CN106497041A - A kind of carbon fiber reinforced flame-resistant insulation type PA66/PP electric armour clamp material and preparation method thereof - Google Patents

Abstract

The invention discloses a kind of carbon fiber reinforced flame-resistant insulation type PA66/PP electric armour clamp material, and its preparation technology, it is characterized in that, with PA66, carbon fiber, glass fibre, polypropylene, melamine cyanurate, Firebrake ZB, hypo-aluminum orthophosphate, bamboo charcoal, silicone rubber, aqueous polyurethane, maleic anhydride inoculated polypropylene, bovine serum albumin solution, crystal whisker of hexa potassium titanate, graphene oxide, multi-walled carbon nano-tubes, epoxy resin, hollow glass micropearl, dibutyl phthalate, dimethicone, polyamide, maleic anhydride is grafted POE, red phosphorus, phenolic resin etc. is raw material.The present invention is coated to melamine cyanurate using Firebrake ZB, obtains composite flame-retardant agent；With bovine serum albumin modified glass-fiber surface, the glass fiber compound material for preparing graphite oxide cladding using electrostatic absorption principle；Fibre reinforced PA66 has excellent mechanical property, self lubricity and electric conductivity；Obtain a kind of carbon fiber reinforced flame-resistant insulation type PA66/PP electric armour clamp material.

Description

A kind of carbon fiber reinforced flame-resistant insulation type PA66/PP electric armour clamp 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 carbon fiber reinforced flame-resistant insulation type PA66/PP 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.Fibre reinforced PA66 has excellent mechanical property, self-lubricating Property and electric conductivity etc., but in view of gold utensil is used for outdoor high-altitude, use environment is severe, and nylon is in long-term water, illumination and warm In the presence of degradable.

Pan Renhang is in its Master's thesis《Carbon fiber surface modification and the research of reinforced PA66 composite》In, first by carbon Fiber carries out electrochemical surface treatment, introduces active group such as-C-OH and-COOH in carbon fiber surface, then using autogamy Polyurethane (PU) sizing agent starching process is carried out to carbon fiber, finally by carbon fiber by extruding pelletization and injection method system For into carbon fiber reinforced nylon 66 (CFRPA66).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 have excellent mechanical property, self lubricity and electric conductivity；With bovine serum albumin modified glass Fiber surface, the glass fiber compound material for preparing graphite oxide cladding using electrostatic absorption principle；Multi-walled carbon nano-tubes plus Enter to improve the mechanical property and vitrification point of PA66 fibers；With red phosphorus as fire retardant, phenolic resin is with the addition of, using melting Blending method is prepared for polypropylene (PP)/polyamide 66 (PA66) blend, with maleic anhydride grafting POE as bulking agent, improves The tensile strength of blend and elongation at break；Obtain a kind of carbon fiber reinforced flame-resistant insulation type PA66/PP electric armour clamp material Material.

Content of the invention

The invention mainly solves the technical problem of providing a kind of carbon fiber reinforced flame-resistant insulation type PA66/PP electric power gold Tool material and its preparation technology, the electric armour clamp material made according to the technique have light weight, weather-proof, fire-retardant premium properties.

The technical problem to be solved is realized using following technical scheme：

PA66 22-30, polypropylene (PP) 10-14, carbon fiber 9-15, glass fibre 5-8, melamine cyanurea

Hydrochlorate 2-4, Firebrake ZB 2-5, hypo-aluminum orthophosphate 2-5, bamboo charcoal 1-3, silicone rubber 2-3, aqueous polyurethane 1-3, maleic anhydride connect Branch polypropylene 2-5, bovine serum albumin solution 1-2, crystal whisker of hexa potassium titanate 2-3, graphene oxide 1-2, epoxy resin 2-5, empty Heart glass microballoon 3-4, dibutyl phthalate 1-3, dimethicone 1-2, polyamide 1-2, maleic anhydride are grafted POE 1- 3, multi-walled carbon nano-tubes 3-6, red phosphorus 3-7, phenolic resin 1-3, antiaging agent MBP 1-2, NaOH solution, NH₄HCO₃, acetone, HCl solution, appropriate.

A kind of preparation method of carbon fiber reinforced flame-resistant insulation type PA66/PP electric armour clamp material, it is characterised in that press Following steps are 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 dry 1-2h in 110-160 DEG C；By hypo-aluminum orthophosphate, bamboo charcoal in 100-140 DEG C dry 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 dries 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, soaking and washing processes 0.5-1h in acetone, and in HCl solution, hydroxylating processes 1-2h, washes 3-5 Secondary, 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 adjust pH value of solution 3-6, stand 0.5-1h, rinse 3-5 time, and 60-90 DEG C of drying obtains Graphene The glass fiber compound material of cladding；

D. epoxy resin is put in 70-90 DEG C of water-bath, adds resulting material in hollow glass micropearl and c, mix 1-2h, It is subsequently adding dibutyl phthalate, dimethicone, polyamide, mixing and stirring, cold curing 1-2h, by maleic acid Acid anhydride grafting POE dries 3-5 h in 75-95 DEG C of vacuum drying oven, stand-by；

E., PA66 is dried in 80-110 DEG C of vacuum drying oven gains in 2-4h, with multi-walled carbon nano-tubes, polypropylene, a, b Material and other surplus stocks are added in homogenizers and are sufficiently mixed to obtain premix material, by resulting material in premix material and d respectively from The main charge door of double screw extruder and side loading mouth blanking, in 240-270 DEG C of extruding pelletization, are subsequently put into particle in baking oven 2-4h is dried in 110-130 DEG C, then sample is injected into injection machine in 250-280 DEG C, obtain final product a kind of carbon fiber reinforced exhausted Edge flame retardant type PA66/PP electric armour clamp materials.

The present invention reaction mechanism and have the beneficial effect that：

（1）There is hypo-aluminum orthophosphate (AHP) phosphorus content height, good flame retardation effect, 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 the fire resistance for improving material；Tripolycyanamide Cyanurate（MCA）It is a kind of typical nitrogen system bittern-free fire retardant, odorless, tasteless, decomposition temperature are high, and low-smoke low-toxicity, using boric acid Zinc is controlled to MCA, makes Firebrake ZB dispersed deposition on MCA surfaces, MCA is coated, be 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 carbon fiber Electrochemical surface treatment, introduces active group such as-C-OH and-COOH in carbon fiber surface, then with aqueous polyurethane to carbon Fiber carries out starching process, has more preferable interfacial combined function after process with PA66, and prepared composite also has 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, graphite oxide cladding is prepared using electrostatic absorption principle Glass fiber compound material, with excellent flexible and heat stability.Crystal whisker of hexa potassium titanate hardness is low, not easy to wear to flour milling, The compatibility with organic polymer matrix is projected, good dispersion in polymeric matrix.

（4）With dibutyl phthalate as plasticizer, with dimethicone as defoamer, with polyamide as firming agent, Based on epoxy resin, packing material is hollow glass micropearl and glass fibre, is prepared for glass fibre/glass microballoon/ring Epoxy resin composite material, have the advantages that lightweight, Gao Biqiang, multifunctionality.

（5）With red phosphorus as fire retardant, phenolic resin is with the addition of, polypropylene (PP)/polyamides is prepared for using melt-blending process Amine 66 (PA66) blend, with good fire resistance, weather resistance be good, stability；With maleic anhydride grafting POE as increasing Hold agent, improve tensile strength and the elongation at break of blend；The addition of multi-walled carbon nano-tubes improves the power of PA66 fibers Learn performance and vitrification point.

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 carbon fiber reinforced flame-resistant insulation type PA66/PP electric armour clamp material, by the raw material system of following weight parts (g) ?：

PA66 26, polypropylene (PP) 14, carbon fiber 9, glass fibre 5, melamine cyanurate 2, boron

Sour zinc 5, hypo-aluminum orthophosphate 2, bamboo charcoal 1, silicone rubber 2, aqueous polyurethane 1, maleic anhydride inoculated polypropylene 2, bovine serum albumin White solution 2, crystal whisker of hexa potassium titanate 3, graphene oxide 1, epoxy resin 5, hollow glass micropearl 4, dibutyl phthalate 3, Dimethicone 1, polyamide 1, maleic anhydride are grafted POE 3, multi-walled carbon nano-tubes 6, red phosphorus 7, phenolic resin 3, antiaging agent MBP 1, NaOH solution, NH₄HCO₃, acetone, HCl solution, appropriate.

A kind of preparation method of carbon fiber reinforced flame-resistant insulation type PA66/PP electric armour clamp material, it is characterised in that press Following steps are carried out：

A. add NaOH solution in melamine cyanurate, stir, add Firebrake ZB, 80-90 DEG C of intensification to react 1h, Thick white product is obtained, sucking filtration, washing 3 times dry 1h in 140-160 DEG C；Hypo-aluminum orthophosphate, bamboo charcoal are dried at 130-140 DEG C After 2h, 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 500-550 DEG C, be subsequently placed in Electrolyte NH₄HCO₃In, be electrolysed 150s at 70-80 DEG C, wash 3 times, 110-120 DEG C dries 1h, then with silicone rubber, the poly- ammonia of aqueouss Ester mixes；Maleic anhydride inoculated polypropylene is dried after 1 h in 80-90 DEG C of vacuum drying oven, is treated with the former mixing and ball milling 1h With；

C. by glass fibre, soaking and washing processes 01h in acetone, and in HCl solution, hydroxylating processes 1h, washes 3 times, in cattle Submergence 1h in serum albumin solution, washes 3 times, the dispersion liquid of addition crystal whisker of hexa potassium titanate and graphene oxide, uniform stirring, Ultrasonic disperse, adjusts pH value of solution 4-5, stands 1h, rinses 3 times, and 70-80 DEG C of drying obtains the glass fibre composite wood of graphene coated Material；

D. epoxy resin is put in 80-90 DEG C of water-bath, adds resulting material in hollow glass micropearl and c, mix 1h, so Dibutyl phthalate, dimethicone, polyamide are added afterwards, maleic anhydride is connect by mixing and stirring, cold curing 2h Branch POE dries 3h in 80-90 DEG C of vacuum drying oven, stand-by；

E., PA66 is dried in 100-110 DEG C of vacuum drying oven gains in 2h, with multi-walled carbon nano-tubes, polypropylene, a, b Material and other surplus stocks are added in homogenizers and are sufficiently mixed to obtain premix material, by resulting material in premix material and d respectively from The main charge door of double screw extruder and side loading mouth blanking, in 250-260 DEG C of extruding pelletization, are subsequently put into particle in baking oven 2h is dried in 110-120 DEG C, then sample is injected into injection machine in 260-270 DEG C, obtain final product a kind of carbon fiber reinforced insulation Flame retardant type PA66/PP electric armour clamp materials.

A kind of performance inspection of carbon fiber reinforced flame-resistant insulation type PA66/PP electric armour clamp material prepared by above-described embodiment Survey result as follows：

Through hydrolytic resistance（Ethylene glycol, 130 DEG C, 50h）After test, tensile strength rate of change is 33%, and bending strength rate of change is 41%, impact strength rate of change is 128%, and weight rate is 14%；Bending property loss rate ＜ 50%, meets use requirement；

Through heat ageing（150 DEG C, 2000h）Test, tensile strength rate of change are 22%, and bending strength rate of change is 17%, and impact is strong Degree rate of change is 13%, meets the requirement of loss rate ＜ 25%；

Through photoaging（2000h）Test, tensile strength rate of change are 21%, and bending strength rate of change is 16%, and impact strength changes Rate is 12%, meets the requirement of loss rate ＜ 30%.

Claims (2)

1. a kind of carbon fiber reinforced flame-resistant insulation type PA66/PP electric armour clamp material, it is characterised in that by following weight parts Raw material is obtained：

PA66 22-30, polypropylene (PP) 10-14, carbon fiber 9-15, glass fibre 5-8, melamine cyanurea

Hydrochlorate 2-4, Firebrake ZB 2-5, hypo-aluminum orthophosphate 2-5, bamboo charcoal 1-3, silicone rubber 2-3, aqueous polyurethane 1-3, maleic anhydride connect Branch polypropylene 2-5, bovine serum albumin solution 1-2, crystal whisker of hexa potassium titanate 2-3, graphene oxide 1-2, epoxy resin 2-5, empty Heart glass microballoon 3-4, dibutyl phthalate 1-3, dimethicone 1-2, polyamide 1-2, maleic anhydride are grafted POE 1- 3, multi-walled carbon nano-tubes 3-6, red phosphorus 3-7, phenolic resin 1-3, antiaging agent MBP 1-2, NaOH solution, NH₄HCO₃, acetone, HCl solution, appropriate.

2. the preparation of a kind of carbon fiber reinforced flame-resistant insulation type PA66/PP electric armour clamp material 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 dry 1-2h in 110-160 DEG C；By hypo-aluminum orthophosphate, bamboo charcoal in 100-140 DEG C dry 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 dries 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, soaking and washing processes 0.5-1h in acetone, and in HCl solution, hydroxylating processes 1-2h, washes 3-5 Secondary, 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 adjust pH value of solution 3-6, stand 0.5-1h, rinse 3-5 time, and 60-90 DEG C of drying obtains Graphene The glass fiber compound material of cladding；

D. epoxy resin is put in 70-90 DEG C of water-bath, adds resulting material in hollow glass micropearl and c, mix 1-2h, It is subsequently adding dibutyl phthalate, dimethicone, polyamide, mixing and stirring, cold curing 1-2h, by maleic acid Acid anhydride grafting POE dries 3-5 h in 75-95 DEG C of vacuum drying oven, stand-by；

E., PA66 is dried in 80-110 DEG C of vacuum drying oven gains in 2-4h, with multi-walled carbon nano-tubes, polypropylene, a, b Material and other surplus stocks are added in homogenizers and are sufficiently mixed to obtain premix material, by resulting material in premix material and d respectively from The main charge door of double screw extruder and side loading mouth blanking, in 240-270 DEG C of extruding pelletization, are subsequently put into particle in baking oven 2-4h is dried in 110-130 DEG C, then sample is injected into injection machine in 250-280 DEG C, obtain final product a kind of carbon fiber reinforced exhausted Edge flame retardant type PA66/PP electric armour clamp materials.