CN106566241A - Insulation flame-retardant glass fiber reinforced PA66/PPS/PES power fitting material and preparation method thereof - Google Patents

Insulation flame-retardant glass fiber reinforced PA66/PPS/PES power fitting material and preparation method thereof Download PDF

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CN106566241A
CN106566241A CN201610960875.5A CN201610960875A CN106566241A CN 106566241 A CN106566241 A CN 106566241A CN 201610960875 A CN201610960875 A CN 201610960875A CN 106566241 A CN106566241 A CN 106566241A
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glass fiber
pps
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flame
dried
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余炜
马世虎
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Maanshan Huaneng Electric Power Line Accessories Co Ltd
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Maanshan Huaneng Electric Power Line Accessories Co Ltd
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    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
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    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
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    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers

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Abstract

The invention discloses an insulation flame-retardant glass fiber reinforced PA66/PPS/PES power fitting material and a preparation process thereof, wherein PA66, glass fibre, melamine cyanurate, zinc borate, aluminum hypophosphite, bamboo charcoal, carbon fibre, silicon rubber, waterborne polyurethane, maleic anhydride grafted polypropylene, bovine serum albumin solution, potassium hexatitanate whisker, graphene oxide, a multiwalled carbon nanotube, polyphenylene sulfide, polyether sulfone, hydroxy acrylic resin, tripoli, aliphatic polyisocyanate and the like are used as raw materials. Melamine cyanurate is coated by zinc borate, so that a composite flame retardant is obtained; the surface of the glass fibre is modified by bovine serum albumin; a glass fibre composite material coated by graphite oxide is prepared by utilization of an electrostatic adsorption principle; a tripoli-containing acrylate polyurethane composite coating is prepared; the tripoli-containing acrylate polyurethane composite coating is coated on the PA66, so that a coating is formed; better corrosion resistance and good mechanical property can be realized; and thus, the insulation flame-retardant glass fiber reinforced PA66/PPS/PES power fitting material is obtained.

Description

A kind of flame-resistant insulation type glass fiber reinforced PA66/PPS/PES electric armour clamps material and its system Preparation Method
Technical field
The present invention relates to electric armour clamp Material Field, and in particular to a kind of flame-resistant insulation type glass fiber reinforced PA66/PPS/PES Electric armour clamp material, and its preparation technology.
Background technology
Gold utensil is the vitals during power transmission, for the purpose of energy-saving and emission-reduction, develops new easy processing, recyclable Plastics electric armour clamp material there is important practical significance.Glass fiber reinforced PA66 composite has good mechanical performance, ratio Little, electrical insulation capability is superior and many merits such as easy processing molding for weight, but in view of gold utensil is used for outdoor high-altitude, use environment is disliked It is bad, and nylon is degradable in the presence of long-term water, illumination and heat.
Chao Fen is in paper《The preparation and performance study of novel plastic electric armour clamp material》In, make functional agglomerate by oneself, improve The long-term resistant to hydrolysis of glass fiber reinforced PA66 material and ageing-resistant performance, so as to obtain the novel plastic electric power for meeting use requirement Gold utensil material.PA66 and other auxiliary agents are added to be sufficiently mixed in homogenizer by different proportion respectively and obtains premix material, will Premix material and glass from the main charge door and side loading mouth blanking extruding pelletization of double screw extruder, are subsequently put on particle respectively 4h is dried in 120 DEG C in baking oven, then sample is injected into injection machine.But the material weatherability for obtaining is not enough, and does not possess Fire resistance.
The present invention with hypo-aluminum orthophosphate as fire retardant, with bamboo charcoal as synergist, using Firebrake ZB to melamine cyanurate Coated, obtained composite flame-retardant agent；With maleic anhydride inoculated polypropylene as bulking agent, the silicone rubber with nucleocapsid structure is as toughness reinforcing Agent, fibre reinforced PA66 has excellent mechanical property, self lubricity and electric conductivity；With bovine serum albumin modified glass Fiber surface, using electrostatic absorption principle the glass fiber compound material of graphite oxide cladding is prepared；Multi-walled carbon nano-tubes plus Enter to improve the mechanical property and vitrification point of PA66 fibers；The acroleic acid polyurethane composite coating containing tripoli is prepared for, It is sprayed on PA66 and forms coating, with more preferable corrosion resistance, good mechanical property；Obtain a kind of flame-resistant insulation type glass Reinforced plastic PA66/PPS/PES electric armour clamp materials.
The content of the invention
The invention mainly solves the technical problem of providing a kind of flame-resistant insulation type glass fiber reinforced PA66/PPS/PES electric power Gold utensil material and its preparation technology, the electric armour clamp material made according to the technique has light weight, weather-proof, fire-retardant, insulation excellent Benign energy.
The technical problem to be solved is realized using following technical scheme：
PA66 30-39, glass fibre 15-24, melamine cyanurate 3-6, Firebrake ZB 2-5, hypophosphorous acid
Aluminum 2-5, bamboo charcoal 1-3, carbon fiber 4-7, silicone rubber 2-5, aqueous polyurethane 1-3, maleic anhydride inoculated polypropylene 2-4, cattle Serum albumin solution 1-3, crystal whisker of hexa potassium titanate 1-3, graphene oxide 1-2, multi-walled carbon nano-tubes 2-5, polyphenylene sulfide 2-4, Polyether sulfone 3-4, ethylene-acrylate-glycidyl methacrylate copolymer 1-2, Hydroxylated acrylic resin 2-4, tripoli 1-3, aliphatic polymeric isocyanate 1-2, NaOH solution, NH4HCO3, acetone, HCl solution, appropriate dimethylbenzene.
A kind of preparation method of flame-resistant insulation type glass fiber reinforced PA66/PPS/PES electric armour clamp materials, it is characterised in that Carry out according to the following steps：
A. add NaOH solution in melamine cyanurate, stir, add Firebrake ZB, 60-90 DEG C of reaction 1- of intensification 2h, obtains thick white product, and sucking filtration, washing 3-5 time are dried 1-2h in 110-160 DEG C；By hypo-aluminum orthophosphate, bamboo charcoal in 100-140 DEG C drying 1-2h after, mix with the former, superfine grinding obtains composite flame-retardant agent；
B. carbon fiber is placed in desizing furnace, under nitrogen protection, high temperature desizing process is carried out in 400-600 DEG C, be subsequently placed in Electrolyte NH4HCO3In, be electrolysed 90-150s at 50-90 DEG C, wash 3-5 time, 90-130 DEG C is dried 1-2h, then with silicone rubber, water Property polyurethane mixing；Maleic anhydride inoculated polypropylene is dried after 1-2 h in 70-90 DEG C of vacuum drying oven, is mixed with the former Ball milling 1-2h is stand-by；
C. by glass fibre, in acetone soaking and washing processes 0.5-1h, and hydroxylating processes 1-2h in HCl solution, washes 3-5 Secondary, the submergence 0.5-1h in bovine serum albumin solution is washed 3-5 time, adds dividing for crystal whisker of hexa potassium titanate and graphene oxide Dispersion liquid, uniform stirring, ultrasonic disperse adjusts pH value of solution 3-6, stands 0.5-1h, rinses 3-5 time, and 60-90 DEG C of drying obtains Graphene The glass fiber compound material of cladding；
D. PA66 is dried into 1-2h in 70-90 DEG C of vacuum drying oven, with multi-walled carbon nano-tubes, polyphenylene sulfide, polyether sulfone, second Resulting material is added and is sufficiently mixed in homogenizer in alkene-acrylate-glycidyl ester copolymer and a, b Premix material, by the main charge door respectively from double screw extruder of resulting material in premix material and c and side loading mouth blanking, in 250-290 DEG C of extruding pelletization, particle is subsequently put in baking oven and be dried 2-4h in 110-130 DEG C, then with injection machine in 280- 310 DEG C are injected into sample；
E. Hydroxylated acrylic resin 10: 3-5 is added in dimethylbenzene, adds tripoli under high speed dispersion condition, ball milling 1-2h, with Aliphatic polymeric isocyanate mix homogeneously, using the resulting surface of material prepares coating in d of aerial spraying mode, room temperature is dried in the air It is dry, obtain final product a kind of flame-resistant insulation type glass fiber reinforced PA66/PPS/PES electric armour clamp materials.
The present invention reaction mechanism and have the beneficial effect that：
（1）Hypo-aluminum orthophosphate (AHP) has the advantages that phosphorus content height, good flame retardation effect, and the addition of synergist bamboo charcoal can promote AHP Degraded generates phosphoric acid and pyrophosphoric acid, and in solid phase, phosphoric acid and pyrophosphoric acid can promote PA66 to be degraded into charcoal, and produce after degrading Fine and close layer of charcoal can prevent oxygen and heat transfer to inside polymeric matrix, be conducive to improving the fire resistance of material；Tripolycyanamide Cyanurate (MCA) is a kind of typical nitrogen system bittern-free fire retardant, and odorless, tasteless, decomposition temperature is high, low-smoke low-toxicity, using boric acid Zinc is controlled to MCA, makes Firebrake ZB dispersed deposition on MCA surfaces, and MCA is coated, and is separated into less independent reaction System so that the viscosity of reaction system remains at a relatively low level.
（2）Fibre reinforced PA66 has excellent mechanical property, self lubricity and electric conductivity, first carries out on carbon fiber Electrochemical surface treatment, introduces active group such as-C-OH and-COOH, then with aqueous polyurethane to carbon in carbon fiber surface Fiber carries out starching process, and more preferable interfacial combined function is possessed with PA66 after process, and prepared composite also possesses more High mechanical property, with maleic anhydride inoculated polypropylene as bulking agent, the silicone rubber with nucleocapsid structure is as toughener.
（3）With bovine serum albumin modified glass-fiber surface, using electrostatic absorption principle graphite oxide cladding is prepared Glass fiber compound material, with excellent flexible and heat stability.Crystal whisker of hexa potassium titanate hardness is low, it is not easy to wear to flour milling, The compatibility with organic polymer matrix is projected, the good dispersion in polymeric matrix.
（4）The addition of multi-walled carbon nano-tubes improves the mechanical property and vitrification point of PA66 fibers；Tripoli has micro- Rice-shaped silicon oxide and the kaolinic combinative structure of nano-sheet, advantageously improve permeability resistance and mechanical property, are prepared for containing There is the acroleic acid polyurethane composite coating of tripoli, be sprayed on PA66 and form coating, with more preferable corrosion resistance, good power Learn performance.
（5）Polyphenylene sulfide (PPS) has excellent heat stability, chemical resistance, anti-flammability, electrical insulating property etc. excellent Point, polyether sulfone (PES) has excellent heat resistance, physical and mechanical propertiess, insulating properties, resistance to impact etc., with PA66 with PPS, PES carry out blending and modifying, with ethylene-acrylate-glycidyl methacrylate copolymer as compatilizer, composite wood The mechanical property of material, mechanical performance, impact strength are significantly improved.
Specific embodiment
In order that technological means, creation characteristic, reached purpose and effect that the present invention is realized are easy to understand, tie below Specific embodiment is closed, the present invention is expanded on further.
Embodiment
A kind of flame-resistant insulation type glass fiber reinforced PA66/PPS/PES electric armour clamp materials, by the raw material of following weight parts (g) It is obtained：
PA66 39, glass fibre 15, melamine cyanurate 3, Firebrake ZB 2, hypo-aluminum orthophosphate 2, bamboo charcoal 1, carbon fiber 4, silicon rubber Glue 2, aqueous polyurethane 3, maleic anhydride inoculated polypropylene 4, bovine serum albumin solution 1, crystal whisker of hexa potassium titanate 1, graphite oxide Alkene 2, multi-walled carbon nano-tubes 5, polyphenylene sulfide 4, polyether sulfone 4, ethylene-acrylate-glycidyl methacrylate copolymer 1, Hydroxylated acrylic resin 2, tripoli 1, aliphatic polymeric isocyanate 1, NaOH solution, NH4HCO3, acetone, HCl solution, dimethylbenzene In right amount.
A kind of preparation method of flame-resistant insulation type glass fiber reinforced PA66/PPS/PES electric armour clamp materials, it is characterised in that Carry out according to the following steps：
A. add NaOH solution in melamine cyanurate, stir, add Firebrake ZB, heat up 80 DEG C of reaction 1h, obtains white Color viscous product, sucking filtration, washing 3 times, in 130 DEG C 1h is dried；It is mixed with the former after hypo-aluminum orthophosphate, bamboo charcoal are dried into 1h at 120 DEG C Close, superfine grinding obtains composite flame-retardant agent；
B. carbon fiber is placed in desizing furnace, under nitrogen protection, high temperature desizing process is carried out in 550 DEG C, be subsequently placed in electrolysis Liquid NH4HCO3In, 150s is electrolysed at 70 DEG C, wash 3 times, 120-130 DEG C is dried 1h, then mixes with silicone rubber, aqueous polyurethane； It is stand-by with the former mixing and ball milling 1h after maleic anhydride inoculated polypropylene is dried into 1h in 80-90 DEG C of vacuum drying oven；
C. by glass fibre, in acetone soaking and washing processes 0.5h, and hydroxylating processes 1h in HCl solution, washes 3 times, Submergence 0.5h in bovine serum albumin solution, washes 3 times, adds the dispersion liquid of crystal whisker of hexa potassium titanate and graphene oxide, uniformly Stirring, ultrasonic disperse adjusts pH value of solution 5, stands 0.5h, rinses 3 times, and 80-90 DEG C of drying obtains the glass fibre of graphene coated Composite；
D., PA66 is dried in 70-80 DEG C of vacuum drying oven 1h, with multi-walled carbon nano-tubes, polyphenylene sulfide, polyether sulfone, ethylene- Resulting material is added and is sufficiently mixed in homogenizer in acrylate-glycidyl ester copolymer and a, b Premix material, by the main charge door respectively from double screw extruder of resulting material in premix material and c and side loading mouth blanking, in 270- 290 DEG C of extruding pelletizations, particle is subsequently put in baking oven be dried 2h in 110-130 DEG C, then with injection machine in 290-310 DEG C of note Penetrate into sample；
E. Hydroxylated acrylic resin 10: 3 is added in dimethylbenzene, tripoli, ball milling 1h, with fat is added under high speed dispersion condition Adoption isocyanates mix homogeneously, using the resulting surface of material prepares coating in d of aerial spraying mode, room temperature is dried, Obtain final product a kind of flame-resistant insulation type glass fiber reinforced PA66/PPS/PES electric armour clamp materials.
A kind of performance of flame-resistant insulation type glass fiber reinforced PA66/PPS/PES electric armour clamp materials prepared by above-described embodiment Testing result is as follows：
Jing hydrolytic resistances（Ethylene glycol, 135 DEG C, 48h）After test, tensile strength rate of change is 42%, and bending strength rate of change is 40%, impact strength rate of change is 134%, and weight rate is 12%；Bending property loss rate ＜ 50%, meets use requirement；
Jing heat ageings（150 DEG C, 2000h）Test, tensile strength rate of change is 14%, and bending strength rate of change is 12%, and impact is strong Degree rate of change is 10%, meets the requirement of loss rate ＜ 25%；
Jing photoaging（2000h）Test, tensile strength rate of change is 19%, and bending strength rate of change is 15%, impact strength change Rate is 9%, meets the requirement of loss rate ＜ 30%.

Claims (2)

1. a kind of flame-resistant insulation type glass fiber reinforced PA66/PPS/PES electric armour clamp materials, it is characterised in that by following weight parts Raw material be obtained：
PA66 30-39, glass fibre 15-24, melamine cyanurate 3-6, Firebrake ZB 2-5, hypophosphorous acid
Aluminum 2-5, bamboo charcoal 1-3, carbon fiber 4-7, silicone rubber 2-5, aqueous polyurethane 1-3, maleic anhydride inoculated polypropylene 2-4, cattle Serum albumin solution 1-3, crystal whisker of hexa potassium titanate 1-3, graphene oxide 1-2, multi-walled carbon nano-tubes 2-5, polyphenylene sulfide 2-4, Polyether sulfone 3-4, ethylene-acrylate-glycidyl methacrylate copolymer 1-2, Hydroxylated acrylic resin 2-4, tripoli 1-3, aliphatic polymeric isocyanate 1-2, NaOH solution, NH4HCO3, acetone, HCl solution, appropriate dimethylbenzene.
2. the preparation of a kind of flame-resistant insulation type glass fiber reinforced PA66/PPS/PES electric armour clamp materials according to claim 1 Method, it is characterised in that carry out according to the following steps：
A. add NaOH solution in melamine cyanurate, stir, add Firebrake ZB, 60-90 DEG C of reaction 1- of intensification 2h, obtains thick white product, and sucking filtration, washing 3-5 time are dried 1-2h in 110-160 DEG C；By hypo-aluminum orthophosphate, bamboo charcoal in 100-140 DEG C drying 1-2h after, mix with the former, superfine grinding obtains composite flame-retardant agent；
B. carbon fiber is placed in desizing furnace, under nitrogen protection, high temperature desizing process is carried out in 400-600 DEG C, be subsequently placed in Electrolyte NH4HCO3In, be electrolysed 90-150s at 50-90 DEG C, wash 3-5 time, 90-130 DEG C is dried 1-2h, then with silicone rubber, water Property polyurethane mixing；Maleic anhydride inoculated polypropylene is dried after 1-2 h in 70-90 DEG C of vacuum drying oven, is mixed with the former Ball milling 1-2h is stand-by；
C. by glass fibre, in acetone soaking and washing processes 0.5-1h, and hydroxylating processes 1-2h in HCl solution, washes 3-5 Secondary, the submergence 0.5-1h in bovine serum albumin solution is washed 3-5 time, adds dividing for crystal whisker of hexa potassium titanate and graphene oxide Dispersion liquid, uniform stirring, ultrasonic disperse adjusts pH value of solution 3-6, stands 0.5-1h, rinses 3-5 time, and 60-90 DEG C of drying obtains Graphene The glass fiber compound material of cladding；
D. PA66 is dried into 1-2h in 70-90 DEG C of vacuum drying oven, with multi-walled carbon nano-tubes, polyphenylene sulfide, polyether sulfone, second Resulting material is added and is sufficiently mixed in homogenizer in alkene-acrylate-glycidyl ester copolymer and a, b Premix material, by the main charge door respectively from double screw extruder of resulting material in premix material and c and side loading mouth blanking, in 250-290 DEG C of extruding pelletization, particle is subsequently put in baking oven and be dried 2-4h in 110-130 DEG C, then with injection machine in 280- 310 DEG C are injected into sample；
E. Hydroxylated acrylic resin 10: 3-5 is added in dimethylbenzene, adds tripoli under high speed dispersion condition, ball milling 1-2h, with Aliphatic polymeric isocyanate mix homogeneously, using the resulting surface of material prepares coating in d of aerial spraying mode, room temperature is dried in the air It is dry, obtain final product a kind of flame-resistant insulation type glass fiber reinforced PA66/PPS/PES electric armour clamp materials.
CN201610960875.5A 2016-11-04 2016-11-04 Insulation flame-retardant glass fiber reinforced PA66/PPS/PES power fitting material and preparation method thereof Pending CN106566241A (en)

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CN110684217A (en) * 2019-10-17 2020-01-14 中山市华洋塑胶颜料有限公司 Ultra-dispersed ceramic white master batch and preparation method and application thereof
CN114133760A (en) * 2021-11-15 2022-03-04 宁国中奕橡塑有限公司 High-temperature corrosion-resistant composite material with excellent mechanical properties and preparation method thereof
CN116675930A (en) * 2023-08-04 2023-09-01 苏州亚通生物医疗科技有限公司 Polypropylene material for PCR (polymerase chain reaction) plate and preparation method thereof
CN117659700A (en) * 2024-01-31 2024-03-08 广州辰东新材料有限公司 Polyphenylene sulfide composite material for integrated explosion-proof device of power battery, and preparation and application thereof
CN117659700B (en) * 2024-01-31 2024-04-30 广州辰东新材料有限公司 Polyphenylene sulfide composite material for integrated explosion-proof device of power battery, and preparation and application thereof

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Application publication date: 20170419