CN110437563A - A kind of poly- (biasfluoroethylene-hexafluoropropylene) organic and inorganic insulating composite material and preparation method thereof of magnetism - Google Patents

A kind of poly- (biasfluoroethylene-hexafluoropropylene) organic and inorganic insulating composite material and preparation method thereof of magnetism Download PDF

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CN110437563A
CN110437563A CN201910622359.5A CN201910622359A CN110437563A CN 110437563 A CN110437563 A CN 110437563A CN 201910622359 A CN201910622359 A CN 201910622359A CN 110437563 A CN110437563 A CN 110437563A
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biasfluoroethylene
hexafluoropropylene
magnetism
cooh
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马海龙
郭臣
唐阔海
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Xiamen Minyao Trading Co Ltd
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Abstract

The present invention relates to magnetic insulating composite material preparation technical fields, and disclose a kind of poly- (biasfluoroethylene-hexafluoropropylene) the organic and inorganic insulating composite material and preparation method thereof of magnetism, including following raw material, poly- (biasfluoroethylene-hexafluoropropylene), multi-walled carbon nanotube, glacial acetic acid, dilute hydrochloric acid, magnetic Nano nickel oxide, titanate coupling agent.Poly- (biasfluoroethylene-hexafluoropropylene) monomer is vinylidene and hexafluoropropene structural formula are as follows:

Description

A kind of poly- (biasfluoroethylene-hexafluoropropylene) organic and inorganic insulating composite material of magnetism And preparation method thereof
Technical field
The present invention relates to magnetic insulating composite material technical field of composite preparation, specially it is a kind of it is magnetic it is poly- (partially Vinyl fluoride-hexafluoropropene) organic and inorganic insulating composite material.
Background technique
In recent years, with the multifunction of electrical equipment and electronic equipment, lightness and miniaturization, there is an urgent need to exhausted by people The higher control cable of edge has high heat resistance, LSOH anti-flaming, oil resistant and soft in these equipments and equipment It is soft equal using characteristic, and in the place of some high and low heat, select traditional polyvinyl chloride and Kynoar insulation control cable Sheath is no longer satisfied above-mentioned characteristic requirements, and someone has developed one kind with polytetrafluoroethylene (PTFE), perfluoroalkoxy resin at present With the fluorine plastic insulating control cable sheath and silicon rubber insulation glass braid control electricity that fluorinated ethylene propylene polymer is representative Cable, but the disadvantages of these products generally have dielectric constant relatively low, and damping characteristic is poor can not meet the use of people well Demand.
Poly- (biasfluoroethylene-hexafluoropropylene) has good machining property and higher dielectric constant and excellent Chemical corrosion resistance the advantages that be applied to the fields such as electric and fluorocarbon coating, but poly- (biasfluoroethylene-hexafluoropropylene) Regularity by crystallinity, crystal form type and strand etc. influences, and limits the extensive of poly- (biasfluoroethylene-hexafluoropropylene) It uses, the unique texture of carbon nanotube determines that it has many special physics and chemical property, forms the C=of carbon nanotube C covalent bond is the most stable of chemical bond of nature, so that carbon nanotube has very excellent mechanical property, carbon nanotube It is likely to become a kind of novel high intensity carbon fiber material, not only with the intrinsic person's character of carbon materials, but also with metal material Conductive and thermal conductivity.
Summary of the invention
(1) the technical issues of solving
In view of the deficiencies of the prior art, the present invention provides poly- (biasfluoroethylene-hexafluoropropylene) of a kind of magnetism it is organic- Inorganic insulation composite material, solves that existing fluorine plastic insulating control cable dielectric constant is relatively low, and damping characteristic is poor, causes absolutely The problems such as edge effect is poor, while solving poly- (biasfluoroethylene-hexafluoropropylene) again by crystallinity, crystal form type and molecule The problems such as regularity of chain etc. influences, its performance is greatly reduced.
(2) technical solution
To achieve the above object, the invention provides the following technical scheme: a kind of poly- (vinylidene-hexafluoro third of magnetism Alkene) organic and inorganic insulating composite material and preparation method thereof, the raw material including following parts by weight proportion, 60-85 parts are poly- (inclined Vinyl fluoride-hexafluoropropene), 2-5 parts of multi-walled carbon nanotubes, 5-10 parts of magnetic Nano nickel oxide, 3-8 parts of glacial acetic acids, 5-10 parts it is dilute Hydrochloric acid, 1-3 part titanate coupling agent.
Preferably, poly- (biasfluoroethylene-hexafluoropropylene) monomer is vinylidene and hexafluoropropene, vinylidene-fluoride units Content is 75-80%, and hexafluoropropene unit content is 20-25%, and Polymer Molecular Weight is 500~560kg/mol, knot Structure formula are as follows:.
Preferably, the multi-walled carbon nanotube is the allotrope of carbon, and the outer diameter of multi-walled carbon nanotube is 15-30nm, Internal diameter is 1-3nm, length 2.5-4um.
Preferably, the content of NiO is 98.2-99.5% in the magnetic Nano nickel oxide.
Preferably, the glacial acetic acid is the CH that concentration is 97-98%3CH2COOH solution, substance withdrawl syndrome 16.5- 17.1mol/L, density 1.231-1.045g/cm3。
Preferably, it is 20%-21% that the dilute hydrochloric acid, which is concentration, and substance withdrawl syndrome is 6.05-6.17 mol/L, density For 1.103-1.113g/cm3。
Preferably, the titanate coupling agent is isopropyl three (dioctyl phosphoric acid acyloxy) titanate esters.
Preferably, poly- (biasfluoroethylene-hexafluoropropylene) the organic and inorganic insulating composite material of the magnetism, preparation method The following steps are included:
(1) multi-walled carbon nanotube of preparation acidification: 3-8 parts of glacial acetic acids are successively weighed, 5-10 parts of dilute hydrochloric acid are put into and are passed through N2 Three-necked bottle in, add 2-5 parts of multi-walled carbon nanotubes, N will be passed through2Three-necked bottle be placed in processor for ultrasonic wave, surpassed Sonication 1-1.5h, ultrasound after by three-necked bottle heating water bath to 75-80 DEG C, react 12-15h, taken out after fully reacting Filtered material is distilled water washing by 2000-3000mL, remaining acetate and hydrochloride is removed, in material is in by filter Property, material is placed in baking oven and is heated to 85-90 DEG C of drying moisture, obtains the acidification multi-wall carbon nano-tube of black powder solid Pipe, COOH-MWCNTs-HCl nanoparticle；
(2) 5-10 parts of magnetic Nano nickel oxide are weighed, is added in 500mL beaker, sequentially adds 200ml distilled water, and COOH-MWCNTs-HCl nanoparticle made from above-mentioned steps (1), heating water bath make to 60-65 DEG C of at the uniform velocity stirring 2-3h COOH-MWCNTs-HCl nanoparticle and magnetism NiO are uniformly mixed, then material is transferred into high-pressure hydrothermal reaction kettle, and temperature is 105-110 DEG C, heating reaction 6-8h makes magnetic NiO be adhering completely to COOH-MWCNTs-HCl nanoparticle surface, is prepared into To the functional nano filler of magnetic NiO modification COOH-MWCNTs-HCl；
(3) weigh in 60-85 parts of poly- (biasfluoroethylene-hexafluoropropylene) 1000mL beakers, add 200 mL distilled water, The nanoparticle and 1-3 of magnetism NiO obtained modification COOH-MWCNTs-HCl in 300mL ethylene glycol and above-mentioned steps (2) Part titanate coupling agent, heating water bath quickly stir 30-40min to 70-75 DEG C, make poly- (biasfluoroethylene-hexafluoropropylene) and The nanoparticle of magnetic NiO modification COOH-MWCNTs-HCl is uniformly mixed, and after stirring stirring completely, by material filtering, passes through steaming Distilled water is washed to ethylene glycol and is completely removed, then material is placed in 85-90 DEG C of baking oven and dries moisture, obtains poly- (vinylidene- Hexafluoropropene)-magnetism NiO modification COOH-MWCNTs-HCl functional material；
(4) mixture is placed in melt blending in kneading machine, melt blending temperature is 250-270 DEG C, and the blending time is 40- 60min, then it is hot-forming by vulcanizing press, hot pressing temperature is 220-230 DEG C, and hot pressing time 20-30min finally leads to Sheet-punching machine is crossed to form to obtain magnetic poly- (biasfluoroethylene-hexafluoropropylene) organic and inorganic insulating composite material.
(3) beneficial technical effect
Compared with prior art, the present invention has following beneficial technical effect:
1, poly- (biasfluoroethylene-hexafluoropropylene) the organic and inorganic insulating composite material of the magnetism, uses poly- (vinylidene- Hexafluoropropene) main component as material, poly- (biasfluoroethylene-hexafluoropropylene) is compared to traditional polyvinyl chloride and gathers inclined fluorine Ethylene has good machining property and higher dielectric constant and excellent chemical corrosion resistance, is more suitable for Manufacture insulation control cable sheath.
2, poly- (biasfluoroethylene-hexafluoropropylene) the organic and inorganic insulating composite material of the magnetism, passes through glacial acetic acid and dilute salt Acid acidification many walls nanotube, successfully prepares COOH-MWCNTs-HCl functional nano filler, and COOH-MWCNTs-HCl is functional Nanofiller enhances the interfacial interaction between poly- (biasfluoroethylene-hexafluoropropylene) compared to more carbon nanotubes, promotes The generation of the metastable β crystalline substance of poly- (biasfluoroethylene-hexafluoropropylene), keeps COOH-MWCNTs-HCl functional nano filler equal Even dispersion is simultaneously attached on the matrix of poly- (biasfluoroethylene-hexafluoropropylene) polymer, improves crystallinity, the knot of composite material Brilliant temperature and melting temperature generally improve the mechanical performance and mechanical property of composite material.
3, poly- (biasfluoroethylene-hexafluoropropylene) the organic and inorganic insulating composite material of the magnetism, passes through the multi wall in acidification The magnetic NiO of functional modification in carbon nanotube, makes the wall carbon nano tube of acidification be easier to be evenly distributed on poly- (vinylidene- Hexafluoropropene) on polymeric matrix, the COOH-MWCNTs-HCl nanoparticle of magnetic NiO modification is in poly- (vinylidene-hexafluoro Propylene) crystallization process is as nucleating agent, and relatively more carbon nanotube, COOH-MWCNTs-HCl nanoparticle more prevents Asia The β crystal phase of stable state changes the crystal structure of poly- (biasfluoroethylene-hexafluoropropylene) matrix, improves to the α crystal transition of stable state The crystallinity of poly- (biasfluoroethylene-hexafluoropropylene), magnetic NiO modification COOH-MWCNTs-HCl nanoparticle improve with it is poly- (partially Vinyl fluoride-hexafluoropropene) interfacial effect between matrix, so that composite material is enhanced the ability of dissipation energy, to improve resistance Damping characteristics and dielectric constant, reduce electrical loss, increase disruptive field intensity, strengthen the insulating properties of composite material, preferably answer For manufacturing insulation control cable sheath.
Specific embodiment
To achieve the above object, the invention provides the following technical scheme: to achieve the above object, the present invention provides following skill Art scheme: a kind of poly- (biasfluoroethylene-hexafluoropropylene) organic and inorganic insulating composite material and preparation method thereof of magnetism, including The raw material of following parts by weight proportion, 60-85 parts of poly- (vinylidene-hexafluoropropene), 2-5 parts of multi-walled carbon nanotubes, 3-8 parts Glacial acetic acid, 5-10 part dilute hydrochloric acid are acidified many walls nanotube by glacial acetic acid and dilute hydrochloric acid, successfully prepare COOH-MWCNTs-HCl Functional nano filler, COOH-MWCNTs-HCl functional nano filler enhance and poly- (inclined fluorine compared to more carbon nanotubes Ethylene-hexafluoropropene) between interfacial interaction, promote the life of the metastable β crystalline substance of poly- (biasfluoroethylene-hexafluoropropylene) At, make the dispersion of COOH-MWCNTs-HCl functional nano uniform filling and be attached to poly- (biasfluoroethylene-hexafluoropropylene) polymerization On the matrix of object, the crystallinity, crystallization temperature and melting temperature of composite material are improved
5-10 parts of magnetic Nano nickel oxide are made by the magnetic NiO of functional modification on the multi-walled carbon nanotube of acidification The wall carbon nano tube of acidification is easier to be evenly distributed on poly- (biasfluoroethylene-hexafluoropropylene) polymeric matrix, magnetic NiO modification COOH-MWCNTs-HCl nanoparticle in poly- (vinylidene-hexafluoropropene) crystallization process as nucleating agent, relatively more carbon Nanotube, COOH-MWCNTs-HCl nanoparticle more prevent α crystal transition of the metastable β crystal phase to stable state, change The crystal structure of poly- (biasfluoroethylene-hexafluoropropylene) matrix, improves the crystallinity of poly- (biasfluoroethylene-hexafluoropropylene), magnetic Property NiO modification COOH-MWCNTs-HCl nanoparticle improve with poly- (biasfluoroethylene-hexafluoropropylene) matrix between interface effect It answers, composite material is made to enhance the ability of dissipation energy, to improve damping characteristic and dielectric constant, reduce electrical loss, increase Big disruptive field intensity, 1-3 part titanate coupling agents, poly- (biasfluoroethylene-hexafluoropropylene) monomer are vinylidene and hexafluoropropene, Vinylidene-fluoride units content be 75-80%, hexafluoropropene unit content be 20-25%, Polymer Molecular Weight be 500~ 560kg/mol, structural formula are as follows:Multi-walled carbon nanotube is the allotrope of carbon, more The outer diameter of wall carbon nano tube is 15-30nm, internal diameter 1-3nm, length 2.5-4um, the content of NiO in magnetic Nano nickel oxide For 98.2-99.5%, glacial acetic acid is the CH that concentration is 97-98%3CH2COOH solution, substance withdrawl syndrome 16.5- 17.1mol/L, density 1.231-1.045g/cm3, dilute hydrochloric acid is that concentration is 20%-21%, substance withdrawl syndrome 6.05- 6.17mol/L, density are 1.103-1.113 g/cm3, titanate coupling agent is isopropyl three (dioctyl phosphoric acid acyloxy) titanium Acid esters, magnetic poly- (biasfluoroethylene-hexafluoropropylene) organic and inorganic insulating composite material, preparation method the following steps are included:
(1) multi-walled carbon nanotube of preparation acidification: 3-8 parts of glacial acetic acids are successively weighed, 5-10 parts of dilute hydrochloric acid are put into and are passed through N2 Three-necked bottle in, add 2-5 parts of multi-walled carbon nanotubes, N will be passed through2Three-necked bottle be placed in processor for ultrasonic wave, surpassed Sonication 1-1.5h, ultrasound after by three-necked bottle heating water bath to 75-80 DEG C, react 12-15h, taken out after fully reacting Filtered material is distilled water washing by 2000-3000mL, remaining acetate and hydrochloride is removed, in material is in by filter Property, material is placed in baking oven and is heated to 85-90 DEG C of drying moisture, obtains the acidification multi-wall carbon nano-tube of black powder solid Pipe, COOH-MWCNTs-HCl nanoparticle；
(2) 5-10 parts of magnetic Nano nickel oxide are weighed, is added in 500mL beaker, sequentially adds 200ml distilled water, and COOH-MWCNTs-HCl nanoparticle made from above-mentioned steps (1), heating water bath make to 60-65 DEG C of at the uniform velocity stirring 2-3h COOH-MWCNTs-HCl nanoparticle and magnetism NiO are uniformly mixed, then material is transferred into high-pressure hydrothermal reaction kettle, and temperature is 105-110 DEG C, heating reaction 6-8h makes magnetic NiO be adhering completely to COOH-MWCNTs-HCl nanoparticle surface, is prepared into To the functional nano filler of magnetic NiO modification COOH-MWCNTs-HCl；
(3) weigh in 60-85 parts of poly- (biasfluoroethylene-hexafluoropropylene) 1000mL beakers, add 200 mL distilled water, The nanoparticle and 1-3 of magnetism NiO obtained modification COOH-MWCNTs-HCl in 300mL ethylene glycol and above-mentioned steps (2) Part titanate coupling agent, heating water bath quickly stir 30-40min to 70-75 DEG C, make poly- (biasfluoroethylene-hexafluoropropylene) and The nanoparticle of magnetic NiO modification COOH-MWCNTs-HCl is uniformly mixed, and after stirring stirring completely, by material filtering, passes through steaming Distilled water is washed to ethylene glycol and is completely removed, then material is placed in 85-90 DEG C of baking oven and dries moisture, obtains poly- (vinylidene- Hexafluoropropene)-magnetism NiO modification COOH-MWCNTs-HCl functional material；
(4) mixture is placed in melt blending in kneading machine, melt blending temperature is 250-270 DEG C, and the blending time is 40- 60min, then it is hot-forming by vulcanizing press, hot pressing temperature is 220-230 DEG C, and hot pressing time 20-30min finally leads to Sheet-punching machine is crossed to form to obtain magnetic poly- (biasfluoroethylene-hexafluoropropylene) organic and inorganic insulating composite material.
Poly- (biasfluoroethylene-hexafluoropropylene) the organic and inorganic insulating composite material of the magnetism, uses poly- (vinylidene-six Fluoropropene) main component as material, poly- (biasfluoroethylene-hexafluoropropylene) is compared to traditional polyvinyl chloride and polyvinylidene fluoride Alkene has good machining property and higher dielectric constant and excellent chemical corrosion resistance, is more suitable for making Insulation control cable sheath is made, poly- (biasfluoroethylene-hexafluoropropylene) the organic and inorganic insulating composite material of the magnetism passes through ice Acetic acid and dilute hydrochloric acid are acidified many walls nanotube, successfully prepare COOH-MWCNTs-HCl functional nano filler, COOH-MWCNTs- HCl functional nano filler enhances the interface phase between poly- (biasfluoroethylene-hexafluoropropylene) compared to more carbon nanotubes Interaction promotes the generation of the metastable β crystalline substance of poly- (biasfluoroethylene-hexafluoropropylene), makes COOH-MWCNTs-HCl function Property nanofiller is uniformly dispersed and is attached on the matrix of poly- (biasfluoroethylene-hexafluoropropylene) polymer, and composite wood is improved Crystallinity, crystallization temperature and the melting temperature of material generally improve the mechanical performance and mechanical property of composite material.
Poly- (biasfluoroethylene-hexafluoropropylene) the organic and inorganic insulating composite material of the magnetism, passes through the multi wall carbon in acidification The magnetic NiO of functional modification on nanotube, makes the wall carbon nano tube of acidification be easier to be evenly distributed on poly- (vinylidene-six Fluoropropene) on polymeric matrix, the COOH-MWCNTs-HCl nanoparticle of magnetic NiO modification is in poly- (vinylidene-hexafluoro third Alkene) crystallization process is as nucleating agent, and relatively more carbon nanotube, COOH-MWCNTs-HCl nanoparticle more prevents metastable The β crystal phase of state changes the crystal structure of poly- (biasfluoroethylene-hexafluoropropylene) matrix, improves poly- to the α crystal transition of stable state The crystallinity of (biasfluoroethylene-hexafluoropropylene), magnetic NiO modification COOH-MWCNTs-HCl nanoparticle improve and poly- (inclined fluorine Ethylene-hexafluoropropene) interfacial effect between matrix, so that composite material is enhanced the ability of dissipation energy, to improve damping Characteristic and dielectric constant, reduce electrical loss, increase disruptive field intensity, strengthen the insulating properties of composite material, preferably apply In manufacture insulation control cable sheath.
Embodiment 1:
(1) multi-walled carbon nanotube of preparation acidification: 3 parts of glacial acetic acids are successively weighed, 5 parts of dilute hydrochloric acid are put into and are passed through N2Three necks In bottle, 2 parts of multi-walled carbon nanotubes are added, N will be passed through2Three-necked bottle be placed in processor for ultrasonic wave, carry out ultrasonic treatment 1- 1.5h, ultrasound after by three-necked bottle heating water bath to 75-80 DEG C, react 12-15h, filtered, will be taken out after fully reacting Material after filter distills water washing by 2000-3000mL, removes remaining acetate and hydrochloride, until material is in neutrality, by object Material, which is placed in baking oven, is heated to 85-90 DEG C of drying moisture, obtains the acidification multi-walled carbon nanotube of black powder solid, COOH- MWCNTs-HCl nanoparticle 1；
(2) it weighs 5 parts of magnetic Nano nickel oxide, is added in 500mL beaker, sequentially add 200ml distilled water, and on COOH-MWCNTs-HCl nanoparticle made from step (1) is stated, heating water bath makes COOH- to 60-65 DEG C of at the uniform velocity stirring 2-3h MWCNTs-HCl nanoparticle and magnetism NiO are uniformly mixed, then material is transferred into high-pressure hydrothermal reaction kettle, temperature 105- 110 DEG C, heating reaction 6-8h makes magnetic NiO be adhering completely to COOH-MWCNTs-HCl nanoparticle surface, magnetic is prepared Property NiO modification COOH-MWCNTs-HCl functional nano filler 1；
(3) it weighs in 84 parts of poly- (biasfluoroethylene-hexafluoropropylene) 1000mL beakers, adds 200mL distilled water, 300mL The nanoparticle and 1 part of metatitanic acid of magnetism NiO obtained modification COOH-MWCNTs-HCl in ethylene glycol and above-mentioned steps (2) Ester coupling agent, heating water bath quickly stir 30-40min to 70-75 DEG C, make poly- (biasfluoroethylene-hexafluoropropylene) and magnetism NiO The nanoparticle for modifying COOH-MWCNTs-HCl is uniformly mixed, and after stirring stirring completely, material filtering is washed by distillation It washs to ethylene glycol and completely removes, then material is placed in 85-90 DEG C of baking oven and dries moisture, obtain poly- (vinylidene-hexafluoro third Alkene)-magnetism NiO modification COOH-MWCNTs-HCl functional material 1；
(4) mixture is placed in melt blending in kneading machine, melt blending temperature is 250-270 DEG C, and the blending time is 40- 60min, then it is hot-forming by vulcanizing press, hot pressing temperature is 220-230 DEG C, and hot pressing time 20-30min finally leads to Sheet-punching machine is crossed to form to obtain magnetic poly- (biasfluoroethylene-hexafluoropropylene) organic and inorganic insulating composite material component 1.
Embodiment 2:
(1) multi-walled carbon nanotube of preparation acidification: 4 parts of glacial acetic acids are successively weighed, 6 parts of dilute hydrochloric acid are put into and are passed through N2Three necks In bottle, 3 parts of multi-walled carbon nanotubes are added, N will be passed through2Three-necked bottle be placed in processor for ultrasonic wave, carry out ultrasonic treatment 1- 1.5h, ultrasound after by three-necked bottle heating water bath to 75-80 DEG C, react 12-15h, filtered, will be taken out after fully reacting Material after filter distills water washing by 2000-3000mL, removes remaining acetate and hydrochloride, until material is in neutrality, by object Material, which is placed in baking oven, is heated to 85-90 DEG C of drying moisture, obtains the acidification multi-walled carbon nanotube of black powder solid, COOH- MWCNTs-HCl nanoparticle 2；
(2) it weighs 7 parts of magnetic Nano nickel oxide, is added in 500mL beaker, sequentially add 200ml distilled water, and on COOH-MWCNTs-HCl nanoparticle made from step (1) is stated, heating water bath makes COOH- to 60-65 DEG C of at the uniform velocity stirring 2-3h MWCNTs-HCl nanoparticle and magnetism NiO are uniformly mixed, then material is transferred into high-pressure hydrothermal reaction kettle, temperature 105- 110 DEG C, heating reaction 6-8h makes magnetic NiO be adhering completely to COOH-MWCNTs-HCl nanoparticle surface, magnetic is prepared Property NiO modification COOH-MWCNTs-HCl functional nano filler 2；
(3) it weighs in 79 parts of poly- (biasfluoroethylene-hexafluoropropylene) 1000mL beakers, adds 200mL distilled water, 300mL The nanoparticle and 1 part of metatitanic acid of magnetism NiO obtained modification COOH-MWCNTs-HCl in ethylene glycol and above-mentioned steps (2) Ester coupling agent, heating water bath quickly stir 30-40min to 70-75 DEG C, make poly- (biasfluoroethylene-hexafluoropropylene) and magnetism NiO The nanoparticle for modifying COOH-MWCNTs-HCl is uniformly mixed, and after stirring stirring completely, material filtering is washed by distillation It washs to ethylene glycol and completely removes, then material is placed in 85-90 DEG C of baking oven and dries moisture, obtain poly- (vinylidene-hexafluoro third Alkene)-magnetism NiO modification COOH-MWCNTs-HCl functional material 2；
(4) mixture is placed in melt blending in kneading machine, melt blending temperature is 250-270 DEG C, and the blending time is 40- 60min, then it is hot-forming by vulcanizing press, hot pressing temperature is 220-230 DEG C, and hot pressing time 20-30min finally leads to Sheet-punching machine is crossed to form to obtain magnetic poly- (biasfluoroethylene-hexafluoropropylene) organic and inorganic insulating composite material component 2.
Embodiment 3:
(1) multi-walled carbon nanotube of preparation acidification: 6 parts of glacial acetic acids are successively weighed, 8 parts of dilute hydrochloric acid are put into and are passed through N2Three necks In bottle, 4 parts of multi-walled carbon nanotubes are added, N will be passed through2Three-necked bottle be placed in processor for ultrasonic wave, carry out ultrasonic treatment 1- 1.5h, ultrasound after by three-necked bottle heating water bath to 75-80 DEG C, react 12-15h, filtered, will be taken out after fully reacting Material after filter distills water washing by 2000-3000mL, removes remaining acetate and hydrochloride, until material is in neutrality, by object Material, which is placed in baking oven, is heated to 85-90 DEG C of drying moisture, obtains the acidification multi-walled carbon nanotube of black powder solid, COOH- MWCNTs-HCl nanoparticle 3；
(2) it weighs 8 parts of magnetic Nano nickel oxide, is added in 500mL beaker, sequentially add 200ml distilled water, and on COOH-MWCNTs-HCl nanoparticle made from step (1) is stated, heating water bath makes COOH- to 60-65 DEG C of at the uniform velocity stirring 2-3h MWCNTs-HCl nanoparticle and magnetism NiO are uniformly mixed, then material is transferred into high-pressure hydrothermal reaction kettle, temperature 105- 110 DEG C, heating reaction 6-8h makes magnetic NiO be adhering completely to COOH-MWCNTs-HCl nanoparticle surface, magnetic is prepared Property NiO modification COOH-MWCNTs-HCl functional nano filler 3；
(3) it weighs in 72 parts of poly- (biasfluoroethylene-hexafluoropropylene) 1000mL beakers, adds 200mL distilled water, 300mL The nanoparticle and 2 parts of metatitanic acids of magnetism NiO obtained modification COOH-MWCNTs-HCl in ethylene glycol and above-mentioned steps (2) Ester coupling agent, heating water bath quickly stir 30-40min to 70-75 DEG C, make poly- (biasfluoroethylene-hexafluoropropylene) and magnetism NiO The nanoparticle for modifying COOH-MWCNTs-HCl is uniformly mixed, and after stirring stirring completely, material filtering is washed by distillation It washs to ethylene glycol and completely removes, then material is placed in 85-90 DEG C of baking oven and dries moisture, obtain poly- (vinylidene-hexafluoro third Alkene)-magnetism NiO modification COOH-MWCNTs-HCl functional material 3；
(4) mixture is placed in melt blending in kneading machine, melt blending temperature is 250-270 DEG C, and the blending time is 40- 60min, then it is hot-forming by vulcanizing press, hot pressing temperature is 220-230 DEG C, and hot pressing time 20-30min finally leads to Sheet-punching machine is crossed to form to obtain magnetic poly- (biasfluoroethylene-hexafluoropropylene) organic and inorganic insulating composite material component 3.
Embodiment 4:
(1) multi-walled carbon nanotube of preparation acidification: 8 parts of glacial acetic acids are successively weighed, 10 parts of dilute hydrochloric acid are put into and are passed through N2Three In neck bottle, 5 parts of multi-walled carbon nanotubes are added, N will be passed through2Three-necked bottle be placed in processor for ultrasonic wave, be ultrasonically treated 1-1.5h, ultrasound after by three-necked bottle heating water bath to 75-80 DEG C, react 12-15h, filtered, will be taken out after fully reacting Material after filter distills water washing by 2000-3000mL, removes remaining acetate and hydrochloride, until material is in neutrality, by object Material, which is placed in baking oven, is heated to 85-90 DEG C of drying moisture, obtains the acidification multi-walled carbon nanotube of black powder solid, COOH- MWCNTs-HCl nanoparticle 4；
(2) it weighs 10 parts of magnetic Nano nickel oxide, is added in 500mL beaker, sequentially add 200 ml distilled water, and on COOH-MWCNTs-HCl nanoparticle made from step (1) is stated, heating water bath makes COOH- to 60-65 DEG C of at the uniform velocity stirring 2-3h MWCNTs-HCl nanoparticle and magnetism NiO are uniformly mixed, then material is transferred into high-pressure hydrothermal reaction kettle, temperature 105- 110 DEG C, heating reaction 6-8h makes magnetic NiO be adhering completely to COOH-MWCNTs-HCl nanoparticle surface, magnetic is prepared Property NiO modification COOH-MWCNTs-HCl functional nano filler 4；
(3) it weighs in 64 parts of poly- (biasfluoroethylene-hexafluoropropylene) 1000mL beakers, adds 200mL distilled water, 300mL The nanoparticle and 3 parts of metatitanic acids of magnetism NiO obtained modification COOH-MWCNTs-HCl in ethylene glycol and above-mentioned steps (2) Ester coupling agent, heating water bath quickly stir 30-40min to 70-75 DEG C, make poly- (biasfluoroethylene-hexafluoropropylene) and magnetism NiO The nanoparticle for modifying COOH-MWCNTs-HCl is uniformly mixed, and after stirring stirring completely, material filtering is washed by distillation It washs to ethylene glycol and completely removes, then material is placed in 85-90 DEG C of baking oven and dries moisture, obtain poly- (vinylidene-hexafluoro third Alkene)-magnetism NiO modification COOH-MWCNTs-HCl functional material 4；
(4) mixture is placed in melt blending in kneading machine, melt blending temperature is 250-270 DEG C, and the blending time is 40- 60min, then it is hot-forming by vulcanizing press, hot pressing temperature is 220-230 DEG C, and hot pressing time 20-30min finally leads to Sheet-punching machine is crossed to form to obtain magnetic poly- (biasfluoroethylene-hexafluoropropylene) organic and inorganic insulating composite material component 4.

Claims (8)

1. a kind of poly- (biasfluoroethylene-hexafluoropropylene) organic and inorganic insulating composite material and preparation method thereof of magnetism, including with The raw material of lower parts by weight proportion, it is characterised in that: 60-85 parts poly- (biasfluoroethylene-hexafluoropropylene), 2-5 parts of multi-wall carbon nano-tubes Pipe, 5-10 parts of magnetic Nano nickel oxide, 3-8 parts of glacial acetic acids, 5-10 parts of dilute hydrochloric acid, 1-3 parts of titanate coupling agents.
2. according to claim 1 a kind of poly- (biasfluoroethylene-hexafluoropropylene) the organic and inorganic insulating composite material of magnetism and Preparation method, it is characterised in that: poly- (biasfluoroethylene-hexafluoropropylene) monomer is vinylidene and hexafluoropropene, inclined fluorine Acetate unit content is 75-80%, and hexafluoropropene unit content is 20-25%, Polymer Molecular Weight is 500~ 560kg/mol, structural formula are as follows:
3. according to claim 1 a kind of poly- (biasfluoroethylene-hexafluoropropylene) the organic and inorganic insulating composite material of magnetism and Preparation method, it is characterised in that: the multi-walled carbon nanotube is the allotrope of carbon, and the outer diameter of multi-walled carbon nanotube is 15-30nm, internal diameter 1-3nm, length 2.5-4um.
4. according to claim 1 a kind of poly- (biasfluoroethylene-hexafluoropropylene) the organic and inorganic insulating composite material of magnetism and Preparation method, it is characterised in that: the content of NiO is 98.2-99.5% in the magnetic Nano nickel oxide.
5. according to claim 1 a kind of poly- (biasfluoroethylene-hexafluoropropylene) the organic and inorganic insulating composite material of magnetism and Preparation method, it is characterised in that: the glacial acetic acid is the CH that concentration is 97-98%3CH2COOH solution, substance withdrawl syndrome are 16.5-17.1mol/L density 1.231-1.045g/cm3。
6. according to claim 1 a kind of poly- (biasfluoroethylene-hexafluoropropylene) the organic and inorganic insulating composite material of magnetism and Preparation method, it is characterised in that: the dilute hydrochloric acid is that concentration is 20%-21%, substance withdrawl syndrome 6.05-6.17mol/ L, density 1.103-1.113g/cm3。
7. according to claim 1 a kind of poly- (biasfluoroethylene-hexafluoropropylene) the organic and inorganic insulating composite material of magnetism and Preparation method, it is characterised in that: the titanate coupling agent is isopropyl three (dioctyl phosphoric acid acyloxy) titanate esters.
8. according to claim 1 a kind of poly- (biasfluoroethylene-hexafluoropropylene) the organic and inorganic insulating composite material of magnetism and Preparation method, it is characterised in that: poly- (biasfluoroethylene-hexafluoropropylene) the organic and inorganic insulating composite material of the magnetism, system Preparation Method the following steps are included:
(1) multi-walled carbon nanotube of preparation acidification: 3-8 parts of glacial acetic acids are successively weighed, 5-10 parts of dilute hydrochloric acid are put into and are passed through N2Three necks In bottle, 2-5 parts of multi-walled carbon nanotubes are added, N will be passed through2Three-necked bottle be placed in processor for ultrasonic wave, be ultrasonically treated 1-1.5h, ultrasound after by three-necked bottle heating water bath to 75-80 DEG C, react 12-15h, filtered, will be taken out after fully reacting Material after filter distills water washing by 2000-3000mL, removes remaining acetate and hydrochloride, until material is in neutrality, by object Material, which is placed in baking oven, is heated to 85-90 DEG C of drying moisture, obtains the acidification multi-walled carbon nanotube of black powder solid, COOH- MWCNTs-HCl nanoparticle；
(2) it weighs 5-10 parts of magnetic Nano nickel oxide, is added in 500mL beaker, sequentially add 200ml distilled water and above-mentioned COOH-MWCNTs-HCl nanoparticle made from step (1), heating water bath make COOH- to 60-65 DEG C of at the uniform velocity stirring 2-3h MWCNTs-HCl nanoparticle and magnetism Ni0 are uniformly mixed, then material is transferred into high-pressure hydrothermal reaction kettle, temperature 105- 110 DEG C, heating reaction 6-8h makes magnetic NiO be adhering completely to COOH-MWCNTs-HCl nanoparticle surface, magnetic is prepared Property NiO modification COOH-MWCNTs-HCl functional nano filler；
(3) it weighs in 60-85 parts of poly- (biasfluoroethylene-hexafluoropropylene) 1000mL beakers, adds 200mL distilled water, 300mL second The nanoparticle and 1-3 parts of titanate esters of magnetism NiO obtained modification COOH-MWCNTs-HCl in glycol and above-mentioned steps (2) Coupling agent, heating water bath quickly stir 30-40min to 70-75 DEG C, repair poly- (biasfluoroethylene-hexafluoropropylene) and magnetism NiO The nanoparticle for adoring COOH-MWCNTs-HCl is uniformly mixed, after stirring stirring completely, by material filtering, by distilling water washing It is completely removed to ethylene glycol, then material is placed in 85-90 DEG C of baking oven and dries moisture, obtain poly- (vinylidene-hexafluoro third Alkene)-magnetism NiO modification COOH-MWCNTs-HCl functional material.
CN201910622359.5A 2019-07-10 2019-07-10 A kind of poly- (biasfluoroethylene-hexafluoropropylene) organic and inorganic insulating composite material and preparation method thereof of magnetism Withdrawn CN110437563A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103183885A (en) * 2011-12-28 2013-07-03 清华大学 Carbon nanotube composite membrane
CN105153604A (en) * 2015-07-29 2015-12-16 中南大学 Dielectric composite material based on carbon nanotube
CN105949683A (en) * 2016-04-29 2016-09-21 武汉理工大学 Polymer-based flexible composite material having both ferroelectric properties and ferromagnetic properties, and preparation method thereof
CN108570201A (en) * 2018-05-10 2018-09-25 深圳清华大学研究院 dielectric composite material and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103183885A (en) * 2011-12-28 2013-07-03 清华大学 Carbon nanotube composite membrane
CN105153604A (en) * 2015-07-29 2015-12-16 中南大学 Dielectric composite material based on carbon nanotube
CN105949683A (en) * 2016-04-29 2016-09-21 武汉理工大学 Polymer-based flexible composite material having both ferroelectric properties and ferromagnetic properties, and preparation method thereof
CN108570201A (en) * 2018-05-10 2018-09-25 深圳清华大学研究院 dielectric composite material and preparation method thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
安宁丽等: "Fe3O4-碳纳米管/聚偏氟乙烯复合材料的制备与性能", 《复合材料学报》 *
杨永平等: "《新知新语》", 30 June 2010, 河南人民出版社 *
王飞鹏等: "新型铁电共聚物——偏氟乙烯-六氟丙烯的研究", 《材料导报》 *
陈林等: "聚偏氟乙烯/酸化多壁碳纳米管复合材料的制备及性能", 《工程塑料应用》 *

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Application publication date: 20191112