the raw materials for preparing the high-performance electric meter shell material.
Comparative example 4
The same procedure as in example 1 was followed, except that polyethylene was absent from the raw materials used to prepare the high performance electricity meter housing material.
Comparative example 5
The preparation process was substantially the same as that of example 1, except that the modified flame retardant was absent from the raw materials for preparing the high-performance electricity meter housing material.
Comparative example 6
The same procedure as in example 1 was followed, except that the insulating assistant was absent from the raw materials for preparing the high-performance electricity meter case material.
Comparative example 7
The high-performance electric power meter shell material is prepared by adopting the method described in the specific example 1 in Chinese patent application document 'an electric power meter shell material (publication number: CN 104479255A)'.
Comparative example 8
The preparation process is basically the same as that of the example 1, except that the raw materials for preparing the high-performance electric power meter shell material comprise 14 parts of polyvinyl chloride, 10 parts of chitin, 3 parts of polyethylene, 13 parts of modified flame retardant and 0.8 part of insulating assistant.
Comparative example 9
The preparation process is basically the same as that of the example 1, except that the raw materials for preparing the high-performance electric power meter shell material comprise 26 parts of polyvinyl chloride, 5 parts of chitin, 9 parts of polyethylene, 7 parts of modified flame retardant and 0.9 part of insulating assistant.
Comparative example 10
The preparation process is basically the same as that of the example 1, except that the raw materials for preparing the high-performance electric power meter shell material comprise 27 parts of polyvinyl chloride, 10 parts of chitin, 3 parts of polyethylene, 8 parts of modified flame retardant and 5 parts of insulating auxiliary agent.
The products obtained in examples 1 to 3 and comparative examples 1 to 10 were subjected to a fire resistance test in accordance with UL94 standard and a high temperature compressive strength in accordance with YB/T5201 standard, and the results are shown in the following tables.
| Experimental project | UL94 fire resistance | High temperature compressive strength/MPa | Volume resistivity Ω × cm × 1014 |
| Example 1 | V-0 | 265 | 6.8 |
| Example 2 | V-0 | 263 | 6.6 |
| Example 3 | V-0 | 259 | 6.7 |
| Comparative example 1 | V-3 | 136 | 3.2 |
| Comparative example 2 | V-1 | 256 | 5.8 |
| Comparative example 3 | V-1 | 252 | 5.6 |
| Comparative example 4 | V-2 | 248 | 5.5 |
| Comparative example 5 | V-1 | 238 | 5.4 |
| Comparative example 6 | V-2 | 243 | 5.3 |
| Comparative example 7 | V-6 | 103 | 2.3 |
| Comparative example 8 | V-2 | 145 | 3.4 |
| Comparative example 9 | V-3 | 146 | 3.6 |
| Comparative example 10 | V-3 | 142 | 3.7 |
From the above table, it can be seen that:
(1) as can be seen from the data of examples 1 to 3 and comparative example 7, the fire resistance of the high performance electricity meter case material prepared in examples 1 to 3 is significantly higher than that of the electricity meter case material prepared in comparative example 7; meanwhile, as can be seen from the data of examples 1 to 3, example 1 is the most preferred example.
(2) As can be seen from the data of the example 1 and the comparative examples 1 to 6, the polyvinyl chloride, the chitin, the polyethylene, the modified flame retardant and the insulating assistant play a synergistic role in preparing the high-performance electric power meter shell material, and the fire resistance of the high-performance electric power meter shell material is synergistically improved; this is:
polyvinyl chloride, chitin, polyethylene, a modified flame retardant and an insulating auxiliary agent are used as a reinforcing system, polyvinyl chloride is used as a basic electric meter shell material, chitin and polyethylene are used as fire-resistant fillers, the surfaces of the chitin and the polyethylene contain a large number of hydroxyl groups, and the hydroxyl groups can be connected with unsaturated bonds on the surface of the polyvinyl chloride under the connecting action of the insulating auxiliary agent, so that the chitin and the polyethylene surround the polyvinyl chloride, the surface area of the polyvinyl chloride is increased, more contact areas are obtained when the basic electric meter shell material is used, the fire resistance of the polyvinyl chloride is reinforced by the fire-resistant fillers wrapped outside the polyvinyl chloride, and the fire resistance of the polyvinyl chloride is effectively improved, wherein the organic modified montmorillonite has a good barrier effect, and alkyl ammonium salts contained in the organic modified montmorillonite are subjected to Hofmann degradation when being heated, the acidic points with catalytic activity are formed, the formation of the carbon layer is promoted, the formation of the carbon layer can provide more cross-linked spaces for polyethylene, the polyethylene is connected to polyvinyl chloride in a cross-linked mode, after more polyethylene is obtained from unsaturated bonds on the periphery of the polyvinyl chloride, the polyethylene can well play a role in isolating oxygen, the fire resistance of the polyvinyl chloride is further effectively improved, chitin and a modified fire retardant which have fire resistance are matched, and the chitin and the modified fire retardant are distributed on all parts on the periphery of the polyvinyl chloride under the connecting effect of an insulating assistant, so that all positions on the surface of the polyvinyl chloride have strong fire resistance.
The added modified flame retardant takes the asphalt and the polyaryl phosphate as raw materials, takes potassium persulfate as an initiator to prepare a core, and then takes a silane coupling agent KH-550 as a connecting intermediate between the core and a shell layer to realize that the diatomite, the sepiolite powder, the nano aluminum hydroxide, the antimony trioxide, the zinc borate and the aluminum polyphosphate are connected to the periphery of the core through the silane coupling agent KH-550 to form the shell layer, because the diatomite, the sepiolite powder, the nano aluminum hydroxide, the antimony trioxide, the zinc borate and the aluminum polyphosphate are all refractory fillers, on one hand, the modified granulated flame retardant is endowed with good flame retardant effect on the periphery of the core, and simultaneously, the prepared modified granulated flame retardant is formed due to the formation of the core shell, the surface area of the granulated modified flame retardant is smaller, in a reinforcing system, the insulating assistant can further connect the modified flame retardant to the periphery of polyvinyl chloride, the granulation modified flame retardant with smaller surface area can be more uniformly distributed on the outer surface of the polyvinyl chloride, so that the polyvinyl chloride forms a grid structure, the chitin and the polyethylene can be connected to the polyvinyl chloride by the insulating auxiliary agent in the grid structure, and the reinforcement of the flame retardant property of the polyvinyl chloride is effectively realized under the combined action of the modified flame retardant, the chitin and the polyethylene.
Meanwhile, the silane coupling agent KH-550 is migrated to the surface of the fire-resistant monomer main material after being heated to form a high molecular gradient material, so that an inorganic heat insulation protective layer with Si-C and Si-O bonds is generated, and KH-550 can be connected between hydroxyl on the surface of the fire-resistant filler and the fire-resistant monomer main material, so that the diatomite, the aluminum polyphosphate, the sepiolite powder, the nano aluminum hydroxide, the antimony trioxide and the zinc borate are wrapped on the periphery of the fire-resistant monomer main material, and the fire resistance of the monomer main material is further improved by the fire resistance of the fire-resistant filler.
In addition, the added insulating auxiliary agent is obtained by uniformly mixing pine oil, boron carbide, kapok and potassium acetate, heating, preserving heat and continuously stirring in the heat preservation process, then adding hydrogen-containing silicone oil and bismaleimide to be uniformly mixed, heating, preserving heat, vacuumizing, cooling, adding polyvinyl sulfonic acid and epoxy resin to be uniformly mixed, heating, preserving heat, stirring, cooling to room temperature, then adding methyl tetrahydrophthalic anhydride to be uniformly mixed, heating, preserving heat, cooling to room temperature, adding methyl silicone oil to be uniformly mixed, stirring, evacuating, defoaming and cooling to room temperature, wherein the epoxy resin is used as a base resin, polyvinyl sulfonic acid, hydrogen-containing silicone oil and bismaleimide are used as organic modifying auxiliary agents, pine oil, boron carbide, kapok and potassium acetate are used as insulating fillers, the surface of the insulating fillers is modified by the organic modifying auxiliary agents, and the combination of hydroxyl on the surface of the insulating fillers and unsaturated bonds of the organic modifying auxiliary agents is realized, and the curing effect of the methyl tetrahydrophthalic anhydride is applied to the preparation of the insulating electricity meter shell material, so that the excellent insulating property of the pine oil, the boron carbide, the kapok and the potassium acetate insulating filler is reinforced in the electricity meter shell material, and the reinforcing effect on the insulating property of the electricity meter shell material is realized.
(3) As can be seen from the data of comparative examples 8-10, the weight ratio of polyvinyl chloride, chitin, polyethylene, modified flame retardant, and insulating aid is not (15-25): (6-9): (4-8): (9-12): (1-3), the fire resistance value of the obtained electricity meter case material is very different from that of examples 1-3, much smaller than that of examples 1-3, and not much different from that of the prior art (comparative example 7). In the embodiments 1 to 3 of the invention, when the high-performance electric power meter shell material is prepared, the weight ratio of polyvinyl chloride, chitin, polyethylene, modified flame retardant and insulating auxiliary agent is controlled to be (15-25): (6-9): (4-8): (9-12): and (1-3) the polyvinyl chloride is used as the main raw material of a reinforcing system, the chitin, the polyethylene and the modified flame retardant are used as the fire-resistant reinforcing auxiliary agent, and under the connection action of the insulating auxiliary agent, the hydroxyl on the surface of the fire-resistant reinforcing auxiliary agent is combined with the unsaturated bond on the surface of the main material polyvinyl chloride, so that the fire resistance of the chitin, the polyethylene and the modified flame retardant is fully utilized, and the fire resistance reinforcement of the polyvinyl chloride is realized.
(4) By adding vinyl triethoxysilane and hexachlorocyclotriphosphazene into the base material, the vinyl triethoxysilane contains organic silicon functional groups, and the organic silicon functional groups on the vinyl triethoxysilane replace chlorine atoms in the vinyl triethoxysilane, the abundant silicon elements can be utilized to reduce the amount of phosphorus and nitrogen in the flame retardant in the process of preparing the base material, so that the fire resistance of the shell material of the electric meter is improved.
The above description should not be taken as limiting the invention to the embodiments, but rather, as will be apparent to those skilled in the art to which the invention pertains, numerous simplifications or substitutions may be made without departing from the spirit of the invention, which shall be deemed to fall within the scope of the invention as defined by the claims appended hereto.
Claims (6)
1. The high-performance electric meter shell material is characterized by comprising the following raw materials: polyvinyl chloride, polyethylene, a modified flame retardant, nano silicon dioxide, glass fiber, methyl methacrylate, polylactic acid, decabromodiphenylethane, chitin, di (2, 3-dichloropropyl) octyl phosphate, tri (neopentyl glycol phosphate) methylamine, an insulating assistant, vinyl triethoxysilane and hexachlorocyclotriphosphazene;
the modified flame retardant comprises the following raw materials in parts by weight: 8-12 parts of asphalt, 1-5 parts of potassium persulfate, 2-5 parts of polyaryl phosphate, 3-6 parts of polypropylene, 4-8 parts of silane coupling agent KH-550, 3-9 parts of kieselguhr, 2-6 parts of aluminum polyphosphate, 4-8 parts of sepiolite powder, 3-9 parts of nano aluminum hydroxide, 2-5 parts of antimony trioxide and 4-8 parts of zinc borate;
the insulating auxiliary agent comprises the following raw materials in parts by weight: 4-7 parts of pine oil, 3-6 parts of boron carbide, 2-5 parts of kapok, 1-4 parts of potassium acetate, 3-6 parts of hydrogen-containing silicone oil, 1-5 parts of bismaleimide, 2-6 parts of polyvinyl sulfonic acid, 1-4 parts of epoxy resin, 3-5 parts of methyl tetrahydrophthalic anhydride and 4-8 parts of methyl silicone oil;
the weight ratio of the polyvinyl chloride, the chitin, the polyethylene, the modified flame retardant and the insulating auxiliary agent is (15-25): (6-9): (4-8): (9-12): (1-3).
2. The high-performance electric meter shell material as recited in claim 1, wherein the weight ratio of the polyvinyl chloride, the chitin, the polyethylene, the modified flame retardant and the insulating assistant is 21.3: 7.2: 5.8: 10.8: 2.3.
3. the high-performance electric meter shell material as claimed in claim 1, which is characterized by comprising the following raw materials in parts by weight: 15-25 parts of polyvinyl chloride, 4-8 parts of polyethylene, 9-12 parts of modified flame retardant, 3-6 parts of nano silicon dioxide, 1-5 parts of glass fiber, 1-3 parts of methyl methacrylate, 2-5 parts of polylactic acid, 4-8 parts of decabromodiphenylethane, 6-9 parts of chitin, 3-9 parts of di (2, 3-dichloropropyl) octyl phosphate, 2-5 parts of tri (neopentyl glycol phosphate) methylamine, 1-3 parts of insulating assistant, 4-8 parts of vinyl triethoxysilane and 8-12 parts of hexachlorocyclotriphosphazene.
4. The high-performance electric power meter shell material as recited in claim 1, wherein the modified flame retardant is prepared by the following process: uniformly mixing the asphalt, the polypropylene, the potassium persulfate and the polyaryl phosphate, heating to 60-80 ℃, keeping the temperature for 2-4h to obtain a core, adding a silane coupling agent KH-550, the kieselguhr, the sepiolite powder, the nano aluminum hydroxide, the antimony trioxide, the zinc borate and the aluminum polyphosphate into the core, uniformly mixing, stirring at the rotation speed of 650 plus 850r/min for 10-30min, adjusting the pH to 3.5-5.0, heating to 65-75 ℃, keeping the temperature for 0.5-1.5h to form a shell layer on the periphery of the core, washing, drying in vacuum at 65-75 ℃ to constant weight, and cooling to room temperature to obtain the modified flame retardant.
5. The high-performance electric power meter shell material as recited in claim 1, wherein the insulating aid is prepared by the following process: mixing oleum Pini, boron carbide, kapok and potassium acetate uniformly, heating to 100-, then adding hydrogen-containing silicone oil and bismaleimide, mixing uniformly, heating to 135 ℃ at 125-, then adding methyl tetrahydrophthalic anhydride, mixing uniformly, heating to 80-120 ℃, preserving heat for 1-3h, cooling to room temperature, adding methyl silicone oil, mixing uniformly, stirring at the rotating speed of 650 plus 850r/min for 20-40min, evacuating, removing bubbles, and cooling to room temperature to obtain the insulating assistant.
6. A method for preparing a high performance electric power meter casing material according to any of claims 1-5, characterized in that it comprises the following steps:
s1, uniformly mixing ethylene propylene rubber, styrene butadiene rubber and ammonium polyphosphate, heating to 120-;
s2, uniformly mixing polyvinyl chloride and fluorocarbon resin, heating to 110-130 ℃, preserving heat for 20-40min, adding chitin, polyethylene, silicon-hydrogen-containing group, cellulose ether, carbon black N330, glass fiber, sodium silicate, chlorinated paraffin, dimethyl silicone oil, expanded vermiculite, a promoter TMDT, zinc oxide, stearic acid and an anti-aging agent RD, uniformly mixing, stirring at the rotating speed of 850-1050r/min for 1-2h, continuously heating to 80-90 ℃, preserving heat for 5-15min, adding a modified flame retardant and an insulating assistant, uniformly mixing, stirring at the rotating speed of 2500-3500r/min for 5-15min, and cooling to room temperature to obtain a modified material;
s3, heating the base material obtained in the step S1 to 110-.
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| CN114874549A (en) * | 2022-06-14 | 2022-08-09 | 秦建涛 | Universal meter pincer-type meter shell material and preparation method thereof |
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