CN108610630A - A kind of preparation method of high temperature dielectric properties pbo fiber composite material - Google Patents

A kind of preparation method of high temperature dielectric properties pbo fiber composite material Download PDF

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CN108610630A
CN108610630A CN201810458322.9A CN201810458322A CN108610630A CN 108610630 A CN108610630 A CN 108610630A CN 201810458322 A CN201810458322 A CN 201810458322A CN 108610630 A CN108610630 A CN 108610630A
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pbo fiber
composite material
pbo
preparation
dielectric properties
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CN108610630B (en
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张春华
王娟
赵蕾
曹莹莹
张麒
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Harbin Institute of Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/06—Inorganic compounds or elements
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/08—Organic compounds
    • D06M10/10—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds

Abstract

A kind of preparation method of high temperature dielectric properties pbo fiber composite material, purpose is to improve composite material interface active force in the case of guarantee pbo fiber cyanate composite material good dielectric properties, solves the problems such as pbo fiber surface is smooth low with resin boundary surface adhesive strength.Preparation method：One, hyperbranched PBO polymer grafting liquid is prepared；Two, the infiltration processing of pbo fiber beam；Three, the depickling processing of pbo fiber beam；Four, the irradiation grafting processing of pbo fiber beam；Five, the preparation of pbo fiber cyanate composite material.The present invention utilizes Co60Gamma-ray radiation method is in the hyperbranched PBO polymer of pbo fiber surface grafting, increase the interface bond strength of pbo fiber cyanate composite material, boundary strength increase rate is 32 ~ 45.65%, and processing pbo fiber cyanate composite material is made with good dielectric properties, be conducive to the wave-penetrating composite material of preparation structure function integration.

Description

A kind of preparation method of high temperature dielectric properties pbo fiber composite material
Technical field
The invention belongs to pbo fiber technical field of composite preparation, and in particular to a kind of high temperature dielectric properties pbo fiber The preparation method of composite material.
Background technology
Aerospace craft needs fly in 300 DEG C or more hot environments, this is high temperatures to aircraft radome material More stringent requirements are proposed for energy.In antenna system field, preparation structure function integration composite material is particularly important.However it is good High temperature dielectric properties be built upon and stablize solid structural behaviour on the basis of.Although pbo fiber has excellent high temperature resistant With dielectric properties, but surface lack active group cause interfacial adhesion weaker with roughness, composite property is special It is that high-temperature behavior is undesirable, limits the use of pbo fiber.Therefore, there is an urgent need to pbo fiber carry out surface active with it is coarse Change is handled, and is increased it and is acted on resin boundary surface chemical bonding and cast setting, strong with the interface cohesion of resin to improve it There is good interface performance just can guarantee that the maximum of its dielectric properties plays for degree, pbo fiber composite material.Therefore, PBO is prepared Fibre fire resistant composite material is of great significance.
Two are carried out to pbo fiber using graphene oxide and APTMS in the patent of invention of Publication No. CN103820996A First grafting is handled, and pbo fiber, publication number are modified using zinc oxide nanowire in the patent of invention of Publication No. CN103628305A To utilize Co in the patent of invention of CN1544745A60 Gamma-ray irradiation in pbo fiber surface grafting epoxychloropropane, these three Method is improved pbo fiber composite material interface shear strength, but graphene oxide has suction in first method Wave property is unfavorable for preparing dielectric composite material；Zinc oxide nanowire is small molecule in second method, and it is multiple to be unfavorable for high temperature resistant Condensation material；Epoxychloropropane heat resistance is bad in the third method.Therefore there is an urgent need to find a kind of heat-resisting and be situated between with good The graft of electrical property, hyperbranched PBO polymer is made in laboratory, which by oneself, to be had good heat resistance and not inhales wave substance, as Pbo fiber graft is a selection well.
Invention content
The purpose of the present invention is to solve existing pbo fiber interface performance and the problems of high temperature resistance difference, provide one The preparation method of kind high temperature dielectric properties pbo fiber composite material, this method are to carry out surface active and roughening to pbo fiber It handles, then the hyperbranched poly benzo oxazole that dielectric properties are excellent with heat resistance grafting pbo fiber is made with cyanate High-temperature dielectric composite material can improve PBO composite material interfaces performance and high temperature dielectric properties simultaneously, and the material of preparation is with excellent Different dielectric properties, interface performance and heat resistance.
To achieve the above object, the technical solution adopted by the present invention is as follows：
A kind of preparation method of high temperature dielectric properties pbo fiber composite material, the method include the following steps：
Step 1：The preparation of grafting liquid：By the homemade hyperbranched PBO polymer in laboratory and polyphosphoric acids with 1：125 ~ 150 Mass ratio is placed in 500 mL three-necked bottles, and electric mixer is used to make with the rotating speed stirring of 100 ~ 500 r/min under nitrogen atmosphere It is completely dissolved, and grafting liquid is made；
Step 2：The infiltration of pbo fiber is handled：It takes 10 ~ 20 laboratories m to make clean pbo fiber by oneself, pbo fiber beam is made, Both ends are fastened with polytetrafluoroethylene tape, and pbo fiber beam is placed in grafting liquid made from step 1, are carried out ultrasound, are made pbo fiber Beam is fully infiltrated with grafting liquid；
Step 3：The depickling of pbo fiber beam is handled：The pbo fiber beam that step 2 obtains is placed in equipped with 1000 mL distilled water In beaker, using constant temperature blender with magnetic force heating water bath, every 10 min replaces the distilled water in beaker to wash away pbo fiber beam table The polyphosphoric acids in face；
Step 4：The radiation treatment of pbo fiber beam：Pbo fiber beam in step 3 is placed in the test tube of 50 mL, is utilized Co60 Pbo fiber Shu Liyong polyphosphoric acids after irradiation is washed 5 ~ 10 min to remove not by gamma-ray irradiation pbo fiber beam Then hyperbranched PBO polymer in grafting recycles 1 ~ 2 h of distillation water washing to remove the polyphosphoric acids on fibre bundle surface, will Washed pbo fiber beam is placed in 50 ~ 60 DEG C of 24 ~ 48 h of drying in drying box；
Step 5：The preparation of pbo fiber cyanate composite material：By 60 ~ 66 beam in step 4（Per 22 cm of Shu Changwei）PBO is fine Dimension, is fully infiltrated in 10 ~ 12 g cyanates at a temperature of 80 ~ 90 DEG C, then puts in a mold, cured using vulcanizer, Curing cycle is 100 DEG C/3 ~ 4 h+135 DEG C/3 ~ 4 h+180 DEG C/3 ~ 4 h, and solidifying pressure is 10 ~ 15 MPa.
The advantageous effect of the present invention compared with the existing technology is：Hyperbranched PBO polymer is dissolved in polyphosphoric acids by the present invention Grafting liquid is made, utilizes Co60 Hyperbranched poly benzo oxazole grafting pbo fiber is prepared in gamma-ray irradiation.Pbo fiber cyanic acid Ester composite material interface performance significantly improves, and interface shear strength increase rate is 32 ~ 45.65%, and pbo fiber cyanogen obtained Acid esters composite material has good dielectric properties, especially at 300 DEG C, processed pbo fiber cyanate composite material dielectric damage Consumption is significantly less than the dielectric loss of untreated pbo fiber cyanate composite material, this is conducive to prepare heat resistant structure function one The wave-penetrating composite material of body.
Description of the drawings
Fig. 1 is the infared spectrum of pbo fiber after predose；
Fig. 2 is the SEM photograph of predose pbo fiber；
Fig. 3 is the SEM photograph of pbo fiber after irradiation；
Fig. 4 is the interface shear strength comparison diagram of pbo fiber cyanate composite material after predose；
Fig. 5 is the dielectric constant comparison diagram of predose pbo fiber cyanate composite material at different temperatures；
Fig. 6 is the dielectric constant comparison diagram of pbo fiber cyanate composite material at different temperatures after irradiation；
Fig. 7 is the dielectric loss comparison diagram of predose pbo fiber cyanate composite material at different temperatures；
Fig. 8 is the dielectric loss comparison diagram of pbo fiber cyanate composite material at different temperatures after irradiation.
Specific implementation mode
Technical scheme of the present invention is further described with reference to the accompanying drawings and examples, however, it is not limited to this, Every to be modified to technical solution of the present invention or equivalent replacement, range without departing from the spirit of the technical scheme of the invention should all Cover among protection scope of the present invention.
There are a large amount of terminal reactive groups for hyperbranched PBO polymer, and generally in branch shape structure, inside has a large amount of micro- sky Gap, have lower dielectric constant, using hyperbranched PBO polymer to pbo fiber carry out bulk graft, then with cyanate system Standby high temperature resistant composite, can obtain excellent interface performance and dielectric properties.
Specific implementation mode one：What present embodiment was recorded is a kind of system of high temperature dielectric properties pbo fiber composite material Preparation Method, the method include the following steps：
Step 1：The preparation of grafting liquid：By the homemade hyperbranched PBO polymer in laboratory and polyphosphoric acids with 1：125 ~ 150 Mass ratio is placed in 500 mL three-necked bottles, and electric mixer is used to make with the rotating speed stirring of 100 ~ 500 r/min under nitrogen atmosphere It is completely dissolved, and grafting liquid is made；The electric mixer is the DJ1C reinforcement electric mixers of Jintan the earth production；
Step 2：The infiltration of pbo fiber is handled：It takes 10 ~ 20 laboratories m to make clean pbo fiber by oneself, pbo fiber beam is made, Both ends are fastened with polytetrafluoroethylene tape, and pbo fiber beam is placed in grafting liquid made from step 1, are carried out ultrasound, are made pbo fiber Beam is fully infiltrated with grafting liquid；
Step 3：The depickling of pbo fiber beam is handled：The pbo fiber beam that step 2 obtains is placed in equipped with 1000 mL distilled water In beaker, using constant temperature blender with magnetic force heating water bath, every 10 min replaces the distilled water in beaker to wash away pbo fiber beam table The polyphosphoric acids in face；The constant temperature blender with magnetic force is purchased from Zhong great instrument plants of Jintan City, model DF-1 heat collecting type constant temperature magnetic Power blender；
Step 4：The radiation treatment of pbo fiber beam：Pbo fiber beam in step 3 is placed in the test tube of 50 mL, is utilized Co60 Pbo fiber Shu Liyong polyphosphoric acids after irradiation is washed 5 ~ 10 min to remove not by gamma-ray irradiation pbo fiber beam Then hyperbranched PBO polymer in grafting recycles 1 ~ 2 h of distillation water washing to remove the polyphosphoric acids on fibre bundle surface, will Washed pbo fiber beam is placed in 50 ~ 60 DEG C of 24 ~ 48 h of drying in drying box；The drying box has purchased from the permanent science and technology in Shanghai one Limit company, model DZF-6000 type vacuum drying chambers；
Step 5：The preparation of pbo fiber cyanate composite material：By 60 ~ 66 beam in step 4（Per 22 cm of Shu Changwei）PBO is fine Dimension, is fully infiltrated in 10 ~ 12 g cyanates at a temperature of 80 ~ 90 DEG C, then puts in a mold, cured using vulcanizer, Curing cycle is 100 DEG C/3 ~ 4 h+135 DEG C/3 ~ 4 h+180 DEG C/3 ~ 4 h, and solidifying pressure is 10 ~ 15 MPa.The sulphur Change machine is purchased from Zhengzhou Yi Shida hydraulic pressure Co., Ltd, the hydraulic flat vulcanizer of model 257-350-350.
Specific implementation mode two：A kind of high temperature dielectric properties pbo fiber composite material described in specific implementation mode one Preparation method, in step 1, the electric stirring time is 4 ~ 6 h, and whipping temp is 110 ~ 160 DEG C.
Specific implementation mode three：A kind of high temperature dielectric properties pbo fiber composite material described in specific implementation mode one Preparation method, in step 2, the ultrasonic time is 5 ~ 10 min, and ultrasonic power is 120 W.
Specific implementation mode four：A kind of high temperature dielectric properties pbo fiber composite material described in specific implementation mode one Preparation method, in step 3, the water bath heating temperature is 80 ~ 90 DEG C, and the time is 1 ~ 2 h.
Specific implementation mode five：A kind of high temperature dielectric properties pbo fiber composite material described in specific implementation mode one Preparation method, in step 4, the Co60 Gamma-ray irradiation dosage is 30 ~ 40 kGy, and irradiation time is 15 ~ 20 h.
Embodiment 1：
A kind of preparation method of high temperature dielectric properties pbo fiber composite material follows these steps to realize：
Step 1：The preparation of grafting liquid：2.4 laboratories the g hyperbranched PBO polymer of homemade two generations carboxy blocking is weighed to be placed in In 500 mL three-necked bottles, 300 g polyphosphoric acids are added, 5 h of electric stirring keeps it completely molten at 160 DEG C under nitrogen atmosphere Solution, wherein rotating speed are 300 r/min, and grafting liquid is made；
Step 2：The infiltration of pbo fiber is handled：The homemade clean pbo fiber in 15 laboratories m is taken, fibre bundle, both ends are made It is fastened with polytetrafluoroethylene tape, fibre bundle is placed in the grafting liquid in step 1, carry out 10 min of ultrasound, ultrasonic power is 120 W make pbo fiber fully be infiltrated with grafting liquid；
Step 3：The depickling of pbo fiber beam is handled：Fibre bundle in step 2 is placed in the beaker equipped with 1000 mL distilled water In, 1 h of heating water bath at 90 DEG C, every 10 min replace the distilled water in beaker to wash away the poly phosphorus on pbo fiber beam surface Acid is replaced 6 times altogether；
Step 4：The radiation treatment of pbo fiber beam：Fiber in step 3 is placed in the coupon of 50 mL, utilizes 30 kGy Co60 Fibre bundle after irradiation is washed 5min to remove on non-grafted by 15 h of gamma-ray irradiation fibre bundle using polyphosphoric acids Hyperbranched PBO polymer, then recycle distillation water washing 1h to remove the polyphosphoric acids on fibre bundle surface；By washed fiber Beam is placed in 60 DEG C of vacuum drying ovens dry 24 h；
Step 5：The preparation of pbo fiber cyanate composite material：63 beams in step 4 (per 22 cm of Shu Changwei) pbo fiber is filled 90 DEG C of 12 g cyanates point are infiltrated on, are then put in a mold, the type produced using Zhengzhou Yi Shida hydraulic pressure Co., Ltd Number for 257-350-350 hydraulic flat vulcanizer cure, curing cycle be 100 DEG C/3 h+135 DEG C/4 h+180 DEG C/3 H, solidifying pressure are 15 MPa.
The untreated pbo fiber of 1 beam and each 3 cm of processed pbo fiber are taken respectively, and fibre fine crushing is cut into scissors It is red to survey its using the method that the Nexus670 type infrared spectrometers of NICOLET Co., Ltds of U.S. production utilize KBr tablettings for dimension end Outer collection of illustrative plates, to observe untreated pbo fiber and difference of the processed pbo fiber in composed structure.
Fig. 1 is the infared spectrum of pbo fiber after predose, is found out by figure, fiber is in 3434 cm after irradiation-1For end carboxyl In-OH stretching vibration absworption peak, therefore carboxy blocking hyperbranched PBO polymer, success on fibre grafting after irradiation It is prepared for hyperbranched poly benzo oxazole grafting pbo fiber, increases the active site on pbo fiber surface.
Fig. 2 is the SEM photograph of predose pbo fiber, as seen from the figure, pbo fiber surface smoother.Fig. 3 is spoke According to the SEM photograph of rear pbo fiber, as seen from the figure, it is poly- that uniform hyperbranched PBO is uniform-distribution on pbo fiber Object is closed, particle diameter distribution increases the surface roughness of pbo fiber in 150 ~ 200 nm.
Predose pbo fiber and pbo fiber monofilament after irradiation are adhesive in two-sided on specimen holder respectively first, in PBO Fiber drips AB glue with double faced adhesive tape abutting edge point one keeps it fully fixed.Secondly using the needle point of 1 mL needle tubings by cyanate ester compositions （Cyanate is 20 with cobalt naphthenate and nonyl phenol mass ratio：1：40）It drops on monofilament.Then sample is placed in baking oven and is cured, Curing cycle is 100 DEG C/3 h+135 DEG C/4 h+180 DEG C/3 h.The FA-620 types produced using Japanese Dong Rong Co., Ltd. Composite material interface evaluating apparatus measures predose pbo fiber and tree of the diameter at 100 ~ 200 μm on pbo fiber after irradiation The interface shear strength of fat ball tests 40, calculates the average value of interface shear strength respectively.
Fig. 4 is pbo fiber cyanate composite material interface shear strength comparison diagram, wherein predose pbo fiber cyanogen after predose Acid esters composite material interface shear strength is 32.20 MPa, and pbo fiber cyanate composite material interface shear strength is after irradiation 46.90 MPa, then pbo fiber cyanate composite material is cut compared to predose pbo fiber cyanate composite material interface after irradiating Shearing stress improves 45.65 %.This illustrates the modified reactivity point for increasing pbo fiber, increase fiber and resin it Between cast setting effect, improve interfacial adhesion strength.
Respectively by two part of 12 g cyanate, 0.6 g cobalt naphthenates and nonyl phenol mixture（Cobalt naphthenate and nonyl phenol matter Amount is than being 1:40）, 0.24 g benzyl dimethylamines（BDMA）Be placed in dixie cup, 90 DEG C be uniformly mixed, respectively with 63 beam original sample PBO Fiber, 63 beams processing pbo fiber carry out rubbing glue, keep fiber abundant with resin infiltration, are subsequently placed in 90 DEG C of molds, reach solidifying Glue point is forced into 15 MPa, is cured, and curing cycle is 100 DEG C/3 h+135 DEG C/4 h+180 DEG C/3 h.Cure Laminate is cut into the sample that size is 15 mm*6 mm*2 mm by Cheng Hou, opening mold.It is tried after taking predose sample and irradiation Sample positive and negative is coated silver electrode liquid and is placed in 200 DEG C of 10 min of solidification of miniature heating furnace, then uses Changzhou same by each 2 of sample The TH2827C types dielectric loss tester of favour Electronics Co., Ltd. production characterizes PBO/CE composite material dielectric properties. It is tested respectively at 18 DEG C（Room temperature）, 100 DEG C, 200 DEG C, 300 DEG C 1000 MHz of Hz ~ 1 dielectric constant and dielectric damage Consume the factor.
Fig. 5 is the dielectric constant comparison diagram of predose pbo fiber cyanate composite material at different temperatures, and Fig. 6 is The dielectric constant comparison diagram of pbo fiber cyanate composite material at different temperatures after irradiation, by Fig. 5 and Fig. 6 it is found that predose The dielectric constant of pbo fiber cyanate composite material increases with temperature and is increased afterwards, and irradiated sample compares predose sample Dielectric constant slightly increases, but still has good dielectric properties.
Fig. 7 is the dielectric loss comparison diagram of predose pbo fiber cyanate composite material at different temperatures, and Fig. 8 is The dielectric loss comparison diagram of pbo fiber cyanate composite material at different temperatures after irradiation, by Fig. 7 and Fig. 8 it is found that 18 DEG C ~ 200 DEG C, the dielectric loss of pbo fiber cyanate composite material changes unobvious after predose, when temperature reaches 300 DEG C, The dielectric loss of pbo fiber cyanate composite material sample is much smaller than predose pbo fiber cyanate composite material sample after irradiation The dielectric loss of product, improves dielectric properties.The interface performance of irradiated sample has compared with predose sample significantly to be promoted, favorably In improving wave-penetrating composite material mechanical performance, be conducive to the wave-penetrating composite material of preparation structure function integration.
Embodiment 2：
A kind of preparation method of high temperature dielectric properties pbo fiber composite material follows these steps to realize：
Step 1：The preparation of grafting liquid：It weighs 2 laboratories the g self-control hyperbranched PBO polymer of two generation carboxy blockings and is placed in 500 In mL three-necked bottles, 300 g polyphosphoric acids are added, electric stirring 5h makes it completely dissolved at 160 DEG C under nitrogen atmosphere, wherein Rotating speed is 200 r/min, and grafting liquid is made；
Step 2：The infiltration of pbo fiber is handled：The homemade clean pbo fiber in 15 laboratories m is taken, fibre bundle, both ends are made It is fastened with polytetrafluoroethylene tape.Fibre bundle is placed in the grafting liquid in step 1,10 min of ultrasound are carried out, ultrasonic power is 120 W make pbo fiber fully be infiltrated with grafting liquid；
Step 3：The depickling of pbo fiber beam is handled：Fibre bundle in step 2 is placed in the beaker equipped with 1000 mL distilled water In, 1 h of heating water bath at 90 DEG C, every 10 min replace the distilled water in beaker to wash away the poly phosphorus on pbo fiber beam surface Acid is replaced 6 times altogether；
Step 4：The radiation treatment of pbo fiber beam：Fiber in step 3 is placed in the coupon of 50 mL, utilizes 30 kGy Co60 15 h of gamma-ray irradiation fibre bundle；Fibre bundle after irradiation is non-grafted to remove using polyphosphoric acids washing 5min On hyperbranched PBO polymer, then recycle distillation water washing 1h to remove the polyphosphoric acids on fibre bundle surface；By washed fibre Dimension beam is placed in 60 DEG C of vacuum drying ovens dry 24 h；
Step 5：The preparation of pbo fiber cyanate composite material：63 beams in step 4 (per 22 cm of Shu Changwei) pbo fiber is filled 90 DEG C of 12 g cyanates point are infiltrated on, are then put in a mold, the model produced using Zhengzhou Yi Shida hydraulic pressure Co., Ltd Curing for the hydraulic flat vulcanizer of 257-350-350, curing cycle is 100 DEG C/3 h+135 DEG C/4 h+180 DEG C/3 h, Solidifying pressure is 15 MPa.
Predose pbo fiber cyanate composite material interface shear strength is 32.20 MPa, pbo fiber cyanic acid after irradiation Ester composite material interface shear strength is 45.03 MPa, then pbo fiber cyanate composite material compares predose PBO after irradiating Fiber cyanate composite material interface shear strength improves 39.84 %.This illustrates the modified activity for increasing pbo fiber Point improves the interfacial adhesion strength of fibre resin.
Embodiment 3：
A kind of preparation method of high temperature dielectric properties pbo fiber composite material follows these steps to realize：
Step 1：The preparation of grafting liquid：2.4 laboratories the g self-control amino-terminated hyperbranched PBO polymer of a generation is weighed to be placed in In 500 mL three-necked bottles, 300 g polyphosphoric acids are added, 5 h of electric stirring keeps it completely molten at 110 DEG C under nitrogen atmosphere Solution, wherein rotating speed are 200 r/min, and grafting liquid is made；
Step 2：The infiltration of pbo fiber is handled：The homemade clean pbo fiber in 10 laboratories m is taken, fibre bundle, both ends are made It is fastened with polytetrafluoroethylene tape.Fibre bundle is placed in the grafting liquid in step 1,10 min of ultrasound are carried out, ultrasonic power is 120 W make pbo fiber fully be infiltrated with grafting liquid；
Step 3：The depickling of pbo fiber beam is handled：Fibre bundle in step 2 is placed in the beaker equipped with 1000 mL distilled water In, 1 h of heating water bath at 90 DEG C, every 10 min replace the distilled water in beaker to wash away the poly phosphorus on pbo fiber beam surface Acid is replaced 6 times altogether；
Step 4：The radiation treatment of pbo fiber beam：Fiber in step 3 is placed in the coupon of 50 mL, utilizes 30 kGy Co60 15 h of gamma-ray irradiation fibre bundle；Fibre bundle after irradiation is non-grafted to remove using polyphosphoric acids washing 5min On hyperbranched PBO polymer, then recycle distillation water washing 1h to remove the polyphosphoric acids on fibre bundle surface；By washed fibre Dimension beam is placed in 60 DEG C of vacuum drying ovens dry 24 h；
Step 5：The preparation of pbo fiber cyanate composite material：63 beams in step 4 (per 22 cm of Shu Changwei) pbo fiber is filled 90 DEG C of 12 g cyanates point are infiltrated on, are then put in a mold, the type produced using Zhengzhou Yi Shida hydraulic pressure Co., Ltd Number for 257-350-350 hydraulic flat vulcanizer cure, curing cycle be 100 DEG C/3 h+135 DEG C/4 h+180 DEG C/3 H, solidifying pressure are 15 MPa.
Predose pbo fiber cyanate composite material interface shear strength is 32.20 MPa, pbo fiber cyanic acid after irradiation Ester composite material interface shear strength is 43.95 MPa, then pbo fiber cyanate composite material compares predose PBO after irradiating Fiber cyanate composite material interface shear strength improves 36.49 %.This illustrates modified to increase the coarse of pbo fiber Degree, improves the interfacial adhesion strength of fibre resin.
Embodiment 4：
A kind of preparation method of high temperature dielectric properties pbo fiber composite material follows these steps to realize：
Step 1：The preparation of grafting liquid：It weighs the laboratories the 2g self-control amino-terminated hyperbranched PBO polymer of a generation and is placed in 500 In mL three-necked bottles, 300 g polyphosphoric acids are added, 5 h of electric stirring makes it completely dissolved at 110 DEG C under nitrogen atmosphere, Middle rotating speed is 200 r/min, and grafting liquid is made；
Step 2：The infiltration of pbo fiber is handled：The homemade clean pbo fiber in 15 laboratories m is taken, fibre bundle, both ends are made It is fastened with polytetrafluoroethylene tape.Fibre bundle is placed in the grafting liquid in step 1,10 min of ultrasound are carried out, ultrasonic power is 120 W make pbo fiber fully be infiltrated with grafting liquid；
Step 3：The depickling of pbo fiber beam is handled：Fibre bundle in step 2 is placed in the burning of 1000 mL equipped with distilled water In cup, 1 h of heating water bath at 90 DEG C, every 10 min replace the distilled water in beaker to wash away the poly on pbo fiber beam surface Phosphoric acid is replaced 6 times altogether；
Step 4：The radiation treatment of pbo fiber beam：Fiber in step 3 is placed in the coupon of 50 mL, utilizes 30 kGy Co60 15 h of gamma-ray irradiation fibre bundle；Fibre bundle after irradiation is non-grafted to remove using polyphosphoric acids washing 5min On hyperbranched PBO polymer, then recycle distillation water washing 1h to remove the polyphosphoric acids on fibre bundle surface；By washed fibre Dimension beam is placed in 60 DEG C of vacuum drying ovens dry 24 h；
Step 5：The preparation of pbo fiber cyanate composite material：63 beams in step 4 (per 22 cm of Shu Changwei) pbo fiber is filled 90 DEG C of 12 g cyanates point are infiltrated on, are then put in a mold, the type produced using Zhengzhou Yi Shida hydraulic pressure Co., Ltd Number for 257-350-350 hydraulic flat vulcanizer cure, curing cycle be 100 DEG C/3 h+135 DEG C/4 h+180 DEG C/3 H, solidifying pressure are 15 MPa.
Predose pbo fiber cyanate composite material interface shear strength is 32.20 MPa, pbo fiber cyanic acid after irradiation Ester composite material interface shear strength is 42.50 MPa, then pbo fiber cyanate composite material compares predose PBO after irradiating Fiber cyanate composite material interface shear strength improves 32 %.This illustrates the modified phase for increasing pbo fiber with resin Interreaction force.

Claims (5)

1. a kind of preparation method of high temperature dielectric properties pbo fiber composite material, it is characterised in that：The method includes following Step：
Step 1：The preparation of grafting liquid：By the homemade hyperbranched PBO polymer in laboratory and polyphosphoric acids with 1：125 ~ 150 Mass ratio is placed in 500 mL three-necked bottles, and electric mixer is used to make with the rotating speed stirring of 100 ~ 500 r/min under nitrogen atmosphere It is completely dissolved, and grafting liquid is made；
Step 2：The infiltration of pbo fiber is handled：It takes 10 ~ 20 laboratories m to make clean pbo fiber by oneself, pbo fiber beam is made, Both ends are fastened with polytetrafluoroethylene tape, and pbo fiber beam is placed in grafting liquid made from step 1, are carried out ultrasound, are made pbo fiber Beam is fully infiltrated with grafting liquid；
Step 3：The depickling of pbo fiber beam is handled：The pbo fiber beam that step 2 obtains is placed in equipped with 1000 mL distilled water In beaker, using constant temperature blender with magnetic force heating water bath, every 10 min replaces the distilled water in beaker to wash away pbo fiber beam table The polyphosphoric acids in face；
Step 4：The radiation treatment of pbo fiber beam：Pbo fiber beam in step 3 is placed in the test tube of 50 mL, is utilized Co60 Pbo fiber Shu Liyong polyphosphoric acids after irradiation is washed 5 ~ 10 min to remove not by gamma-ray irradiation pbo fiber beam Then hyperbranched PBO polymer in grafting recycles 1 ~ 2 h of distillation water washing to remove the polyphosphoric acids on fibre bundle surface, will Washed pbo fiber beam is placed in 50 ~ 60 DEG C of 24 ~ 48 h of drying in drying box；
Step 5：The preparation of pbo fiber cyanate composite material：By 60 ~ 66 beam in step 4（Per 22 cm of Shu Changwei）PBO is fine Dimension, is fully infiltrated in 10 ~ 12 g cyanates at a temperature of 80 ~ 90 DEG C, then puts in a mold, cured using vulcanizer, Curing cycle is 100 DEG C/3 ~ 4 h+135 DEG C/3 ~ 4 h+180 DEG C/3 ~ 4 h, and solidifying pressure is 10 ~ 15 MPa.
2. a kind of preparation method of high temperature dielectric properties pbo fiber composite material according to claim 1, feature exist In：In step 1, the electric stirring time is 4 ~ 6 h, and whipping temp is 110 ~ 160 DEG C.
3. a kind of preparation method of high temperature dielectric properties pbo fiber composite material according to claim 1, feature exist In：In step 2, the ultrasonic time is 5 ~ 10 min, and ultrasonic power is 120 W.
4. a kind of preparation method of high temperature dielectric properties pbo fiber composite material according to claim 1, feature exist In：In step 3, the water bath heating temperature is 80 ~ 90 DEG C, and the time is 1 ~ 2 h.
5. a kind of preparation method of high temperature dielectric properties pbo fiber composite material according to claim 1, feature exist In：In step 4, the Co60 Gamma-ray irradiation dosage is 30 ~ 40 kGy, and irradiation time is 15 ~ 20 h.
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