CN106566240A - Antistatic corrosion inhibition type glass-fiber-reinforced PA66 electric power fitting material and preparation method thereof - Google Patents

Antistatic corrosion inhibition type glass-fiber-reinforced PA66 electric power fitting material and preparation method thereof Download PDF

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CN106566240A
CN106566240A CN201610960874.0A CN201610960874A CN106566240A CN 106566240 A CN106566240 A CN 106566240A CN 201610960874 A CN201610960874 A CN 201610960874A CN 106566240 A CN106566240 A CN 106566240A
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corrosion inhibition
dried
inhibition type
type glass
fiber
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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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Abstract

The invention discloses an antistatic corrosion inhibition type glass-fiber-reinforced PA66 electric power fitting material and a preparation process thereof. The antistatic corrosion inhibition type glass-fiber-reinforced PA66 electric power fitting material is characterized in that PA66, glass fibers, melamine cyanurate, zinc borate, aluminium hypophosphite, bamboo charcoal, carbon fibers, silicone rubber, waterborne polyurethane, maleic anhydride grafted polypropylene, a bovine serum albumin solution, potassium hexatitanate whiskers, oxidized graphene, a multiwalled carbon nanotube, sodium dodecyl benzene sulfonate, sodium tungstate, hydroxy acrylic resin, silica, aliphatic polyisocyanate and the like serve as raw materials. According to the material, the zinc borate is adopted to wrap the melamine cyanurate, and composite flame retardant is obtained; bovine serum albumin is utilized to modify the glass fiber surfaces, and a glass fiber composite material wrapped with graphite oxide is prepared through an electrostatic adsorption principle; an acrylate polyurethane composite coating containing the silica is prepared, the composite coating is sprayed on the PA66 to form a paincoat, and better corrosion resistance and good mechanical performance are achieved; and the antistatic corrosion inhibition type glass-fiber-reinforced PA66 electric power fitting material is prepared.

Description

A kind of antistatic corrosion inhibition type glass fiber reinforced PA66 electric armour clamp material and preparation method thereof
Technical field
The present invention relates to electric armour clamp Material Field, and in particular to a kind of antistatic corrosion inhibition type glass fiber reinforced PA66 electric power gold Tool 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；Dodecylbenzene sodium sulfonate (SDBS) It is a kind of small molecule anionic surfactant, sodium tungstate and dodecylbenzene sodium sulfonate have the effect of synergistic slow corrosion, chooses SDBS, with paraffin as adhesive, obtains a kind of antistatic corrosion inhibition type glass fiber reinforced PA66 electric armour clamp material as antistatic additive.
The content of the invention
The invention mainly solves the technical problem of providing a kind of antistatic corrosion inhibition type glass fiber reinforced PA66 electric armour clamp material Material and its preparation technology, the electric armour clamp material made according to the technique have light weight, weather-proof, fire-retardant, antistatic, inhibition it is excellent Benign energy.
The technical problem to be solved is realized using following technical scheme：
PA66 32-40, glass fibre 15-23, melamine cyanurate 3-7, Firebrake ZB 2-5, hypophosphorous acid
Aluminum 2-4, bamboo charcoal 1-3, carbon fiber 4-7, silicone rubber 2-5, aqueous polyurethane 1-4, 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, detergent alkylate sulphur Sour sodium 5-8, paraffin 1-2, sodium tungstate 2-5, Hydroxylated acrylic resin 2-5, tripoli 1-2, aliphatic polymeric isocyanate 1-2, NaOH Solution, NH4HCO3, acetone, HCl solution, appropriate dimethylbenzene.
A kind of preparation method of antistatic corrosion inhibition type glass fiber reinforced PA66 electric armour clamp material, it is characterised in that by following Step is carried out：
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, dodecylbenzene sodium sulfonate, stone Resulting material is added in homogenizer and is sufficiently mixed to obtain premix material in wax, sodium tungstate and a, b, by gains in premix material and c Expect main charge door respectively from double screw extruder and side loading mouth blanking, in 250-280 DEG C of extruding pelletization, subsequently put on particle Enter in baking oven and be dried 2-4h in 110-130 DEG C, be then injected into sample in 260-290 DEG C with injection machine；
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 antistatic corrosion inhibition type glass fiber reinforced PA66 electric armour clamp material.
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）It is a kind of typical nitrogen system bittern-free fire retardant, 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）Dodecylbenzene sodium sulfonate (SDBS) is a kind of small molecule anionic surfactant, and it is in the composite Migration rate is fast, is the antistatic property for improving PA66, chooses SDBS as antistatic additive, with paraffin as adhesive, sodium tungstate With the effect that dodecylbenzene sodium sulfonate has synergistic slow corrosion, composite is prepared for using the method for blending.
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 antistatic corrosion inhibition type glass fiber reinforced PA66 electric armour clamp material, is obtained by the raw material of following weight parts (g)：
PA66 36, glass fibre 20, melamine cyanurate 7, Firebrake ZB 5, hypo-aluminum orthophosphate 2, bamboo charcoal 1, carbon fiber 4, silicon rubber Glue 2, aqueous polyurethane 1, maleic anhydride inoculated polypropylene 4, bovine serum albumin solution 3, crystal whisker of hexa potassium titanate 1, graphite oxide Alkene 2, multi-walled carbon nano-tubes 2, dodecylbenzene sodium sulfonate 8, paraffin 1, sodium tungstate 2, Hydroxylated acrylic resin 2, tripoli 1, fat Adoption isocyanates 2, NaOH solution, NH4HCO3, acetone, HCl solution, appropriate dimethylbenzene.
A kind of preparation method of antistatic corrosion inhibition type glass fiber reinforced PA66 electric armour clamp material, it is characterised in that by following Step is carried out：
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 into 1h in 70-80 DEG C of vacuum drying oven, with multi-walled carbon nano-tubes, dodecylbenzene sodium sulfonate, stone Resulting material is added in homogenizer and is sufficiently mixed to obtain premix material in wax, sodium tungstate and a, b, by gains in premix material and c Expect main charge door respectively from double screw extruder and side loading mouth blanking, in 270-280 DEG C of extruding pelletization, subsequently put on particle Enter in baking oven and be dried 2h in 120-130 DEG C, be then injected into sample in 280-290 DEG C with injection machine；
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 antistatic corrosion inhibition type glass fiber reinforced PA66 electric armour clamp material.
A kind of performance detection knot of antistatic corrosion inhibition type glass fiber reinforced PA66 electric armour clamp material prepared by above-described embodiment It is really as follows：
Jing hydrolytic resistances（Ethylene glycol, 135 DEG C, 48h）After test, tensile strength rate of change is 37%, and bending strength rate of change is 42%, impact strength rate of change is 133%, and weight rate is 11%；Bending property loss rate ＜ 50%, meets use requirement；
Jing heat ageings（150 DEG C, 2000h）Test, tensile strength rate of change is 16%, and bending strength rate of change is 12%, and impact is strong Degree rate of change is 13%, meets the requirement of loss rate ＜ 25%；
Jing photoaging（2000h）Test, tensile strength rate of change is 17%, and bending strength rate of change is 15%, impact strength change Rate is 10%, meets the requirement of loss rate ＜ 30%.

Claims (2)

1. a kind of antistatic corrosion inhibition type glass fiber reinforced PA66 electric armour clamp material, it is characterised in that by the raw material of following weight parts It is obtained：
PA66 32-40, glass fibre 15-23, melamine cyanurate 3-7, Firebrake ZB 2-5, hypophosphorous acid
Aluminum 2-4, bamboo charcoal 1-3, carbon fiber 4-7, silicone rubber 2-5, aqueous polyurethane 1-4, 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, detergent alkylate sulphur Sour sodium 5-8, paraffin 1-2, sodium tungstate 2-5, Hydroxylated acrylic resin 2-5, tripoli 1-2, aliphatic polymeric isocyanate 1-2, NaOH Solution, NH4HCO3, acetone, HCl solution, appropriate dimethylbenzene.
2. the preparation method of a kind of antistatic corrosion inhibition type glass fiber reinforced PA66 electric armour clamp material according to claim 1, Characterized in that, carrying 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, dodecylbenzene sodium sulfonate, stone Resulting material is added in homogenizer and is sufficiently mixed to obtain premix material in wax, sodium tungstate and a, b, by gains in premix material and c Expect main charge door respectively from double screw extruder and side loading mouth blanking, in 250-280 DEG C of extruding pelletization, subsequently put on particle Enter in baking oven and be dried 2-4h in 110-130 DEG C, be then injected into sample in 260-290 DEG C with injection machine；
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 antistatic corrosion inhibition type glass fiber reinforced PA66 electric armour clamp material.
CN201610960874.0A 2016-11-04 2016-11-04 Antistatic corrosion inhibition type glass-fiber-reinforced PA66 electric power fitting material and preparation method thereof Pending CN106566240A (en)

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