CN116554553B - Functionalized boron nitride nano-sheet, polyurethane elastomer, polypropylene composite material, and preparation methods and applications thereof - Google Patents

Functionalized boron nitride nano-sheet, polyurethane elastomer, polypropylene composite material, and preparation methods and applications thereof Download PDF

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CN116554553B
CN116554553B CN202310707489.5A CN202310707489A CN116554553B CN 116554553 B CN116554553 B CN 116554553B CN 202310707489 A CN202310707489 A CN 202310707489A CN 116554553 B CN116554553 B CN 116554553B
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boron nitride
bnns
polyurethane elastomer
ball milling
parts
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CN116554553A (en
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张茜
周帆
刘学宝
朱勤芬
朱文英
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Sinostar Cable Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/2224—Magnesium hydroxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C08K2003/382—Boron-containing compounds and nitrogen
    • C08K2003/385—Binary compounds of nitrogen with boron
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Abstract

The invention discloses a functionalized boron nitride nano-sheet, a polyurethane elastomer, a polypropylene composite material and preparation methods and applications thereof, (1) 2, 3-epoxypropyl trimethyl ammonium chloride and diphenyl phosphate are mixed and heated to form a phosphorus-containing eutectic solvent p-DES; (2) Adding hexagonal boron nitride h-BN and p-DES and agate pellets into a ball milling tank for ball milling; (3) Dispersing the mixture after ball milling into a mixed solution of isopropanol and water for ultrasonic treatment; (4) Centrifuging to remove the unpeeled h-BN and P-DES to obtain a functionalized boron nitride nanosheet P-BNNS; (5) Mixing polyester diol and P-BNNS, adding hexamethylene diisocyanate, and adding a chain extender and a catalyst to prepare the P-BNNS modified polyurethane elastomer P-BNNS@PU; (6) P-BNNS@PU is taken as a flame retardant and toughening modifier, an auxiliary agent package is prepared by the P-BNNS@PU, an inorganic flame retardant, a dielectric modifier and an antioxidant, polypropylene resin and the auxiliary agent package are mixed, extruded and granulated to prepare the polypropylene insulating material, and the polypropylene insulating material is applied to the field of cables.

Description

Functionalized boron nitride nano-sheet, polyurethane elastomer, polypropylene composite material, and preparation methods and applications thereof
Technical Field
The invention relates to the technical field of polymer composite materials and cable processing, in particular to a polypropylene composite material and a preparation method and application thereof.
Background
The development of 5G communication has put higher demands on the dielectric constant properties of cable materials. The lower the dielectric constant of the material is, the faster the signal transmission speed is, the delay of the electromagnetic wave signal is reduced, and the transmission loss of the electromagnetic wave signal is also reduced. Therefore, the signal transmission line based on 5G is mainly made of polypropylene. The polypropylene has simple processing and low cost, and the dielectric constant of 2.25-2.3 can barely meet the 5G signal transmission requirement, but has low polypropylene oxygen index, and can not meet the cable with high flame retardant performance requirement, such as a data wire. The flame retardant property of polypropylene can be improved by adding flame retardant filler, but the dielectric constant is easy to rise, so that the prepared product cannot be used as an insulating material for 5G signal transmission. Therefore, the preparation of the polypropylene composite material with high flame retardance and low dielectric property has important significance.
Hexagonal boron nitride (h-BN) is an excellent flame-retardant, low-thermal expansion coefficient and heat-conducting insulating material and is widely used for preparing flame-retardant and low-dielectric polymer matrix composite materials. Compared with blocky boron nitride, the boron nitride nano-sheet has more excellent mechanical property and flame retardant property. However, the preparation of BNNS by stripping bulk h-BN still has the problems of low efficiency, toxic and harmful stripping solvents/auxiliary agents, easy volatilization and the like. Meanwhile, BNNS is used as an inorganic filler, has poor compatibility when being compounded with a polymer, and is well dispersed in the polymer matrix and tightly combined with the matrix through functional modification. Therefore, the adoption of the green solvent/auxiliary agent for high-efficiency stripping preparation of the functional BNNS has important application value.
Disclosure of Invention
The invention aims to provide a polypropylene composite material with good flame retardance and dielectric property and a preparation method thereof, so as to solve the technical problems of the polypropylene material in the field of cable application.
The invention aims to provide a green preparation and functionalization method of boron nitride nanosheets, which improves physical properties of boron nitride, introduces a reactive epoxy functional group and N, P element through non-covalent modification, improves compatibility with a resin matrix, and further improves flame retardant property.
The invention further aims to realize the combination of BNNS and polyurethane through an in-situ combination technology, and the compound is used as a flame retardant for the flame retardance of polypropylene, and simultaneously can solve the brittleness problem caused by adding an inorganic flame retardant as an elastomer.
It is a further object of the present invention to prepare a low dielectric constant polypropylene composite using BNNS in combination with polytetrafluoroethylene wax to modify polypropylene.
In order to achieve the above purpose, the present invention provides the following technical solutions:
in one aspect, the present invention provides a functionalized boron nitride nanosheet, wherein the surface of the functionalized boron nitride nanosheet is covalently modified with a molecular pair containing phosphorus and an epoxy functional group; the lateral dimension of the functionalized boron nitride nano-sheet is 1-5 mu m, and 30-40% of the boron nitride nano-sheet has the lateral dimension of 5 mu m; the edge of the boron nitride nano sheet is curled, and the thickness of the boron nitride nano sheet is 5-10nm.
On the other hand, the invention provides a preparation method of the functionalized boron nitride nano-sheet, which comprises the following steps: adding hexagonal boron nitride h-BN, a phosphorus-containing eutectic solvent P-DES and grinding balls into a ball milling tank for ball milling treatment, dispersing a ball milling mixture obtained after ball milling into a mixed solvent of isopropanol and water, and separating to obtain phosphorus-containing functionalized boron nitride nano-sheets (P-BNNS) after mixing treatment, wherein the phosphorus-containing eutectic solvent P-DES is formed by mixing 2, 3-epoxypropyl trimethyl ammonium chloride (GTMAC) and diphenyl phosphate (SDP).
As one embodiment of the present invention, the grinding balls comprise agate pellets.
As an embodiment of the present invention, the mixing treatment includes removing unpeeled hexagonal boron nitride h-BN by low-speed centrifugation after ultrasonic treatment, and obtaining a dispersion liquid by high-speed centrifugation to obtain phosphorus-containing functionalized boron nitride nanoplatelets (P-BNNS).
As one embodiment of the invention, the time of the ultrasonic treatment is 1-10 h, and the power of the ultrasonic treatment is 100-400W. In one example, it is preferable that the time of the ultrasonic treatment is 2 hours and the power of the ultrasonic treatment is 200W.
As one embodiment of the invention, the low-speed centrifugation speed is 1000-4000rpm, and the centrifugation time is 5-30 min; in one example, it is preferable that the low speed centrifugation is at 2000rpm for 20 minutes.
As one embodiment of the present invention, the high-speed centrifugation is performed at 8000 to 15000rpm for 5 to 20 minutes. In one example, it is preferable that the high-speed centrifugation has a speed of 12000rpm and a centrifugation time of 10min.
As an embodiment of the present invention, the molar ratio of 2, 3-epoxypropyltrimethylammonium chloride (GTMAC) to diphenyl phosphate (SDP) is 4:1 to 1:4, and in one example, is preferably 1:2.
As one embodiment of the invention, the preparation method of the phosphorus-containing eutectic solvent p-DES comprises the following steps: 2, 3-epoxypropyl trimethyl ammonium chloride (GTMAC) and diphenyl phosphate (SDP) are mixed and heated for reaction, and then a phosphorus-containing eutectic solvent (p-DES) is formed.
In one embodiment of the present invention, the heating temperature is 60 to 100℃and the reaction time is 2 to 10 hours.
As one embodiment of the present invention, the mass ratio of the hexagonal boron nitride h-BN and the p-DES is 1:5-50, wherein the ball milling speed is 300-600rpm, and the ball milling time is 2-24h.
As one embodiment of the invention, the ball-milling mixture obtained after ball milling is dispersed in a mixed solvent of isopropanol and water at a concentration of 1-10mg/ml, wherein the volume ratio of the water to the isopropanol is 7:3. In one example, 7:3 is preferred.
In another aspect, the present invention provides a modified polyurethane elastomer comprising functionalized boron nitride nanoplatelets P-BNNS as described above.
In one embodiment of the present invention, the modified polyurethane elastomer has a dielectric constant of 1.8 to 2.2 and a thermal conductivity of 5 to 15W/(m K). In one example of the invention, the modified polyurethane elastomer has a dielectric constant of 1.8 and a thermal conductivity of 12.56W/(m K).
As an embodiment of the present invention, the modified polyurethane elastomer further comprises a polyester diol, a hexamethylene diisocyanate catalyst, and a chain extender.
In another aspect, the invention provides a method for preparing a modified polyurethane elastomer, comprising the steps of:
(1) mixing and heating polyester diol and hexamethylene diisocyanate to perform a prepolymerization reaction;
(2) adding a catalyst, a chain extender and a functionalized boron nitride nanosheet P-BNNS into the reaction system in the step (1), heating for reaction, and uniformly stirring to obtain a mixture to be mixed;
(3) extruding and granulating the mixture to obtain the P-BNNS polyurethane elastomer (P-BNNS@PU).
As an embodiment of the present invention, the following raw materials are provided in parts by weight: 45-70 parts of polyester diol, 5-30 parts of functionalized boron nitride nano-sheet P-BNNS, 15-30 parts of hexamethylene diisocyanate, 2-6 parts of chain extender and 0.01-0.05 part of catalyst.
In one embodiment of the present invention, the chain extender is one of glycol chain extenders.
As one embodiment of the invention, the catalyst is one or more of stannous octoate, dibutyl tin dioctanoate and dibutyl tin laurate.
As one embodiment of the present invention, the temperature of the prepolymerization reaction in the step (1) is 60 to 90℃and the time is 3 to 5 hours.
As one embodiment of the present invention, the heating reaction in the step (2) is carried out at a temperature of 60 to 90 ℃ for a time of 1 to 4 hours.
On the other hand, the invention provides application of the modified polyurethane elastomer in the field of flame retardants, wherein the modified polyurethane elastomer is used as a flame retardant and toughening modifier.
In another aspect, the present invention provides a polypropylene composite comprising a modified polyurethane elastomer as described above, said polypropylene composite having a dielectric constant of no more than 2.3 and a fire rating of V-0.
As an embodiment of the invention, the polypropylene composite material comprises the following components in parts by mass: 50-70 parts of polypropylene resin, 20-30 parts of compound flame retardant, 10-20 parts of dielectric modifier and 0.6 part of antioxidant; the compound flame retardant is P-BNNS@PU: aluminum hydroxide (ATH), magnesium hydroxide (MDH) = (20-40): (20-40): (20-40) mass ratio.
As one embodiment of the present invention, the dielectric modifier is tetrafluoroethylene wax; the antioxidant is antioxidant 168: antioxidant 1010=1: 1 mass ratio.
In another aspect, the present invention provides a method for preparing a polypropylene composite material, the method comprising: and uniformly mixing polypropylene resin granules with the premix of the modified polyurethane elastomer and the rest components, extruding and granulating in an extruder, wherein the screw speed is 300-600rpm, and the processing temperature is 180-220 ℃.
On the other hand, the invention provides application of the polypropylene composite material in the field of insulating materials, and particularly in the field of cables.
The beneficial effects are that:
(1) In the invention, the green eutectic solvent containing phosphorus and epoxy functional groups is adopted to strip and surface modify the massive hexagonal boron nitride, the GTMAC and SDP are subjected to noncovalent modification of h-BNNS through pi-pi interaction by adopting the eutectic solvent formed by hydrogen bonds, and then the eutectic solvent is introduced into the polyurethane elastomer, the functionalized modified boron nitride nano-sheet is covalently connected into the polyurethane matrix through the epoxy groups, so that the compatibility of inorganic filler and polymer is enhanced, and meanwhile, the stripped BNNS forms a sheet layer barrier layer, so that the heat transfer path is effectively prolonged, and the loss of heat in the transfer process is increased, thereby reducing the heat mass transfer efficiency of the material matrix outside and effectively improving the flame retardant property of the material matrix.
(2) According to the invention, the polyurethane elastomer is added into the cable matrix, and the flame retardant effect of the inorganic flame retardant and the flame retardant polyurethane elastomer is utilized to strengthen coke residues, so that a compact protective layer can be rapidly formed on the surface of the material, heat mass transfer between the cable material and the outside and exchange between the cable material and combustible gas are isolated, and the cable has excellent flame retardant property. Meanwhile, the addition of the polyurethane elastomer has a certain toughening and modifying effect, and the damage of the addition of the inorganic flame retardant to the toughness is improved.
(3) The functionalized BNNS not only has flame retardant effect, but also has synergistic effect with the dielectric modifier, so that the dielectric property of the polypropylene composite material is improved, and the cable has excellent electrical property.
Drawings
FIG. 1 is a schematic diagram of the technical route of the present invention.
FIG. 2 is a photograph of a P-BNNS Scanning Electron Microscope (SEM) prepared by delamination in example 1 of the present invention.
Detailed Description
The invention will be further described with reference to the drawings and examples. The invention will be better understood from the following examples. However, it will be readily understood by those skilled in the art that the specific material ratios, process conditions and results thereof described in the examples are illustrative of the present invention and should not be construed as limiting the invention described in detail in the claims.
Examples
The flame-retardant low-dielectric-constant polypropylene insulating material comprises the following raw materials in parts by weight: 55-65 parts of polypropylene resin, 20-30 parts of compound flame retardant, 10-20 parts of dielectric modifier and 0.6 part of antioxidant.
As shown in FIG. 1, the preparation method of the flame-retardant low-dielectric-constant polypropylene insulating material comprises the following steps: raw materials are weighed according to the proportion, the polypropylene granules and the premix of the rest components are put into a high-speed mixer to be mixed uniformly, and then the mixture is added into a double-screw extruder to be extruded and granulated, wherein the screw speed is 300-600rpm, and the processing temperature is 180-220 ℃.
The compound flame retardant is P-BNNS@PU: aluminum hydroxide (ATH), magnesium hydroxide (MDH) = (40-60): (20-40): (20-40) compounding; the dielectric modifier is tetrafluoroethylene wax; the antioxidant is antioxidant 168: antioxidant 1010=1: 1 are compounded.
As a further preferable scheme of the invention, the preparation steps of the P-BNNS@PU are as follows:
(1) mixing and heating polyester diol and hexamethylene diisocyanate to perform a prepolymerization reaction;
(2) adding a catalyst, a chain extender and P-BNNS into the reaction system in the step (1), heating for reaction, and uniformly stirring to obtain a mixture to be mixed;
(3) extruding and granulating the mixture to obtain the P-BNNS polyurethane elastomer.
As a further preferable scheme of the invention, the raw material composition of the P-BNNS@PU comprises the following components in percentage by mass: 45-70 parts of polyester diol, 5-30 parts of P-BNNS, 15-30 parts of hexamethylene diisocyanate, 2-6 parts of chain extender and 0.05-0.1 part of catalyst.
As a further preferable scheme of the invention, the chain extender is one of glycol chain extenders, and the catalyst is one or more of stannous octoate, dibutyl tin dioctanoate and dibutyl tin laurate.
As a further preferable mode of the invention, the temperature of the prepolymerization reaction in the step (1) is 60-90 ℃ and the time is 3-5 h, and the temperature of the heating reaction in the step (2) is 60-90 ℃ and the time is 1-4 h.
As a further preferred scheme of the invention, the surface of the functionalized boron nitride nanosheet is covalently modified with a molecular pair containing phosphorus and epoxy functional groups; the transverse dimension of the functionalized boron nitride nano-sheet is 1-5 mu m, and 30-40% of the boron nitride nano-sheet has 5 mu m; the edge of the boron nitride nano sheet is curled, and the thickness of the boron nitride nano sheet is 1-10nm.
As a further preferable scheme of the invention, the functionalized boron nitride nano-sheet is prepared by performing p-DES assisted h-BN ball milling and then performing ultrasonic stripping by a solution.
As a further preferable scheme of the invention, the mass ratio of the hexagonal boron nitride h-BN to the hexagonal boron nitride p-DES is 1:5-50, wherein the ball milling speed is 300-600rpm, and the ball milling time is 2-24h. The mixture obtained after ball milling is dispersed in a mixed solvent of water and isopropanol at a concentration of 1-10 mg/ml. The volume ratio of the water to the isopropanol is 7:3; the time of the ultrasonic treatment is 2h, and the power of the ultrasonic treatment is 200W. The low-speed centrifugation speed was 2000rpm and the centrifugation time was 20min. The speed of the high-speed centrifugation is 12000rpm, and the centrifugation time is 10min.
As a further preferable scheme of the invention, the phosphorus-containing eutectic solvent (p-DES) is obtained by mixing and heating 2, 3-epoxypropyl trimethyl ammonium chloride (GTMAC) and diphenyl phosphate (SDP), wherein the mol ratio of the GTMAC to the SDP is 1:2, the heating temperature is 60-100 ℃, and the reaction time is 2-10 hours.
The following are specific examples of the present invention, and the technical solutions of the present invention are further described, but the present invention is not limited to these examples. The following raw materials used in the present invention are all commonly used in the art unless otherwise specified.
Example 1
(1) preparation of p-DES: weighing 2, 3-epoxypropyl trimethyl ammonium chloride (GTMAC) and diphenyl phosphate (SDP) in a round-bottom flask, wherein the molar ratio of the GTMAC to the SDP is 1:2, heating to 80 ℃ under the stirring action, and reacting for 4 hours to obtain clear liquid, namely p-DES;
(2) Preparation of functionalized hexagonal boron nitride nanosheets P-BNNS: firstly, 0.5g h-BN and 2.5g of p-DES are put into a ball milling tank, 3 agate pellets with the diameter of 1.2cm, 15 agate pellets with the diameter of 1cm, 10 agate pellets with the diameter of 8mm and 50 agate pellets with the diameter of 6mm (the total mass of all the agate pellets is about 50 g) are put into the ball milling tank, and ball milling is carried out for 24 hours at the speed of 400 rpm;
dispersing the ball-milled mixture in water/isopropanol (volume 7:3) to obtain a concentration of 5mg/mL, and performing ultrasonic treatment with a ultrasonic cytoclasis instrument at a power of 200W for 2 hours;
the sonicated dispersion was centrifuged at 2000rpm for 20min to remove the unpeeled boron nitride nanoplatelets. And centrifuging the supernatant at a high speed of 12000rpm for 10min, and drying overnight to obtain the functionalized boron nitride nano-sheet P-BNNS with the yield of 55%.
FIG. 2 is a scanning electron micrograph of the boron nitride nanoplatelets P-BNNS prepared in this example, from which it can be seen that large and thin boron nitride nanoplatelets are obtained, having a lateral dimension of 1-5 μm and 30-40% of the boron nitride nanoplatelets have a lateral dimension of 5. Mu.m. As shown in fig. 2, the thickness of the boron nitride nano-sheet is only 5-10nm, the edge is very thin, and curling occurs, and the standing boron nitride nano-sheet exists.
(3) Preparation of P-BNNS@PU: the raw materials comprise the following components in mass: 46 parts of polyester diol, 30 parts of P-BNNS, 19 parts of hexamethylene diisocyanate, 4.99 parts of chain extender and 0.01 part of catalyst. Mixing and heating polyester diol and hexamethylene diisocyanate to 80 ℃ for prepolymerization reaction for 4 hours, adding a catalyst, a chain extender and P-BNNS into a reaction system, and continuously stirring and reacting for 3 hours at 80 ℃ to obtain a to-be-mixed material. Extruding and granulating the mixture to obtain the P-BNNS polyurethane elastomer, namely the P-BNNS@PU.
The P-BNNS polyurethane elastomer P-BNNS@PU has a dielectric constant of 1.8 and a thermal conductivity of 12.56 w/(m K).
(4) Preparation of a polypropylene composite material:
the raw materials are weighed according to the following weight percentages of flame-retardant low-dielectric-constant polypropylene insulating materials: 60 parts of polypropylene resin, 25 parts of compound flame retardant, 14.4 parts of polytetrafluoroethylene wax and 0.6 part of antioxidant, wherein the compound flame retardant comprises the following components in percentage by mass: P-BNNS@PU obtained in step 3: aluminum hydroxide (ATH), magnesium hydroxide (MDH) =20: 40:40 mass ratio, the antioxidant is antioxidant 168: antioxidant 1010=1: 1 mass ratio; the components are premixed by a high-speed mixer, and then the mixture is added into a double-screw extruder for extrusion granulation, wherein the screw speed is 500rap, and the processing temperature is 200 ℃.
Example 2
50 parts of polyester diol, 20 parts of P-BNNS, 25 parts of hexamethylene diisocyanate, 4.99 parts of chain extender and 0.01 part of catalyst. The rest of the procedure is the same as in example 1.
Example 3
60 parts of polyester diol, 10 parts of P-BNNS, 25 parts of hexamethylene diisocyanate, 4.99 parts of chain extender and 0.01 part of catalyst. The rest of the procedure is the same as in example 1.
Example 4
70 parts of polyester diol, 5 parts of P-BNNS, 30 parts of hexamethylene diisocyanate, 4.99 parts of chain extender and 0.01 part of catalyst. The rest of the procedure is the same as in example 1.
Example 5
The flame-retardant low-dielectric-constant polypropylene insulating material is prepared by weighing the following raw materials in percentage by weight: 55 parts of polypropylene resin, 25 parts of compound flame retardant, 19.4 parts of polytetrafluoroethylene wax and 0.6 part of antioxidant, wherein the mass ratio of the components of the compound flame retardant is as follows: P-BNNS@PU of example 1: aluminum hydroxide (ATH), magnesium hydroxide (MDH) =20: 40:40. the rest of the procedure is the same as in example 1.
Example 6
The flame-retardant low-dielectric-constant polypropylene insulating material is prepared by weighing the following raw materials in percentage by weight: 65 parts of polypropylene resin, 25 parts of compound flame retardant, 9.4 parts of polytetrafluoroethylene wax and 0.6 part of antioxidant, wherein the compound flame retardant comprises the following components in percentage by mass: P-BNNS@PU of example 1: aluminum hydroxide (ATH), magnesium hydroxide (MDH) =20: 40:40. the rest of the procedure is the same as in example 1.
Example 7
The flame-retardant low-dielectric-constant polypropylene insulating material is prepared by weighing the following raw materials in percentage by weight: 65 parts of polypropylene resin, 20 parts of compound flame retardant, 14.4 parts of polytetrafluoroethylene wax and 0.6 part of antioxidant, wherein the compound flame retardant comprises the following components in percentage by mass: P-BNNS@PU of example 1: aluminum hydroxide (ATH), magnesium hydroxide (MDH) =20: 40:40. the rest of the procedure is the same as in example 1.
Example 8
The flame-retardant low-dielectric-constant polypropylene insulating material is prepared by weighing the following raw materials in percentage by weight: 55 parts of polypropylene resin, 30 parts of compound flame retardant, 14.4 parts of polytetrafluoroethylene wax and 0.6 part of antioxidant, wherein the mass ratio of the components of the compound flame retardant is as follows: P-BNNS@PU of example 1: aluminum hydroxide (ATH), magnesium hydroxide (MDH) =20: 40:40. the rest of the procedure is the same as in example 1.
Comparative example 1 commercially available flame retardant
The raw materials are weighed according to the following weight percentages of the flame-retardant low-dielectric-constant polypropylene insulating material: 60 parts of polypropylene resin, 25 parts of a commercial flame retardant (FP-2200S), 14.4 parts of polytetrafluoroethylene wax and 0.6 part of an antioxidant; flame retardant low dielectric constant polypropylene insulation material was prepared according to the method of example 1.
Comparative example 2 tetrafluoroethylene wax without dielectric modifier
The raw materials are weighed according to the following weight percentages of the flame-retardant low-dielectric-constant polypropylene insulating material: 74.4 parts of polypropylene resin, 25 parts of compound flame retardant and 0.6 part of antioxidant; flame retardant low dielectric constant polypropylene insulation material was prepared according to the method of example 1.
Comparative example 3 the compounded flame retardant did not contain P-BNNS@PU
The raw materials are weighed according to the following weight percentages of the flame-retardant low-dielectric-constant polypropylene insulating material: 60 parts of polypropylene resin, 25 parts of compound flame retardant, 14.4 parts of polytetrafluoroethylene wax and 0.6 part of antioxidant. Wherein the compound flame retardant is aluminum hydroxide (ATH): magnesium hydroxide (MDH) =50: 50. flame retardant low dielectric constant polypropylene insulation material was prepared according to the method of example 1.
Comparative example 4 starting from unpeeled and functionally modified h-BN
The flame-retardant low-dielectric-constant polypropylene insulating material is prepared by taking the block-shaped non-stripped and functionally modified h-BN modified prepared h-BN@PU as a flame retardant and dielectric modifier according to the method in the embodiment 1.
Comparative example 5
The raw materials are weighed according to the following weight percentages of the flame-retardant low-dielectric-constant polypropylene insulating material: 75 parts of polypropylene resin, 14.4 parts of polytetrafluoroethylene wax and 0.6 part of antioxidant; flame retardant low dielectric constant polypropylene insulation material was prepared according to the method of example 1.
The flame retardant low dielectric constant polypropylene insulation materials prepared in the above examples and comparative examples were tested for hardness (Shore D) according to ASTM D2240, tensile strength (MPa) according to ASTM D638, elongation at break (%) according to ASTM D638, dielectric constant according to ASTM D150, and vertical burn test according to UL 94, and the specific results are shown in Table 1.
TABLE 1 flame retardant low dielectric constant polypropylene insulation material Performance
Tensile Strength (MPa) Elongation at break (%) Dielectric constant Vertical burn test
Example 1 18.1 162 2.24 V-0
Example 2 16.4 181 2.22 V-0
Example 3 15.8 186 2.23 V-0
Example 4 14.3 228 2.22 V-0
Example 5 14.9 224 2.20 V-0
Example 6 15.7 213 2.24 V-0
Example 7 13.6 258 2.23 V-0
Example 8 22.8 155 2.24 V-0
Comparative example 1 17.1 154 2.87 V-0
Comparative example 2 15.3 177 2.98 V-0
Comparative example 3 16.6 159 2.44 V-0
Comparative example 4 11.6 151 2.38 V-0
Comparative example 5 14.8 206 2.66 NG
From the results of Table 1, it can be seen that the polypropylene composites prepared using the P-BNNS@PU modified polyurethane elastomer of the present invention have dielectric constants of less than 2.50, indicating lower dielectric constants, and combustion grades of V-0, as compared with the comparative examples. The polypropylene composite material prepared by using the P-BNNS@PU modified polyurethane elastomer has better strength and toughness compared with an inorganic filler modified polypropylene composite material.
The foregoing is only a preferred embodiment of the invention, it being noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the present invention, and such modifications and adaptations are intended to be comprehended within the scope of the invention.

Claims (30)

1. The preparation method of the functionalized boron nitride nano-sheet is characterized by comprising the following steps of: adding hexagonal boron nitride h-BN, a phosphorus-containing eutectic solvent P-DES and grinding balls into a ball milling tank for ball milling treatment, dispersing a ball milling mixture obtained after ball milling into a mixed solvent of isopropanol and water, and separating to obtain phosphorus-containing functionalized boron nitride nano-sheets P-BNNS after mixing treatment, wherein the preparation method of the phosphorus-containing eutectic solvent P-DES comprises the following steps: the 2, 3-epoxypropyl trimethyl ammonium chloride GTMAC and diphenyl phosphate are mixed and heated for reaction, and then the phosphorus-containing eutectic solvent p-DES is formed.
2. A functionalized boron nitride nanosheet according to claim 1, wherein the functionalized boron nitride nanosheet has a lateral dimension of 1-5 μm and 30-40% of the boron nitride nanosheets have a lateral dimension of 5 μm.
3. The functionalized boron nitride nanosheets of claim 1, wherein the thickness of the boron nitride nanosheets is 5-10nm, the edges of the boron nitride nanosheets being curled.
4. The preparation method of the functionalized boron nitride nanosheets is characterized by comprising the following steps: adding hexagonal boron nitride h-BN, a phosphorus-containing eutectic solvent P-DES and grinding balls into a ball milling tank for ball milling treatment, dispersing a ball milling mixture obtained after ball milling into a mixed solvent of isopropanol and water, and separating to obtain phosphorus-containing functionalized boron nitride nano-sheets P-BNNS after mixing treatment, wherein the preparation method of the phosphorus-containing eutectic solvent P-DES comprises the following steps: the 2, 3-epoxypropyl trimethyl ammonium chloride GTMAC and diphenyl phosphate are mixed and heated for reaction, and then the phosphorus-containing eutectic solvent p-DES is formed.
5. The method of claim 4, wherein the milling balls comprise agate pellets.
6. The method according to claim 4, wherein the mixing treatment comprises removing unpeeled hexagonal boron nitride h-BN by low-speed centrifugation after the ultrasonic treatment, and obtaining the dispersion by high-speed centrifugation to obtain phosphorus-containing functionalized boron nitride nanoplatelets P-BNNS.
7. The method of claim 6, wherein the time of the ultrasonic treatment is 2-10 hours and the power of the ultrasonic treatment is 100-400W.
8. The method of claim 6, wherein the low speed centrifugation is at a speed of 1000-4000rpm and the centrifugation time is 5-30min.
9. The method of claim 6, wherein the high speed centrifugation is at a speed of 8000-15000rpm and the centrifugation time is 5-20min.
10. The method of claim 4, wherein the molar ratio of the 2, 3-epoxypropyl trimethyl ammonium chloride GTMAC to diphenyl phosphate is 1:4-4:1.
11. The method of claim 4, wherein the heating temperature is 60 to 100 ℃ and the reaction time is 2 to 10 hours.
12. The method according to claim 4, wherein the mass ratio of the hexagonal boron nitride h-BN and the p-DES is 1:5-50.
13. The method according to claim 4, wherein the ball milling speed is 300-600rpm and the ball milling time is 2-24 hours.
14. The method according to claim 4, wherein the ball-milled mixture obtained after ball milling is dispersed in a mixed solvent of isopropanol and water at a concentration of 1-10mg/ml, and the volume ratio of water to isopropanol is 7:3.
15. A modified polyurethane elastomer comprising functionalized boron nitride nanoplatelets P-BNNS according to any of claims 1-3 or prepared by the method of any of claims 4-14.
16. The modified polyurethane elastomer of claim 15, wherein the modified polyurethane elastomer has a dielectric constant of 1.8 to 2.2 and a thermal conductivity of 5 to 15W/(m K).
17. The modified polyurethane elastomer of claim 15, further comprising a polyester diol, hexamethylene diisocyanate, a catalyst, and a chain extender.
18. The method for producing a modified polyurethane elastomer as claimed in any one of claims 15 to 17, comprising the steps of:
(1) mixing and heating polyester diol and hexamethylene diisocyanate to perform a prepolymerization reaction;
(2) adding a catalyst, a chain extender and a functionalized boron nitride nanosheet P-BNNS into the reaction system in the step (1), heating for reaction, and uniformly stirring to obtain a mixture to be mixed;
(3) extruding and granulating the mixture to obtain the P-BNNS polyurethane elastomer P-BNNS@PU.
19. The method of claim 18, wherein the parts by weight of the raw materials are as follows: 45-70 parts of polyester diol, 5-30 parts of functionalized boron nitride nano-sheet P-BNNS, 15-30 parts of hexamethylene diisocyanate, 2-6 parts of chain extender and 0.01-0.05 part of catalyst.
20. The method of claim 18, wherein the chain extender is one of glycol chain extenders.
21. The method of claim 18, wherein the catalyst is one or more of stannous octoate, dibutyl tin dioctanoate.
22. The process of claim 18, wherein the temperature of the prepolymerization reaction in step (1) is 60 to 90℃for 3 to 5 hours.
23. The method according to claim 18, wherein the heating reaction in step (2) is carried out at a temperature of 60 to 90 ℃ for a time of 1 to 4 hours.
24. A polypropylene composite comprising the modified polyurethane elastomer of any one of claims 15-17.
25. The polypropylene composite of claim 24, wherein the polypropylene composite has a dielectric constant of not greater than 2.3 and a burn rating of V "0.
26. The polypropylene composite according to claim 24, comprising the following components in parts by mass: 50-70 parts of polypropylene resin, 20-30 parts of compound flame retardant, 10-20 parts of dielectric modifier and 0.6 part of antioxidant; the compound flame retardant is the polyurethane elastomer P-BNNS@PU: aluminum hydroxide ATH, magnesium hydroxide mdh= (20-40): (20-40): (20-40) and is compounded.
27. The polypropylene composite of claim 26, wherein the dielectric modifier is tetrafluoroethylene wax.
28. The polypropylene composite according to claim 26, wherein the antioxidant is antioxidant 168: antioxidant 1010=1: 1 are compounded.
29. The polypropylene composite according to claim 24, wherein the polypropylene composite is prepared by a process comprising: and uniformly mixing polypropylene resin granules with the premix of the modified polyurethane elastomer and the rest components, extruding and granulating in an extruder, wherein the screw speed is 300-600rpm, and the processing temperature is 180-220 ℃.
30. Use of a functionalized boron nitride nanoplatelet according to any of claims 1 to 3, or of a modified polyurethane elastomer according to any of claims 15 to 17, or of a polypropylene composite according to any of claims 24 to 29, in the field of insulating materials.
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