CN115418101A - Method for preparing high-thermal-conductivity PA66 composite material by using hyperbranched polyester - Google Patents
Method for preparing high-thermal-conductivity PA66 composite material by using hyperbranched polyester Download PDFInfo
- Publication number
- CN115418101A CN115418101A CN202211065049.6A CN202211065049A CN115418101A CN 115418101 A CN115418101 A CN 115418101A CN 202211065049 A CN202211065049 A CN 202211065049A CN 115418101 A CN115418101 A CN 115418101A
- Authority
- CN
- China
- Prior art keywords
- mixture
- hyperbranched polyester
- composite material
- preparing
- boron nitride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920006150 hyperbranched polyester Polymers 0.000 title claims abstract description 75
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 30
- 229920002302 Nylon 6,6 Polymers 0.000 title claims abstract description 19
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052582 BN Inorganic materials 0.000 claims abstract description 39
- 239000000203 mixture Substances 0.000 claims abstract description 31
- 239000004677 Nylon Substances 0.000 claims abstract description 24
- 229920001778 nylon Polymers 0.000 claims abstract description 24
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- 238000007731 hot pressing Methods 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 12
- 239000011347 resin Substances 0.000 claims abstract description 11
- 229920005989 resin Polymers 0.000 claims abstract description 11
- 238000000227 grinding Methods 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 239000002322 conducting polymer Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 7
- 238000002844 melting Methods 0.000 claims abstract description 5
- 230000008018 melting Effects 0.000 claims abstract description 5
- 239000004570 mortar (masonry) Substances 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000007872 degassing Methods 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 239000011363 dried mixture Substances 0.000 claims 2
- 238000009210 therapy by ultrasound Methods 0.000 claims 2
- 125000003277 amino group Chemical group 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 8
- 239000002861 polymer material Substances 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 description 16
- 238000012545 processing Methods 0.000 description 9
- 229920000587 hyperbranched polymer Polymers 0.000 description 8
- 239000011159 matrix material Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 6
- 239000000945 filler Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000017525 heat dissipation Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a method for preparing a high-thermal-conductivity PA66 composite material by using hyperbranched polyester, which comprises the following steps: (1) Mixing a certain amount of hyperbranched polyester in a certain organic solvent to form a first mixture, wherein the first mixture solution is slightly yellow and clear, which indicates that the mixture is uniformly mixed; (2) And mixing the first mixture with the boron nitride powder according to the proportion, and uniformly stirring. Then, continuously drying the mixture at 80 ℃ for 12 hours, taking out the mixture, grinding the mixture into powder by using a mortar, continuously drying the mixture in an oven at 80 ℃ for 15 hours to fully remove the solvent, and then continuously grinding the mixture to obtain a final white powdery substance; (3) Premixing the white powder obtained in the step (2) with nylon resin according to a ratio, melting and mixing the mixture through a torque rheometer, and finally hot-pressing the mixture into sheets to obtain a heat-conducting polymer material; the method is simple, easy to operate, low in price, mild in preparation conditions, environment-friendly and capable of efficiently and continuously producing the high-thermal-conductivity polymer material in a large scale.
Description
Technical Field
The application relates to the field of preparation of heat-conducting polymers, in particular to a method for preparing a high-heat-conductivity PA66 composite material by using hyperbranched polyester.
Background
The hyperbranched polyester is a novel material which is bred in the development process of hyperbranched polymers, has multiple varieties and wide application fields, is one of main members in hyperbranched polymer families, and is also the hyperbranched polymer which is researched most at present. The branched repeating unit of the hyperbranched polyester takes ester group as a characteristic group and has the characteristics of typical highly branched structure, spheroidal molecular shape, a large number of terminal groups and the like. The hyperbranched polyester has a plurality of synthesis methods, including AB (x) type monomer self-condensation polymerization, multi-branching ring-opening polymerization, multi-functionality monomer copolymerization and the like; the hyperbranched polyester has a large number of active end group functional groups such as hydroxyl and the like, so that the modification of the end groups can be easily carried out, the multifunctional polyester is endowed with the versatility, and the application field of the hyperbranched polyester is expanded; meanwhile, the hyperbranched polyester is synthesized from a wide range of raw materials, and a plurality of monomers are commercialized, so that the hyperbranched polyester has a good popularization and application basis. Therefore, the advantages of unique molecular structure and performance, convenient preparation method, easy industrial production and the like make the novel polyester attract great attention from birth and research and development of researchers.
Nylon 66 (PA 66) is a crystalline polymer with excellent processability, mechanical properties, abrasion resistance and chemical resistance. The heat conduction filler is added into the polymer, so that the thermal behavior of the polymer can be greatly improved, the three types of commonly used heat conduction fillers are respectively metal filler particles, carbon materials and inorganic heat conduction particles, wherein the inorganic heat conduction particles mainly comprise aluminum oxide, aluminum nitride, silicon nitride, boron nitride, silicon carbide, magnesium oxide and the like, and are main fillers for preparing heat conduction insulating polymer materials; however, when the heat-conducting particles are added into the polymer matrix, in order to achieve ideal performance, a large amount of heat-conducting filler is usually added, so that the heat-conducting particles are difficult to uniformly disperse in the organic matrix, and are agglomerated, thereby affecting the mechanical properties, processing fluidity, heat-conducting performance and the like of the polymer composite material. The hyperbranched polymer has the characteristics of a highly branched three-dimensional quasi-spherical molecular structure, a large number of terminal functional groups, no chain entanglement and the like, so that the hyperbranched polymer has unique physical and chemical properties of good solubility, low solution or melt viscosity and the like. The unique three-dimensional topological structure of the hyperbranched polymer is utilized, so that the boron nitride can be better dispersed in the nylon matrix to form a continuous three-dimensional heat-conducting network structure. Therefore, the hyperbranched polymer is used for modifying the boron nitride and is added into the polymer matrix to improve the heat-conducting property of the polymer.
Disclosure of Invention
The application aims to provide a method for preparing a high-thermal-conductivity polymer material by using hyperbranched polyester as an auxiliary agent, and the method has the advantages of simple process, convenience in operation, controllable cost, mild preparation conditions, environmental friendliness and capability of efficiently and continuously producing a large amount of high-molecular materials with good thermal conductivity.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing a heat-conducting polymer material by taking hyperbranched polyester as an auxiliary agent comprises the following steps:
(1) Mixing a certain amount of hyperbranched polyester in a certain organic solvent to form a first mixture, wherein the mixture solution is slightly yellow and clear, which indicates that the mixture is uniformly mixed;
(2) And mixing the first mixture and the boron nitride powder according to the proportion, uniformly stirring, and judging that the mixture is uniformly stirred by naked eyes if no obvious blocky substance exists. Then, continuously drying the mixture at 80 ℃ for 12 hours, taking out the mixture, grinding the mixture into powder by using a mortar, continuously drying the mixture in an oven at 80 ℃ for 15 hours to fully remove the solvent, and continuously grinding the mixture to obtain a final white powdery substance;
(3) Premixing the white powder obtained in the step (2) with nylon resin according to a ratio, melting and mixing the mixture through a torque rheometer, and finally hot-pressing the mixture into a sheet to obtain a heat-conducting polymer material;
wherein, based on the total mass of the hyperbranched polyester, the boron nitride and the nylon being 100%, the mass percentage of the nylon is 1-60%, the mass percentage of the boron nitride is 1-50%, and the mass percentage of the hyperbranched polyester is 0.5-10%.
The invention relates to a nylon high-thermal-conductivity composite material prepared by using nylon and boron nitride as main bodies and through blending and tabletting by a torque rheometer under the assistance of hyperbranched polyester. The hyperbranched polyester is adhered to the surface of the boron nitride, so that the boron nitride is uniformly dispersed in the nylon matrix, the heat-conducting property of the nylon composite material is improved, and the heat-conducting property of the nylon resin is modified by the boron nitride with good heat-conducting property. After hot press molding, boron nitride treated by hyperbranched polyester forms a three-dimensional heat-conducting network in a nylon matrix, and the network heat built between the boron nitride treated by hyperbranched polyester can realize rapid conduction.
In the above technical solution, the hyperbranched polyester (HBPE) has two functions, the first: the special ester group of HBPE has better compatibility with nylon, so that boron nitride can be uniformly mixed in a nylon matrix, agglomeration is prevented, and a continuous three-dimensional heat-conducting network is formed; secondly, the method comprises the following steps: the HBPE has the characteristics of low viscosity, high solubility, low chain entanglement and the like due to the special topological structure, so that the viscosity of a melt can be obviously reduced in the processing process, the processing is simple and convenient, the surface of a product is smooth, and the energy consumption is reduced.
In step (1) of the present invention, the purpose of mixing and sonicating a certain amount of hyperbranched polyester (HBPE) in a certain amount of an organic solvent is to allow the HBPE to be sufficiently dissolved in the organic solvent. The organic solvent is preferably an organic solvent which has good solubility for the HBPE and can be conveniently removed in subsequent treatment, the organic solvents comprise acetone, ethanol + water solution, dichloromethane, tetrahydrofuran, N, N-dimethylformamide and the like, the particularly preferred organic solvent is at least one of N, N-dimethylformamide, dichloromethane and tetrahydrofuran, and the HBPE has the best solubility in the organic solvents, so that branched chains of the HBPE can be completely unfolded and can be uniformly mixed with boron nitride, and the heat-conducting polymer material with better heat-conducting property can be obtained.
Preferably, step (1) may be performed by first dissolving the hyperbranched polyester in an organic solvent and then mixing the hyperbranched polyester solution with boron nitride.
Preferably, in the step (2), the boron nitride and the HBPE are uniformly mixed in the organic solvent by stirring, the stirring time is 0.1 to 24 hours, and the stirring speed is 100 to 1000rad/min. In this embodiment, stirring can make HBPE have more chances to contact boron nitride, and the HBPE contacts the boron nitride and then has hydrogen bond interaction, so that the HBPE adheres to the surface of the boron nitride, thereby obtaining a heat dissipation polymer material with better heat dissipation performance.
Preferably, in the step (2), the solvent is removed by one or a combination of the following ways: blowing (cold air or hot air), drying in an oven, and rotary steaming.
In step (3) of the present invention, if the polymer molecule contains a chemical group which is easily hydrolyzed, the polymer molecule is hydrolyzed by an acid or an alkali, and thus is degraded. The polyamide molecule having-CONH-as a hydrophilic group, which imparts water absorption to the polyamide, and the polyamide molecule having-CH as a water absorption index 2 The proportion is increased and reduced, and the existence of moisture can cause the hydrolysis of amido bonds in the nylon resin during the processing process, so that the molecular weight is reduced, and the physical and mechanical properties of products are reduced. Therefore, the nylon resin needs to be dried in an oven at 80 ℃ for 24 hours before being premixed in a certain ratio to sufficiently remove moisture.
In the step (3), the heat-conducting nylon composite material obtained by blending the torque rheometer is dried in an oven at 80 ℃ for 24 hours in advance before hot pressing into sheets so as to fully remove moisture.
In the step (3), the conditions for hot pressing into the tablet are as follows: the hot pressing temperature is 270-290 deg.C, the hot pressing pressure is 10-20MPa, and the hot pressing process comprises preheating for 3-8min, degassing for 3-5 times, pressing for 5-15min, and cooling for 15-45s. If the temperature is too low during hot pressing into sheets, the polymer cannot completely reach a molten state, and a complete product cannot be obtained. If the temperature is too high, the polymer and the hyperbranched polyester begin to decompose, and the mechanical property and the heat-conducting property of the polymer heat-conducting composite material are influenced.
Compared with the prior art, the invention has the beneficial effects that: the method is simple, easy to operate, low in price, mild in preparation conditions, environment-friendly and capable of efficiently and continuously producing the high-thermal-conductivity polymer material in a large scale. The heat-conducting polymer prepared by the invention has good heat-conducting property.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments of the present application will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and that those skilled in the art can also obtain other related drawings based on the drawings without inventive efforts.
FIG. 1 is a heat-conducting composite material sheet;
FIG. 2 is a process flow of an embodiment of preparing a high thermal conductive polymer material using a hyperbranched polyester as an auxiliary agent;
FIG. 3 is the thermogravimetric changes of the thermally conductive polymer composites at different HBPE contents in examples 1-4;
FIG. 4 is an enlarged schematic view of the thermogravimetric change of the thermally conductive polymer composite of FIG. 3 for showing region A;
FIG. 5 is a graph of the equilibrium torque for the thermally conductive polymer composites of examples 1-4 at different HBPE levels.
FIG. 6 is a graph showing the change in thermal conductivity of the thermally conductive polymer composites of examples 1-4 at different HBPE contents.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the embodiments of the present application will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are not indicated by manufacturers and are commercially available.
In the present invention, the nylon resin may be selected from various kinds, and for example, nylon 66 chips of Huafeng group having a melting point of 262 ℃ and a melt flow rate of 73g/10min may be selected.
In the present invention, the boron nitride includes hexagonal boron nitride, rhombohedral boron nitride, cubic boron nitride, and wurtzite boron nitride, wherein the hexagonal boron nitride is referred to as "white graphite", and the hexagonal boron nitride is exemplarily selected. .
In the present invention, there are many kinds of hyperbranched polyesters, and for example, the hyperbranched polyester can be a heat-resistant aliphatic hyperbranched polyester from wujiang chemical reagent ltd, which has a molecular weight of 1100g/mol, a hydroxyl value of 600 ± 20mg KOH/g, an acid value of less than 20mg KOH/g, and a hydroxyl number of 10.0 to 12.0/mol.
Example 0: HBPE modified boron nitride
In this embodiment, the HBPE-modified boron nitride may be prepared by dissolving-mixing-stirring, and the specific preparation process includes the following steps:
dissolving hyperbranched polyester (the ratio of HBPE to boron nitride is respectively 1/80/1.
Weighing 20g of boron nitride, mixing the boron nitride with the DMF solution of the hyperbranched polyester, and uniformly stirring.
And (3) putting the mixed slurry after stirring into an oven at 80 ℃ for drying for 12 hours, grinding by using a mortar, grinding into powder, continuously putting into the oven for drying for 15 hours, taking out, and continuously grinding by using the mortar, wherein no obvious granular block can be seen by naked eyes.
Examples 1 to 4: influence of thermal conductivity of boron nitride nanoparticles obtained by different hyperbranched polyester modification ratios
1. Preparation of samples
The HBPE modified boron nitride is premixed with nylon 66 resin according to a certain proportion (the mass fractions are 40.5%, 40%, 42% and 44%, respectively).
And (3) blending the premixed materials by using a torque rheometer to obtain a heat-conducting polymer composite material, and grinding the obtained heat-conducting polymer composite material by using a grinder to obtain the granular polymer composite material.
The ground polymer composite was oven-dried at 80 ℃ for 10h and immediately tabletted after removal.
2. Characterization and testing
Testing the thermal conductivity of Polymer composites
(1) Testing the density and the thermal diffusion coefficient of the piece obtained by tabletting according to the calculation formula of the thermal conductivity, wherein lambda = alpha rho C ρ Obtaining the thermal conductivity coefficient, wherein alpha is the thermal diffusion coefficient, rho is the density of the material, C ρ The heat conductivity of the material can be calculated according to the three parameters, and the heat conduction quality of the material is verified. This method allows very accurate calculation of the thermal conductivity of the material as shown in figure 6.
(2) Heat conductivity coefficient tester
The thermal conductivity tester is LFA 467 produced by Germany NETZSCH company
The sample is round, the diameter is 12.7mm, and the maximum thickness is 10mm.
(3) Thermogravimetric analysis of thermally conductive polymer composites
In order to test the content of boron nitride in the thermally conductive composite material, thermogravimetric analysis was performed as shown in fig. 3 and 4.
(4) Rheological properties of thermally conductive polymer composites
In order to test the influence of the proportion of the hyperbranched polymer on the processing flow property of the heat-conducting composite material, the variation of the balance torque with the proportion of the hyperbranched polyester in the processing process is shown in fig. 5
3. Comparison and analysis of test results
The results are shown in table 1:
as can be seen from fig. 3 and 4, the boron nitride is uniformly mixed in the nylon matrix. Provides a good foundation for the subsequent formation of a continuous three-dimensional heat-conducting network.
As can be seen from fig. 5, as the content of the hyperbranched polyester increases, the equilibrium torque generally decreases, and the presence of the hyperbranched polyester improves the processing flowability of the polymer, because the hyperbranched polyester has a highly branched three-dimensional quasi-spherical molecular structure, so that the shear viscosity is low and constant, and the processing rheology can be improved well during processing.
As shown in fig. 6, as the content of the hyperbranched polyester increases, the thermal conductivity generally shows an increasing trend, and it can be seen that a more stable and continuous three-dimensional thermal conductive network is formed by adding the hyperbranched polyester, so that the thermal conductivity is increased.
In summary, the method of the embodiment of the application is simple, easy to operate, low in price, mild in preparation conditions, environment-friendly and capable of efficiently and continuously producing the heat conduction material in a large scale.
The above description is only an example of the present application and is not intended to limit the scope of the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (10)
1. A method for preparing a high-thermal-conductivity PA66 composite material by using hyperbranched polyester comprises the following steps:
(1) Mixing a certain amount of hyperbranched polyester in a certain organic solvent to form a first mixture, wherein the mixture solution is slightly yellow and clear, which indicates that the mixture is uniformly mixed;
(2) Mixing the first mixture with boron nitride powder according to a ratio, uniformly stirring, identifying no obvious blocky substance by naked eyes, judging that the mixture is uniformly stirred, continuously drying the mixture at 80 ℃ for 12 hours, taking out the dried mixture, grinding the dried mixture into powder by using a mortar, continuously drying the powder in an oven at 80 ℃ for 15 hours, sufficiently removing the solvent, and continuously grinding the powder to obtain a final white powdery substance;
(3) Premixing the white powder obtained in the step (2) with nylon resin according to a ratio, melting and mixing the mixture through a torque rheometer, and finally hot-pressing the mixture into sheets to obtain a heat-conducting polymer material;
wherein, based on the total mass of the hyperbranched polyester, the boron nitride and the nylon being 100%, the mass percentage of the nylon is 1-60%, the mass percentage of the boron nitride is 1-50%, and the mass percentage of the hyperbranched polyester is 0.5-10%.
2. The method for preparing the high thermal conductivity PA66 composite material by using the hyperbranched polyester as claimed in claim 1, wherein: the nylon resin is nylon 66, the melting point is 262 ℃, and the content of terminal amino groups is 43 mmol/kg.
3. The method for preparing the high thermal conductivity PA66 composite material by using the hyperbranched polyester as claimed in claim 1, wherein: the boron nitride is hexagonal boron nitride, and the particle size of the particles is 100 nanometers.
4. The method for preparing the high thermal conductivity PA66 composite material by using the hyperbranched polyester as claimed in claim 1, wherein: the hyperbranched polyester is heat-resistant aliphatic hyperbranched polyester, the molecular weight is 1100g/mol, the hydroxyl value is 600 +/-20 mg KOH/g, and the acid value is less than 20mg KOH/g.
5. The method for preparing high thermal conductivity PA66 composite material by using hyperbranched polyester as in one of claims 1 to 4, wherein: the mass percentage of the nylon resin is 50-90%, the mass percentage of the boron nitride is 10-50%, and the mass percentage of the hyperbranched polyester is 0.5-4%.
6. The method for preparing the high thermal conductivity PA66 composite material by using the hyperbranched polyester as claimed in claim 1, wherein: in the step (1), the organic solvent is an organic solvent having good solubility for the hyperbranched polyester, and the preferred organic solvent is at least one of acetone, ethanol, an ethanol + aqueous solution, dichloromethane, tetrahydrofuran and N, N-dimethylformamide.
7. The method for preparing the high thermal conductivity PA66 composite material by using the hyperbranched polyester as claimed in claim 1, wherein: the specific operation of the step (1) is as follows: firstly, dissolving hyperbranched polyester in an organic solvent, and performing ultrasonic treatment to obtain a mixed solution, wherein the ultrasonic treatment time is 0.5-1 h, and the ultrasonic power is 500W.
8. The method for preparing the high thermal conductivity PA66 composite material by using the hyperbranched polyester as claimed in claim 1, wherein: the nylon resin was dried in an oven at 80 ℃ for 24 hours before being premixed in a certain ratio.
9. The method for preparing the high thermal conductivity PA66 composite material by using the hyperbranched polyester as claimed in claim 1, wherein: in the step (3), the blending conditions are as follows: the temperature of the torque rheometer is 270-280 ℃, and the rotating speed is 50-100r/min.
10. The method for preparing the high thermal conductivity PA66 composite material by using the hyperbranched polyester as claimed in claim 1, wherein: in the step (3), the hot pressing sheeting conditions are as follows: the hot pressing temperature is 270-290 deg.C, the hot pressing pressure is 10-20MPa, and the hot pressing process comprises preheating for 3-8min, degassing for 3-5 times, pressing for 5-15min, and cooling for 15-45s for 2-5 times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211065049.6A CN115418101A (en) | 2022-09-01 | 2022-09-01 | Method for preparing high-thermal-conductivity PA66 composite material by using hyperbranched polyester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211065049.6A CN115418101A (en) | 2022-09-01 | 2022-09-01 | Method for preparing high-thermal-conductivity PA66 composite material by using hyperbranched polyester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115418101A true CN115418101A (en) | 2022-12-02 |
Family
ID=84201693
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211065049.6A Pending CN115418101A (en) | 2022-09-01 | 2022-09-01 | Method for preparing high-thermal-conductivity PA66 composite material by using hyperbranched polyester |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115418101A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117024807A (en) * | 2023-08-15 | 2023-11-10 | 浙江元盛塑业股份有限公司 | Method for preparing high-heat-conductivity polymer material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100113668A1 (en) * | 2008-10-30 | 2010-05-06 | E. I. Du Pont De Nemours And Company | Thermoplastic compositon including thermally conductive filler and hyperbranched polyesteramide |
| CN107603211A (en) * | 2017-09-26 | 2018-01-19 | 上海日之升科技有限公司 | A kind of high-fluidity high-toughness Heat conduction nylon composite material and preparation method thereof |
| CN109852044A (en) * | 2018-12-06 | 2019-06-07 | 安徽集虹材料科技有限公司 | Thermally conductive nylon of a kind of boron nitride orientation and preparation method thereof |
-
2022
- 2022-09-01 CN CN202211065049.6A patent/CN115418101A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100113668A1 (en) * | 2008-10-30 | 2010-05-06 | E. I. Du Pont De Nemours And Company | Thermoplastic compositon including thermally conductive filler and hyperbranched polyesteramide |
| CN107603211A (en) * | 2017-09-26 | 2018-01-19 | 上海日之升科技有限公司 | A kind of high-fluidity high-toughness Heat conduction nylon composite material and preparation method thereof |
| CN109852044A (en) * | 2018-12-06 | 2019-06-07 | 安徽集虹材料科技有限公司 | Thermally conductive nylon of a kind of boron nitride orientation and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117024807A (en) * | 2023-08-15 | 2023-11-10 | 浙江元盛塑业股份有限公司 | Method for preparing high-heat-conductivity polymer material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101362852B (en) | Method for preparing polybutylene terephthalate/ethylene-vinyl acetate compound material | |
| CN101117433B (en) | Elastomer-containing polycarbonate-based blending material and method for making same | |
| CN113248900B (en) | Dynamic bond crosslinking high-filling heat-conducting composite material and preparation method and application thereof | |
| CN115418101A (en) | Method for preparing high-thermal-conductivity PA66 composite material by using hyperbranched polyester | |
| CN102964815B (en) | Microscopically well-dispersed high performance nano reinforced nylon composite and preparation method thereof | |
| CN111320832A (en) | Full-biodegradable toughened injection molding master batch and processing technology | |
| CN112662077B (en) | Antistatic graphene-coated aluminum microsphere modified PP composite material and preparation method thereof | |
| CN106947233A (en) | A kind of PC/PA6/ graphene composite materials and preparation method thereof | |
| CN109438905B (en) | Quaternary blending modified ABS material and preparation method thereof | |
| CN110452505A (en) | A kind of thermally conductive polyester composite of high heat resistance and preparation method thereof | |
| CN105400191B (en) | A kind of high heat conduction nylon-graphite-low-melting-point metal composite material and preparation method thereof | |
| CN112143194A (en) | Modified regenerated PC/ABS alloy reclaimed material and preparation method thereof | |
| CN115418100A (en) | Method for preparing high-thermal-conductivity PA66 composite material by using hyperbranched polyamide | |
| CN109206895B (en) | Preparation method of heat-conducting and insulating aromatic nylon alloy material | |
| CN114015223A (en) | PC/PBT alloy material and preparation method and application thereof | |
| CN106893251A (en) | A kind of high-performance ABS/PA6/ graphene composite materials and preparation method thereof | |
| CN109504048B (en) | Thermotropic reversible crosslinking composition modified polylactic acid 3D printing wire and preparation method thereof | |
| CN113845718B (en) | Preparation method of bamboo fiber/basalt fiber/polypropylene environment-friendly composite wire | |
| CN115612224A (en) | Polyvinyl chloride composite material and preparation method thereof | |
| CN111349331A (en) | Mineral-filled PC alloy material with high impact resistance and low warpage and preparation method thereof | |
| CN117024807A (en) | Method for preparing high-heat-conductivity polymer material | |
| CN117304524A (en) | Method for preparing high-heat-conductivity polymer material by taking modified boron nitride nanosheets as fillers | |
| CN115703912B (en) | Low-precipitation temperature-resistant polyvinyl chloride cable material composition and preparation method thereof | |
| CN118108940B (en) | Nylon composite material and preparation method and application thereof | |
| CN106977914A (en) | A kind of 6/ polypropylene of nylon/graphene nanocomposite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20221202 |
|
| RJ01 | Rejection of invention patent application after publication |