CN115304769B - Degradable copolyester based on 4, 4-thiodiphenol, preparation method and application - Google Patents
Degradable copolyester based on 4, 4-thiodiphenol, preparation method and application Download PDFInfo
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- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229920001634 Copolyester Polymers 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000004020 conductor Substances 0.000 claims abstract description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000178 monomer Substances 0.000 claims abstract description 36
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000005886 esterification reaction Methods 0.000 claims abstract description 26
- QABLOFMHHSOFRJ-UHFFFAOYSA-N methyl 2-chloroacetate Chemical compound COC(=O)CCl QABLOFMHHSOFRJ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000032050 esterification Effects 0.000 claims abstract description 23
- 150000005690 diesters Chemical class 0.000 claims abstract description 21
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 19
- BXGYYDRIMBPOMN-UHFFFAOYSA-N 2-(hydroxymethoxy)ethoxymethanol Chemical compound OCOCCOCO BXGYYDRIMBPOMN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002131 composite material Substances 0.000 claims description 88
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 60
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 60
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 53
- 238000001914 filtration Methods 0.000 claims description 40
- 239000000843 powder Substances 0.000 claims description 40
- 239000000047 product Substances 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 239000007787 solid Substances 0.000 claims description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 238000005406 washing Methods 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 24
- 239000012043 crude product Substances 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 12
- 239000004970 Chain extender Substances 0.000 claims description 10
- 239000004593 Epoxy Substances 0.000 claims description 10
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 10
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 10
- -1 compound glycidyl acrylate Chemical class 0.000 claims description 10
- 229940057995 liquid paraffin Drugs 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000012074 organic phase Substances 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 9
- 238000000713 high-energy ball milling Methods 0.000 claims description 9
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 8
- 238000007731 hot pressing Methods 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 4
- BHCMUFPNGREEFT-UHFFFAOYSA-N O(O)O.C(CCC)[Sn]CCCC Chemical compound O(O)O.C(CCC)[Sn]CCCC BHCMUFPNGREEFT-UHFFFAOYSA-N 0.000 claims description 3
- RXCBCUJUGULOGC-UHFFFAOYSA-H dipotassium;tetrafluorotitanium;difluoride Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[K+].[K+].[Ti+4] RXCBCUJUGULOGC-UHFFFAOYSA-H 0.000 claims description 3
- 239000012071 phase Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims 2
- 229920006238 degradable plastic Polymers 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 abstract description 2
- 238000005809 transesterification reaction Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 61
- 239000013256 coordination polymer Substances 0.000 description 56
- 239000003822 epoxy resin Substances 0.000 description 44
- 229920000647 polyepoxide Polymers 0.000 description 44
- 238000012360 testing method Methods 0.000 description 39
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 229920000728 polyester Polymers 0.000 description 24
- 229910052582 BN Inorganic materials 0.000 description 21
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 21
- 238000002390 rotary evaporation Methods 0.000 description 16
- 239000000758 substrate Substances 0.000 description 12
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 11
- 229910052796 boron Inorganic materials 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 10
- FLMGKLCSPCZCKP-UHFFFAOYSA-N [5-(hydroxymethyl)thiophen-2-yl]methanol Chemical compound OCC1=CC=C(CO)S1 FLMGKLCSPCZCKP-UHFFFAOYSA-N 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 229910000831 Steel Inorganic materials 0.000 description 8
- 239000011368 organic material Substances 0.000 description 8
- 238000002791 soaking Methods 0.000 description 8
- 239000010959 steel Substances 0.000 description 8
- 235000012431 wafers Nutrition 0.000 description 7
- 239000000956 alloy Substances 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000002322 conducting polymer Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000011825 aerospace material Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- BYSFLEQBDOJVAR-UHFFFAOYSA-L dibutyltin(2+);dihydroxide Chemical compound [OH-].[OH-].CCCC[Sn+2]CCCC BYSFLEQBDOJVAR-UHFFFAOYSA-L 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000002783 friction material Substances 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011156 metal matrix composite Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/26—Polythioesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
- C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6886—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/28—Nitrogen-containing compounds
- C08K2003/282—Binary compounds of nitrogen with aluminium
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- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a degradable copolyester based on 4, 4-thiodiphenol, a preparation method and application thereof, belonging to the field of degradable plastics. The 4, 4-thiodiphenol and methyl chloroacetate are subjected to phenolic hydroxyl esterification reaction to obtain a diester monomer M, and the diester monomer M, a dihydric alcohol monomer 1, 4-disulfide-2, 5-di (methane mercaptan) and 2, 5-thiophene dimethanol are subjected to transesterification to obtain a novel esterification product. The new esterified product is heated to perform polycondensation reaction and purified to obtain the copolyester with the weight average molecular weight of 20000-30000 g/mol, which has good mechanical property and flexibility, is easy to be degraded by environment and is harmless to the environment. The degradable copolyester prepared by the invention is used for preparing a heat-conducting material matrix.
Description
Technical Field
The invention belongs to the field of degradable plastics, and relates to degradable copolyester based on 4, 4-thiodiphenol, a preparation method and application thereof. 4, 4-thiodiphenol is taken as a raw material and is subjected to phenolic hydroxyl esterification reaction with methyl chloroacetate to obtain a diester monomer M, and the diester monomer M is reacted with 1, 4-dithio-2, 5-di (methane mercaptan) and 2, 5-thiophene dimethanol to synthesize the degradable copolyester based on 4, 4-thiodiphenol, which can be used for preparing a heat conducting material matrix. The material prepared by the invention has good thermal conductivity, mechanical property and electrical property.
Background
The heat conducting material is widely applied to the fields of heat exchange engineering, heating engineering, electronic information engineering and the like. Metal materials have long been commonly selected for use as thermally conductive materials. The range of application of metallic materials is limited due to their poor corrosion resistance. Alloy technology, anticorrosive coating technology and the like are adopted for improving the corrosion resistance of metal, but the heat conduction capacity is greatly reduced. In recent years, some fields with high requirements on heat conducting performance of materials, such as heat exchange engineering, electromagnetic shielding, electronic information, friction materials and the like, have also proposed polymers, such as HDPE, as heat conducting base materials, and have attracted attention of researchers. However, the heat conductivity of the polymer is small, the application of the polymer in the heat conduction field is expanded, and the improvement of the heat conduction performance is a technical key.
With the continuous development of industrial technology, production equipment starts to develop to high frequency, integration and microminiature, and a large amount of heat is generated in the working process, so that higher requirements are put on the heat conducting material. Compared with traditional metal, metal oxide, ceramic material and the like, the high polymer material has better mechanical property, high chemical corrosion resistance and flexible molecular structure ［1］ ([ 1] Yang Juxiang, yang Ying, gu Yuan, etc. ] preparation of thermally conductive Polymer MaterialDevelopment of application thereof [ J]Polymer notification, 2021, 8:1-8.) and low processing and forming cost, and shows wider application in the fields of light-emitting diodes, aerospace materials, electronic components and the like ［2］ (［2］TANG Z, LU S, LIN X, et al. Research Progress on Catechol-Containing Polymers[J]Chinese Journal of Applied Chemistry, 2018, 35 (12): 1399.). The main method for preparing the heat conducting polymer material is divided into two types, wherein the first method is the preparation of the intrinsic heat conducting polymer material, namely, a polymer with complete crystallization and higher structural orientation is designed ［3］ （［3］ELmezayyen A S, Reicha F M, El-Sherbiny I M, et al. Significantly enhanced electroactive β phase crystallization and UV-shielding properties in PVDF nanocomposites flexible films through loading of ATO nanoparticles: Synthesis and formation mechanism[J]European Polymer Journal, 2017, 90:195-208.); the second is to add a thermally conductive filler with excellent properties to the polymer to achieve good conduction of heat inside the material.
With the advent of the 5G era, the power density of electronic devices has been increasing, and in order to ensure safe and reliable operation of electronic devices, high heat conductive materials have been receiving more and more attention. Currently, the substrate materials on the market include epoxy resin (EP) composite materials, organic silicon heat conduction composite materials, ceramic heat conduction materials and the like, and the materials have excellent performances in certain single aspects, but the requirements of the substrate materials cannot be met from the aspect of comprehensive performances. Wu Zhijun ［5］ (preparation of organosilicon Heat-conducting composite Material and its Performance [ J ]]Functional materials 2022,53 (5): 5153-5159.) A silicone composite reported has a thermal conductivity of 1.511W/(m.K), up to [6] (preparation of hexagonal boron nitride-cubic boron nitride/epoxy resin composite Material and thermal Property [ J)]A hexagonal boron nitride epoxy resin (hBN/EP) composite heat-conducting material reported by composite material journal 2022,39 (6): 2599-2606 has a heat conductivity coefficient of 0.444W/(m.K), chen Zhenrui [7] (preparation and research progress of high thermal conductivity Metal matrix composite [ J ]]A silicon/aluminium composite material (Si) reported in powder metallurgy technology 2022,40 (1): 40-52) p The thermal conductivity of the alloy is 6W/(mK) to the upper20W/(m.K). The thermal conductivity coefficients of the polymer composite thermal conductive materials such as organic silicon thermal conductive composite materials and hBN/EP composite thermal conductive materials prepared by the prior art are smaller than the current standard 2W/(m.K), and the thermal conductivity requirements of the substrate materials cannot be met. It is important to improve the composition of the existing polymer-based composite material and develop a composite heat-conducting material with good mechanical property and excellent heat-conducting property.
Disclosure of Invention
Aiming at the problems in the prior art, the invention synthesizes a brand new diester monomer M by taking 4, 4-thiodiphenol as a raw material, and carries out melt polymerization with glycol 1, 4-dithio-2, 5-di (methane mercaptan) and 2, 5-thiophene dimethanol to synthesize the degradable copolyester based on the 4, 4-thiodiphenol. And combining the synthesized copolyester with a material with excellent heat conduction performance, such as aluminum nitride, to form the composite heat conduction material. The heat conducting material has the advantages of good heat conductivity and dielectric property, good mechanical property and flexibility, simple and convenient processing, good mechanical property and excellent heat conducting property, and is a composite heat conducting material with wide market prospect.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
in order to better realize the technical scheme of the invention, the invention discloses a degradable copolyester based on 4, 4-thiodiphenol, a preparation method and application, wherein the preparation method of the polyester comprises the following steps:
1) Preparation of diester monomer M: dissolving 4-6 g of 4, 4-thiodiphenol with the CAS number of 2664-63-3 in 30-50 ml of acetonitrile, adding methyl chloroacetate, wherein the mass ratio of the 4, 4-thiodiphenol to the methyl chloroacetate is 1 (2-2.3), and adding 1-5% of K by mass of the 4, 4-thiodiphenol 2 CO 3 Reacting for 3-4 hours at 80-90 ℃ as a catalyst, filtering to obtain a clear solution after the reaction, evaporating acetonitrile, dissolving with 20-30 ml of chloroform, washing with water for 2-3 times, removing a water phase, and adding 2-3 g of Na into an organic phase 2 SO 4 Drying for 2 hours, filtering, and evaporating the filtrate to remove chloroform to obtain diester monomer M, wherein the structure is shown as formula 2:
2, 2
2) Synthesis of polycondensation crude products: 1, 4-disulfide-2, 5-di (methane mercaptan) with CAS number 136122-15-1 is used as a first alcohol source, 2, 5-thiophene dimethanol is used as a second alcohol source, the prepared monomer M, the first alcohol source and the second alcohol source are added into a reaction vessel according to the mass ratio of 10 (5.1-5.7) (4.3-4.9), a catalyst is added, nitrogen is introduced for protection, stirring reaction is carried out for 3-4 hours at 190-210 ℃ to obtain a new esterification product, the temperature of the new esterification product is continuously raised to 240-260 ℃, the absolute pressure in a reaction system is controlled to be 80-120 Pa, and polycondensation reaction is carried out under full stirring for 3-4 h to obtain a polycondensation crude product;
3) Preparation of degradable copolyester CP: dissolving the polycondensation crude product with chloroform, filtering, taking clear liquid, adding lower alcohol into the clear liquid until precipitation is not increased, centrifugally separating, filtering, washing the obtained solid with ethanol, and drying the filtered solid at 60-70 ℃ for 2-3 h to obtain the degradable copolyester CP based on 4, 4-thiodiphenol.
As a further preferable aspect, the catalyst in the step 2) is one of potassium hexafluorotitanate, dibutyltin oxyhydroxide, methanesulfonic acid, and antimony trioxide, and the amount of the catalyst is 0.05% to 0.10% of the amount of the diester monomer M.
The degradable copolyester based on 4, 4-thiodiphenol as claimed in claims 1 to 4, which can be used for preparing heat-conducting materials, the preparation method comprises the following steps:
1) Mixing and banburying raw materials of the copolyester heat-conducting material: weighing 10 parts by mass of aluminum nitride powder, and drying in vacuum drying equipment at 100 ℃ for 1 hour for later use; weighing 100 parts by mass of the degradable copolyester CP according to claims 1-4, uniformly mixing with 1 part by mass of the chain extender epoxy compound glycidyl acrylate, 0.5 part by mass of the antioxidant 1010 and 1-5 parts by mass of the liquid paraffin, extruding by using a double-screw extruder, granulating, drying, grinding into powder, mixing with aluminum nitride powder by a high-energy ball milling method, and banburying by an internal mixer.
2) And (3) forming and processing a copolyester heat-conducting material: the copolyester heat-conducting material in the step 1) of claim 5 is formed by hot-pressing after the raw materials are mixed and banburying; and obtaining the uniform and compact degradable copolyester CP/aluminum nitride composite heat-conducting material.
Advantageous effects
1. Careful selection of raw materials: the 1, 4-disulfide-2, 5-di (methane mercaptan) adopted by the invention has wide sources and is cheap and easy to obtain. The 1, 4-disulfide-2, 5-di (methane mercaptan) and 2, 5-thiophene dimethanol are bio-based renewable green chemicals, replace petroleum-based monomers as basic raw materials to prepare the copolyester, and can relieve the problem of lack of petroleum resources in the future, so that the synthetic copolyester has the characteristics of low raw material cost, environment friendliness, reproducibility and the like.
2. The mechanical properties of the synthesized copolyester are excellent: the invention introduces an aromatic ring structure with annular rigidity, greatly improves the mechanical property of the polyester, has tensile breaking strength of 73-96 MPa and has breaking elongation of more than 200 percent.
3. Gaolida (a Chinese character) ［6］ (preparation of hexagonal boron nitride-cubic boron nitride/epoxy resin composite Material and thermal Property [ J)]The heat conductivity coefficient of the hexagonal boron nitride epoxy resin (hBN/EP) composite heat conduction material reported by composite material school report, 2022) is 0.444W/(m.K); the heat conductivity coefficient of the self-made CP/aluminum nitride composite heat conducting material is 1.774W/(m.K) -5.380W/(m.K), and is substantially improved compared with the prior art.
Detailed description of the preferred embodiments
The present invention is further illustrated by the following examples, but the present invention is not limited by the examples. The raw materials in the invention are all conventional and commercially available.
Molecular weight testing: intrinsic viscosity was measured with reference to GB/T1632.5-2008 at 25℃with phenol/tetrachloroethane (50/50, wt/wt) as solvent and polyester concentration of 0.5g/dL, measured with an Ubbelohde viscometer.
Mechanical property test: tensile breaking strength test is carried out according to GB/T1040.1-2006 standard; elongation at break is carried out according to GB/T2567-2008 standard; bending performance tests were performed according to GB/T9341-2008 standard;
and (3) testing heat conduction performance: the thermal conductivity was calculated using a round sample of the flat plate method in the longitudinal heat flow method using a TCHM-LT C-MATIC thermal flow meter thermal conductivity tester from Dynatech R/D Company, U.S.A.
Test 5 results the average of the tests was taken.
Yield = 100% x actual yield of target product/theoretical yield of target product.
Example 1:
taking 4-6 g of 4, 4-thiodiphenol with CAS number of 2664-63-3, dissolving in 30-50 ml of acetonitrile, adding methyl chloroacetate, wherein the mass ratio of 4,4 '-thiodiphenol to methyl chloroacetate is 1 (2-2.3), and adding K which is 1-5% of the mass of 4,4' -thiodiphenol 2 CO 3 Reacting for 3-4 h at 80-90 ℃ as a catalyst, filtering to obtain a clear solution after the reaction, removing acetonitrile by rotary evaporation, dissolving with 20-30 ml of chloroform, washing with 100-150 ml of 0.8-1 mol/L NaOH solution, washing with water for 2-3 times, and adding 2-3 g of Na into an organic phase 2 SO 4 Filtering, and removing chloroform by rotary evaporation to obtain diester monomer M.
Into a 50ml one-necked flask, 2.974g (14 mmol) of 1, 4-dithio-2, 5-bis (methanethiol), 1.422g (10 mmol) of 2, 5-thiophenedimethanol, 8.800g (25 mmol) of 2-diester monomer M and 0.008g (0.027 mmol) of antimony trioxide were successively charged. Introducing nitrogen to protect, and stirring at 200 ℃ to react 4h to obtain an esterification product. And continuously heating the esterification product to 240 ℃, controlling the absolute pressure in a reaction system to be about 80 Pa, and reacting 3h to obtain a crude product of the polycondensation product. Adding 30mL of chloroform into the polyester crude product, soaking for 2 hours, and filtering; adding the clear solution into 50ml methanol dropwise to obtain turbid liquid, centrifuging, filtering to obtain solid, washing the obtained solid with ethanol, and drying the filtered solid at 60deg.C for 2h to obtain 11.382g copolyester CP 1 The yield thereof was found to be 86.25%. The molecular weight of the polyester measured by Ubbelohde viscometer is 26800 g/mol, and the copolyester CP 1 The test results of (2) are shown in Table 1.
10g of aluminum nitride powder was weighed and dried in vacuum at 100℃for 1 hour for further use. Weighing the common100g of polyester CP, 1g of chain extender epoxy compound glycidyl acrylate, 0.5g of antioxidant 1010 and 5g of liquid paraffin are uniformly mixed, extruded by a double-screw extruder, granulated, dried, ground into powder, and mixed with aluminum nitride powder by high-energy ball milling into a container (such as a steel tank) of a high-energy ball mill to uniformly mix the powder mixture, and then the mixture is subjected to banburying by a banburying machine and then is subjected to hot-press molding. The materials are crosslinked and solidified through the reaction in the extruder, the high-energy ball mill can fully mix the high-heat-conductivity aluminum nitride with the organic materials, and after banburying, the materials are finally hot-pressed and molded in a vacuum autoclave, thus obtaining the uniform and compact CP/aluminum nitride composite heat-conducting material G 1 . The material was cut into 50mm diameter, 3mm thick discs and coated with a thin layer of heat transfer medium. The TCHM-LT heat conduction tester is adopted for testing, a wafer-shaped sample is placed between a cold-face heater (upper heater) and a hot-face heater (lower heater), and the temperature T of the lower surface of the sample is measured 1 And the upper surface temperature T of the sample u Obtaining thermal resistance R according to a flat plate method in a longitudinal heat flow method S And a thermal conductivity lambda S The temperature of each heater was kept constant during the test, and the test results of the composite materials are shown in table 2.
Gaolida (a Chinese character) ［6］ (preparation of hexagonal boron nitride-cubic boron nitride/epoxy resin composite Material and thermal Property [ J)]The heat conductivity coefficient of the hexagonal boron nitride epoxy resin (hBN/EP) composite heat conduction material reported by composite material school report, 2022) is 0.444W/(m.K); novel CP/aluminum nitride composite heat conduction material G 1 Resistance value R of (2) S =25.31×10 -4 m 2 K/W, coefficient of thermal conductivity lambda S Compared with 1.774W/m.k, the heat conduction performance is greatly improved; its surface resistivity is 2.027 ×10 4 Omega cm is an excellent material for manufacturing circuit substrates.
Example 2:
dissolving 4-6 g of 4, 4-thiodiphenol with the CAS number of 2664-63-3 in 30-50 ml of acetonitrile, adding methyl chloroacetate, wherein the mass ratio of the 4, 4-thiodiphenol to the methyl chloroacetate is 1 (2-2.3), and adding 1-5% of K by mass of the 4, 4-thiodiphenol 2 CO 3 As a means ofThe catalyst reacts for 3-4 hours at 80-90 ℃, a clear solution is obtained after the reaction, acetonitrile is removed by rotary evaporation, the solution is dissolved by 20-30 ml of chloroform, then the solution is washed by 100-150 ml of 0.8-1 mol/L NaOH solution, then the solution is washed by water for 2-3 times, and 2-3 g of Na is added into an organic phase 2 SO 4 Filtering, and removing chloroform by rotary evaporation to obtain diester monomer M.
Into a 50ml one-necked flask, 3.399g (16 mmol) of 1, 4-dithio-2, 5-bis (methanethiol), 1.422g (10 mmol) of 2, 5-thiophenedimethanol, 8.800g (25 mmol) of 2-diester monomer M and 0.006g (0.027 mmol) of potassium hexafluorotitanate were successively charged. Introducing nitrogen to protect, and stirring at 200 ℃ to react 4h to obtain an esterification product. And continuously heating the esterification product to 240 ℃, controlling the absolute pressure in a reaction system to be about 80 Pa, and reacting 3h to obtain a crude product of the polycondensation product. Adding 30mL of chloroform into the polyester crude product, soaking for 2 hours, and filtering; taking clear liquid, dropwise adding into 50ml methanol to obtain turbid liquid, centrifuging, filtering to obtain solid, washing the obtained solid with ethanol, and drying the filtered solid at 60deg.C for 2h to obtain 12.08g copolyester CP 2 The yield thereof was found to be 88.69%. The molecular weight of the polyester measured by Ubbelohde viscometer is 23100 g/mol, and the copolyester CP 2 The test results of (2) are shown in Table 1.
10g of aluminum nitride powder was weighed and dried in vacuum at 100℃for 1 hour for further use. Weighing 100g of copolyester CP, uniformly mixing with 1g of chain extender epoxy compound glycidyl acrylate, 0.5g of antioxidant 1010 and 5g of liquid paraffin, extruding by using a double-screw extrusion reactor, granulating, drying, grinding into powder, loading the powder and 10g of dried aluminum nitride powder into a container (such as a steel tank) of a high-energy ball mill, uniformly mixing the powder mixture, and carrying out hot-press molding after banburying by a banburying machine. The materials are crosslinked and solidified through the reaction in the extruder, the high-energy ball mill can fully mix the high-heat-conductivity aluminum nitride with the organic materials, and after banburying, the materials are finally hot-pressed and molded in a vacuum autoclave, thus obtaining the uniform and compact CP/aluminum nitride composite heat-conducting material G 2 . The composite heat conducting material is cut into wafers with the diameter of 50mm and the thickness of 3mm, and a thin layer of heat conducting medium is coated on the surface. By TCHMThe LT heat conduction tester tests that a wafer-shaped sample is placed between a cold-face heater (upper heater) and a hot-face heater (lower heater), and the temperature T of the lower surface of the sample is measured L And the upper surface temperature T of the sample U Obtaining thermal resistance R according to a flat plate method in a longitudinal heat flow method S And a thermal conductivity lambda S The temperature of each heater was kept constant during the test, and the test results of the composite materials are shown in table 2.
Gaolida (a Chinese character) ［6］ (preparation of hexagonal boron nitride-cubic boron nitride/epoxy resin composite Material and thermal Property [ J)]The heat conductivity coefficient of the hexagonal boron nitride epoxy resin (hBN/EP) composite heat conduction material reported by composite material school report, 2022) is 0.444W/(m.K); novel CP/aluminum nitride composite heat conduction material G 2 Resistance value R of (2) S =22.28×10 -4 m 2 K/W, coefficient of thermal conductivity lambda S Compared with the heat conduction performance of the material is greatly improved, the material is=1.973W/m.k; its surface resistivity is 1.988 ×10 4 Omega cm is an excellent material for manufacturing circuit substrates.
Example 3:
dissolving 4-6 g of 4, 4-thiodiphenol with the CAS number of 2664-63-3 in 30-50 ml of acetonitrile, adding methyl chloroacetate, wherein the mass ratio of the 4, 4-thiodiphenol to the methyl chloroacetate is 1 (2-2.3), and adding 1-5% of K by mass of the 4, 4-thiodiphenol 2 CO 3 Reacting for 3-4 h at 80-90 ℃ as a catalyst, filtering to obtain a clear solution after the reaction, removing acetonitrile by rotary evaporation, dissolving with 20-30 ml of chloroform, washing with 100-150 ml of 0.8-1 mol/L NaOH solution, washing with water for 2-3 times, and adding 2-3 g of Na into an organic phase 2 SO 4 Filtering, and removing chloroform by rotary evaporation to obtain diester monomer M.
Into a 50ml one-necked flask, 2.974g (14 mmol) of 1, 4-dithio-2, 5-bis (methanethiol), 1.706g (12 mmol) of 2, 5-thiophenedimethanol, 8.80g (25 mmol) of 2-diester monomer M and 0.005g (0.020 mmol) of dibutyltin hydroxide were successively charged. Introducing nitrogen to protect, and stirring at 200 ℃ to react 4h to obtain an esterification product. Continuously heating the esterification product to 240 ℃, controlling the absolute pressure in a reaction system to be about 80 Pa, and reacting 3h to obtain the polycondensation productCrude product of the product. Adding 30mL of chloroform into the polyester crude product, soaking for 2 hours, and filtering; adding the clear solution into 50ml methanol dropwise to obtain turbid liquid, centrifuging, filtering to obtain solid, washing the obtained solid with ethanol, and drying the filtered solid at 60deg.C for 2h to obtain 12.026g copolyester CP 3 The yield thereof was found to be 89.21%. The molecular weight of the polyester is 29800 g/mol measured by Ubbelohde viscometer, and the copolyester CP 3 The test results of (2) are shown in Table 1.
10g of aluminum nitride powder was weighed and dried in vacuum at 100℃for 1 hour for further use. Weighing 100g of copolyester CP, uniformly mixing with 1g of chain extender epoxy compound glycidyl acrylate, 0.5g of antioxidant 1010 and 5g of liquid paraffin, extruding by using a double-screw extruder, granulating, drying, grinding into powder, mixing with aluminum nitride powder by high-energy ball milling, putting into a container (such as a steel tank) of a high-energy ball mill, uniformly mixing the powder mixture, banburying by a banburying machine, and hot-pressing to form. The materials are crosslinked and solidified through the reaction in the extruder, the high-energy ball mill can fully mix the high-heat-conductivity aluminum nitride with the organic materials, and after banburying, the materials are finally hot-pressed and molded in a vacuum autoclave, thus obtaining the uniform and compact CP/aluminum nitride composite heat-conducting material G 3 . The composite heat conducting material is cut into wafers with the diameter of 50mm and the thickness of 3mm, and a thin layer of heat conducting medium is coated on the surface. The TCHM-LT heat conduction tester is adopted for testing, a wafer-shaped sample is placed between a cold-face heater (upper heater) and a hot-face heater (lower heater), and the temperature T of the lower surface of the sample is measured L And the upper surface temperature T of the sample U Obtaining thermal resistance R according to a flat plate method in a longitudinal heat flow method S And a thermal conductivity lambda S The temperature of each heater was kept constant during the test, and the test results of the composite materials are shown in table 2.
Gaolida (a Chinese character) ［6］ (preparation of hexagonal boron nitride-cubic boron nitride/epoxy resin composite Material and thermal Property [ J)]The heat conductivity coefficient of the hexagonal boron nitride epoxy resin (hBN/EP) composite heat conduction material reported by composite material school report, 2022) is 0.444W/(m.K); novel CP/aluminum nitride composite heat conduction material G 3 Resistance value R of (2) S =20.09×10 -4 m 2 K/W, coefficient of thermal conductivity lambda S Compared with 2.209W/m.k, the heat conduction performance is greatly improved; its surface resistivity is 1.210×10 4 Omega cm is an excellent material for manufacturing circuit substrates.
Example 4:
dissolving 4-6 g of 4, 4-thiodiphenol with the CAS number of 2664-63-3 in 30-50 ml of acetonitrile, adding methyl chloroacetate, wherein the mass ratio of the 4, 4-thiodiphenol to the methyl chloroacetate is 1 (2-2.3), and adding 1-5% of K by mass of the 4, 4-thiodiphenol 2 CO 3 Reacting for 3-4 h at 80-90 ℃ as a catalyst, filtering to obtain a clear solution after the reaction, removing acetonitrile by rotary evaporation, dissolving with 20-30 ml of chloroform, washing with 100-150 ml of 0.8-1 mol/L NaOH solution, washing with water for 2-3 times, and adding 2-3 g of Na into an organic phase 2 SO 4 Filtering, and removing chloroform by rotary evaporation to obtain diester monomer M.
Into a 50ml one-necked flask, 3.399g (16 mmol) of 1, 4-dithio-2, 5-bis (methanethiol), 1.706g (12 mmol) of 2, 5-thiophenedimethanol, 8.800g (25 mmol) of 2-diester monomer M and 0.002g (0.020 mmol) of methanesulfonic acid were successively charged. Introducing nitrogen to protect, and stirring at 200 ℃ to react 4h to obtain an esterification product. And continuously heating the esterification product to 240 ℃, controlling the absolute pressure in a reaction system to be about 80 Pa, and reacting 3h to obtain a crude product of the polycondensation product. Adding 30mL of chloroform into the polyester crude product, soaking for 2 hours, and filtering; adding the clear solution into 50ml methanol dropwise to obtain turbid liquid, centrifuging, filtering to obtain solid, washing the obtained solid with ethanol, and drying the filtered solid at 60deg.C for 2h to obtain 12.705g copolyester CP 4 The yield thereof was found to be 91.37%. The molecular weight of the polyester measured by Ubbelohde viscometer is 25200 g/mol, and the copolyester CP 4 The test results of (2) are shown in Table 1.
10g of aluminum nitride powder is weighed and dried in vacuum at 100 ℃ for about 1 hour for standby. Weighing 100g of copolyester CP, uniformly mixing with 1g of chain extender epoxy compound glycidyl acrylate, 0.5g of antioxidant 1010 and 5g of liquid paraffin, extruding by a double-screw extruder, granulating, drying, grinding into powder and nitridingThe aluminum powder is put into a container (such as a steel tank) of a high-energy ball mill together for uniform mixing of powder mixture, and then is subjected to hot press processing and molding after banburying. The materials are crosslinked and solidified through the reaction in the extruder, the high-energy ball mill can fully mix the high-heat-conductivity aluminum nitride with the organic materials, and after banburying, the materials are finally hot-pressed and molded in a vacuum autoclave, thus obtaining the uniform and compact CP/aluminum nitride composite heat-conducting material G 4 . The composite heat conducting material is cut into wafers with the diameter of 50mm and the thickness of 3mm, and a thin layer of heat conducting medium is coated on the surface. The TCHM-LT heat conduction tester is adopted for testing, a wafer-shaped sample is placed between a cold-face heater (upper heater) and a hot-face heater (lower heater), and the temperature T of the lower surface of the sample is measured L And the upper surface temperature T of the sample U Obtaining thermal resistance R according to a flat plate method in a longitudinal heat flow method S And a thermal conductivity lambda S The temperature of each heater was kept constant during the test, and the test results of the composite materials are shown in table 2.
Gaolida (a Chinese character) ［6］ (preparation of hexagonal boron nitride-cubic boron nitride/epoxy resin composite Material and thermal Property [ J)]The heat conductivity coefficient of the hexagonal boron nitride epoxy resin (hBN/EP) composite heat conduction material reported by composite material school report, 2022) is 0.444W/(m.K); novel CP/aluminum nitride composite heat conduction material G 4 Resistance value R of (2) S =17.53×10 -4 m 2 K/W, coefficient of thermal conductivity lambda S Compared with the heat conduction performance of the alloy, the alloy has the advantages that the alloy is 2.533W/m.k, and the heat conduction performance is greatly improved; its surface resistivity is 9.865 ×10 3 Omega cm is an excellent material for manufacturing the circuit substrate, can greatly prompt the heat transfer performance of the circuit substrate, and avoids the degradation of the performance of electronic components caused by long-time heating.
Example 5:
dissolving 4-6 g of 4, 4-thiodiphenol with the CAS number of 2664-63-3 in 30-50 ml of acetonitrile, adding methyl chloroacetate, wherein the mass ratio of the 4, 4-thiodiphenol to the methyl chloroacetate is 1 (2-2.3), and adding 1-5% of K by mass of the 4, 4-thiodiphenol 2 CO 3 As a catalyst, reacting for 3-4 hours at 80-90 ℃, filtering after the reaction to obtain a clear solution, removing acetonitrile by rotary evaporation, and usingDissolving 20-30 ml of chloroform, washing with 100-150 ml of 0.8-1 mol/L NaOH solution, washing with water for 2-3 times, and adding 2-3 g of Na into the organic phase 2 SO 4 Filtering, and removing chloroform by rotary evaporation to obtain diester monomer M.
Into a 50ml one-necked flask, 3.824g (18 mmol) of 1, 4-dithio-2, 5-bis (methanethiol), 1.706g (12 mmol) of 2, 5-thiophenedimethanol, 8.800g (25 mmol) of 2-diester monomer M and 0.005g (0.017 mmol) of antimony trioxide were successively charged. Introducing nitrogen to protect, and stirring at 200 ℃ to react 4h to obtain an esterification product. And continuously heating the esterification product to 240 ℃, controlling the absolute pressure in a reaction system to be about 80 Pa, and reacting 3h to obtain a crude product of the polycondensation product. Adding 30mL of chloroform into the polyester crude product, soaking for 2 hours, and filtering; adding the clear solution into 50ml methanol dropwise to obtain turbid liquid, centrifuging, filtering to obtain solid, washing the obtained solid with ethanol, and drying the filtered solid at 60deg.C for 2h to obtain 13.015g copolyester CP 5 The yield thereof was found to be 90.82%. The molecular weight of the polyester measured by Ubbelohde viscometer is 23800 g/mol, and the copolyester CP 5 The test results of (2) are shown in Table 1.
10g of aluminum nitride powder was weighed and dried in vacuum at 100℃for 1 hour for further use. Weighing 100g of copolyester CP, uniformly mixing with 1g of chain extender epoxy compound glycidyl acrylate, 0.5g of antioxidant 1010 and 5g of liquid paraffin, extruding by using a double-screw extruder, granulating, drying, grinding into powder, mixing with aluminum nitride powder by high-energy ball milling, putting into a container (such as a steel tank) of a high-energy ball mill, uniformly mixing the powder mixture, banburying by a banburying machine, and hot-pressing to form. The materials are crosslinked and solidified through the reaction in the extruder, the high-energy ball mill can fully mix the high-heat-conductivity aluminum nitride with the organic materials, and after banburying, the materials are finally hot-pressed and molded in a vacuum autoclave, thus obtaining the uniform and compact CP/aluminum nitride composite heat-conducting material G 5 . The composite heat conducting material is cut into wafers with the diameter of 50mm and the thickness of 3mm, and a thin layer of heat conducting medium is coated on the surface. The TCHM-LT heat conduction tester is adopted for testing, and a wafer-shaped sample is placed in a cold-face heater (upper heater) and a hot-face heater(lower heater) between, measuring the temperature T of the lower surface of the sample L And the upper surface temperature T of the sample U Obtaining thermal resistance R according to a flat plate method in a longitudinal heat flow method S And a thermal conductivity lambda S The temperature of each heater was kept constant during the test, and the test results of the composite materials are shown in table 2.
Gaolida (a Chinese character) ［6］ (preparation of hexagonal boron nitride-cubic boron nitride/epoxy resin composite Material and thermal Property [ J)]The heat conductivity coefficient of the hexagonal boron nitride epoxy resin (hBN/EP) composite heat conduction material reported by composite material school report, 2022) is 0.444W/(m.K); novel CP/aluminum nitride composite heat conduction material G 5 Resistance value R of (2) S =15.24×10 -4 m 2 K/W, coefficient of thermal conductivity lambda S Compared with 2.876W/m.k, the heat conduction performance is greatly improved; its surface resistivity is 7.014 ×10 3 Omega cm is an excellent material for manufacturing circuit substrates. .
Example 6:
dissolving 4-6 g of 4, 4-thiodiphenol with the CAS number of 2664-63-3 in 30-50 ml of acetonitrile, adding methyl chloroacetate, wherein the mass ratio of the 4, 4-thiodiphenol to the methyl chloroacetate is 1 (2-2.3), and adding 1-5% of K by mass of the 4, 4-thiodiphenol 2 CO 3 Reacting for 3-4 h at 80-90 ℃ as a catalyst, filtering to obtain a clear solution after the reaction, removing acetonitrile by rotary evaporation, dissolving with 20-30 ml of chloroform, washing with 100-150 ml of 0.8-1 mol/L NaOH solution, washing with water for 2-3 times, and adding 2-3 g of Na into an organic phase 2 SO 4 Filtering, and removing chloroform by rotary evaporation to obtain diester monomer M.
Into a 50ml one-necked flask, 3.399g (16 mmol) of 1, 4-dithio-2, 5-bis (methanethiol), 1.990g (14 mmol) of 2, 5-thiophenedimethanol, 8.800g (25 mmol) of 2-diester monomer M and 0.004g (0.015 mmol) of dibutyltin oxyhydroxide were successively charged. Introducing nitrogen for protection, and stirring and reacting for 3 hours at 210 ℃ to obtain an esterification product. And continuously heating the esterification product to 240 ℃, controlling the absolute pressure in a reaction system to be about 80 Pa, and reacting 3h to obtain a crude product of the polycondensation product. Adding 30mL of chloroform into the polyester crude product, soaking for 2 hours, and filtering; taking clear liquid and adding 50m drop by dropl in methanol to obtain turbid liquid, centrifuging, filtering to obtain solid, washing the obtained solid with ethanol, and drying the filtered solid at 60deg.C for 2h to obtain 13.101g copolyester CP 6 The yield thereof was found to be 92.33%. The molecular weight of the polyester measured by Ubbelohde viscometer is 22100 g/mol, and the copolyester CP 6 The test results of (2) are shown in Table 1.
10g of aluminum nitride powder was weighed out and kept at 100℃for 1 hour in vacuum for further use. Weighing 100g of copolyester CP, uniformly mixing with 1g of chain extender epoxy compound glycidyl acrylate, 0.5g of antioxidant 1010 and 5g of liquid paraffin, extruding by using a double-screw extruder, granulating, drying, grinding into powder, mixing with aluminum nitride powder by high-energy ball milling, putting into a container (such as a steel tank) of a high-energy ball mill, uniformly mixing the powder mixture, banburying by a banburying machine, and hot-pressing to form. The materials are crosslinked and solidified through the reaction in the extruder, the high-energy ball mill can fully mix the high-heat-conductivity aluminum nitride with the organic materials, and after banburying, the materials are finally hot-pressed and molded in a vacuum autoclave, thus obtaining the uniform and compact CP/aluminum nitride composite heat-conducting material G 6 . The composite heat conducting material is cut into wafers with the diameter of 50mm and the thickness of 3mm, and a thin layer of heat conducting medium is coated on the surface. The TCHM-LT heat conduction tester is adopted for testing, a wafer-shaped sample is placed between a cold-face heater (upper heater) and a hot-face heater (lower heater), and the temperature T of the lower surface of the sample is measured L And the upper surface temperature T of the sample U Obtaining thermal resistance R according to a flat plate method in a longitudinal heat flow method S And a thermal conductivity lambda S The temperature of each heater was kept constant during the test, and the test results of the composite materials are shown in table 2.
Gaolida (a Chinese character) ［6］ (preparation of hexagonal boron nitride-cubic boron nitride/epoxy resin composite Material and thermal Property [ J)]The heat conductivity coefficient of the hexagonal boron nitride epoxy resin (hBN/EP) composite heat conduction material reported by composite material school report, 2022) is 0.444W/(m.K); novel CP/aluminum nitride composite heat conduction material G 6 Resistance value R of (2) S =12.31×10 -4 m 2 K/W, coefficient of thermal conductivity lambda S =3.142W/m·k, in contrast to heat conductionThe performance is greatly improved; its surface resistivity is 5.769 ×10 3 Omega cm is an excellent material for manufacturing circuit substrates.
Example 7:
dissolving 4-6 g of 4, 4-thiodiphenol with the CAS number of 2664-63-3 in 30-50 ml of acetonitrile, adding methyl chloroacetate, wherein the mass ratio of the 4, 4-thiodiphenol to the methyl chloroacetate is 1 (2-2.3), and adding 1-5% of K by mass of the 4, 4-thiodiphenol 2 CO 3 Reacting for 3-4 h at 80-90 ℃ as a catalyst, filtering to obtain a clear solution after the reaction, removing acetonitrile by rotary evaporation, dissolving with 20-30 ml of chloroform, washing with 100-150 ml of 0.8-1 mol/L NaOH solution, washing with water for 2-3 times, and adding 2-3 g of Na into an organic phase 2 SO 4 Filtering, and removing chloroform by rotary evaporation to obtain diester monomer M.
Into a 50ml one-necked flask, 3.399g (16 mmol) of 1, 4-dithio-2, 5-bis (methanethiol), 1.990g (14 mmol) of 2, 5-thiophenedimethanol, 8.800g (25 mmol) of 2-diester monomer M and 0.003g (0.027 mmol) of methanesulfonic acid were successively charged. Introducing nitrogen to protect, and stirring at 200 ℃ to react 4h to obtain an esterification product. And continuously heating the esterification product to 240 ℃, controlling the absolute pressure in a reaction system to be about 80 Pa, and reacting 3h to obtain a crude product of the polycondensation product. Adding 30mL of chloroform into the polyester crude product, soaking for 2 hours, and filtering; adding the clear solution into 50ml methanol dropwise to obtain turbid liquid, centrifuging, filtering to obtain solid, washing the obtained solid with ethanol, and drying the filtered solid at 60deg.C for 2h to obtain 13.206g copolyester CP 7 The yield thereof was found to be 93.07%. The molecular weight of the polyester is 29200 g/mol measured by Ubbelohde viscometer, and the copolyester CP 7 The test results of (2) are shown in Table 1.
10g of aluminum nitride powder was weighed and dried in vacuum at 100℃for 1 hour for further use. Weighing 100g of copolyester CP, uniformly mixing with 1g of chain extender epoxy compound glycidyl acrylate, 0.5g of antioxidant 1010 and 5g of liquid paraffin, extruding by using a double-screw extruder, granulating, drying, grinding into powder, mixing with aluminum nitride powder by high-energy ball milling, and filling into a container (such as a steel tank) of a high-energy ball mill to uniformly mix the powder mixtureMixing, banburying, hot pressing and forming. The materials are crosslinked and solidified through the reaction in the extruder, the high-energy ball mill can fully mix the high-heat-conductivity aluminum nitride with the organic materials, and after banburying, the materials are finally hot-pressed and molded in a vacuum autoclave, thus obtaining the uniform and compact CP/aluminum nitride composite heat-conducting material G 7 . The composite heat conducting material is cut into wafers with the diameter of 50mm and the thickness of 3mm, and a thin layer of heat conducting medium is coated on the surface. The TCHM-LT heat conduction tester is adopted for testing, a wafer-shaped sample is placed between a cold-face heater (upper heater) and a hot-face heater (lower heater), and the temperature T of the lower surface of the sample is measured L And the upper surface temperature T of the sample U Obtaining thermal resistance R according to a flat plate method in a longitudinal heat flow method S And a thermal conductivity lambda S The temperature of each heater was kept constant during the test, and the test results of the composite materials are shown in table 2.
Gaolida (a Chinese character) ［6］ (preparation of hexagonal boron nitride-cubic boron nitride/epoxy resin composite Material and thermal Property [ J)]The heat conductivity coefficient of the hexagonal boron nitride epoxy resin (hBN/EP) composite heat conduction material reported by composite material school report, 2022) is 0.444W/(m.K); novel CP/aluminum nitride composite heat conduction material G 7 Resistance value R of (2) S =9.31×10 -4 m 2 K/W, coefficient of thermal conductivity lambda S Compared with 3.684W/m.k, the heat conduction performance is greatly improved; its surface resistivity is 4.598X10 3 Omega cm is an excellent material for manufacturing circuit substrates.
Example 8:
dissolving 4-6 g of 4, 4-thiodiphenol with the CAS number of 2664-63-3 in 30-50 ml of acetonitrile, adding methyl chloroacetate, wherein the mass ratio of the 4, 4-thiodiphenol to the methyl chloroacetate is 1 (2-2.3), and adding 1-5% of K by mass of the 4, 4-thiodiphenol 2 CO 3 Reacting for 3-4 h at 80-90 ℃ as a catalyst, filtering to obtain a clear solution after the reaction, removing acetonitrile by rotary evaporation, dissolving with 20-30 ml of chloroform, washing with 100-150 ml of 0.8-1 mol/L NaOH solution, washing with water for 2-3 times, and adding 2-3 g of Na into an organic phase 2 SO 4 Filtering, and removing chloroform by rotary evaporation to obtain diester monomer M。
Into a 50ml one-necked flask, 3.399g (16 mmol) of 1, 4-dithio-2, 5-bis (methanethiol), 1.990g (14 mmol) of 2, 5-thiophenedimethanol, 8.800g (25 mmol) of 2-diester monomer M and 0.007g (0.024 mmol) of antimony trioxide were successively charged. Introducing nitrogen to protect, and stirring at 200 ℃ to react 4h to obtain an esterification product. And continuously heating the esterification product to 240 ℃, controlling the absolute pressure in a reaction system to be about 80 Pa, and reacting 3h to obtain a crude product of the polycondensation product. Adding 30mL of chloroform into the polyester crude product, soaking for 2 hours, and filtering; adding the clear solution into 50ml methanol dropwise to obtain turbid liquid, centrifuging, filtering to obtain solid, washing the obtained solid with ethanol, and drying the filtered solid at 60deg.C for 2h to obtain 12.949g copolyester CP 8 The yield thereof was found to be 91.26%. The molecular weight of the polyester is 28100 g/mol measured by Ubbelohde viscometer, and the copolyester CP 8 The test results of (2) are shown in Table 1.
10g of aluminum nitride powder was weighed and dried in vacuum at 100℃for 1 hour for further use. Weighing 100g of copolyester CP, uniformly mixing with 1g of chain extender epoxy compound glycidyl acrylate, 0.5g of antioxidant 1010 and 5g of liquid paraffin, extruding by using a double-screw extruder, granulating, drying, grinding into powder, mixing with aluminum nitride powder by high-energy ball milling, putting into a container (such as a steel tank) of a high-energy ball mill, uniformly mixing the powder mixture, banburying by a banburying machine, and hot-pressing to form. The materials are crosslinked and solidified through the reaction in the extruder, the high-energy ball mill can fully mix the high-heat-conductivity aluminum nitride with the organic materials, and after banburying, the materials are finally hot-pressed and molded in a vacuum autoclave, thus obtaining the uniform and compact CP/aluminum nitride composite heat-conducting material G 8 . The composite heat conducting material is cut into wafers with the diameter of 50mm and the thickness of 3mm, and a thin layer of heat conducting medium is coated on the surface. The TCHM-LT heat conduction tester is adopted for testing, a wafer-shaped sample is placed between a cold-face heater (upper heater) and a hot-face heater (lower heater), and the temperature T of the lower surface of the sample is measured L And the upper surface temperature T of the sample U Obtaining thermal resistance R according to a flat plate method in a longitudinal heat flow method S And a thermal conductivity lambda S The temperature of each heater was kept constant during the test, and the test results of the composite materials are shown in table 2.
Gaolida (a Chinese character) ［6］ (preparation of hexagonal boron nitride-cubic boron nitride/epoxy resin composite Material and thermal Property [ J)]The heat conductivity coefficient of the hexagonal boron nitride epoxy resin (hBN/EP) composite heat conduction material reported by composite material school report, 2022) is 0.444W/(m.K); novel CP/aluminum nitride composite heat conduction material G 8 Resistance value R of (2) S =5.97×10 -4 m 2 K/W, coefficient of thermal conductivity lambda S Compared with polyester prepared by the prior art, the heat conduction performance of the polyester is greatly improved; its surface resistivity is 2.312×10 3 Omega cm is an excellent material for manufacturing circuit substrates.
TABLE 1 copolyester CP in examples 1-8 1 ～CP 8 Comparison of test results of samples with EP mechanical Properties
| Sample of | Mn/(10 4 g/mol) | Tensile breaking strength/MPa | Elongation at break (%) | Flexural Strength/MPa |
| CP 1 | 2.68 | 67.9 | 247.4 | 105.67 |
| CP 2 | 2.31 | 72.6 | 256.1 | 103.55 |
| CP 3 | 2.98 | 69.8 | 255.2 | 113.21 |
| CP 4 | 2.52 | 80.3 | 243.4 | 108.69 |
| CP 5 | 2.38 | 76.6 | 252.3 | 115.24 |
| CP 6 | 2.21 | 92.5 | 261.7 | 120.31 |
| CP 7 | 2.92 | 90.1 | 249.3 | 109.62 |
| CP 8 | 2.81 | 85.2 | 251.7 | 113.55 |
| EP [4] | —— | 44.7 | 291.1 | 31.66 |
[4] Wang Feiyue, liao Guhao, yan Long Synthesis of diaminodiphenyl methane modified ammonium polyphosphate and its use in epoxy resins [ J ]. Polymer science and engineering, 2022,38 (2): 24-31. DOI:10.16865/J. Cnki.1000-7555.2022.0039.
TABLE 2 composite Heat conducting Material H synthesized according to the examples 1 ~H 8 Is of the heat conduction property of (a)
| Sample of | Content wt% of aluminum nitride as heat conducting material | Thermal resistance value R S （×10 -4 m 2 K/W） | Coefficient of thermal conductivity lambda S (W/m·k) |
| G 1 | 20% | 25.31 | 1.774 |
| G 2 | 25% | 22.28 | 1.973 |
| G 3 | 30% | 20.09 | 2.209 |
| G 4 | 35% | 17.53 | 2.533 |
| G 5 | 40% | 15.24 | 2.876 |
| G 6 | 45% | 12.31 | 3.142 |
| G 7 | 50% | 9.31 | 3.684 |
| G 8 | 55% | 5.97 | 5.380 |
| Organosilicon composite material [5] | —— | 23.51 | 1.511 |
| hBN/EP composite material [6] | —— | 80.07 | 0.444 |
[5] Wu Zhijun, zhou Xiaosong, liu Canqun. Preparation of organosilicon heat-conducting composite material and its property [ J ]. Functional material, 2022,53 (5): 5153-5159. DOI:10.3969/J. Issn.1001-9731.2022.05.020.
[6] Gao Lida, li Xiang, zhang Xiaochong, et al, preparation of hexagonal boron nitride-cubic boron nitride/epoxy resin composites and thermal Properties [ J ]. Programming of composites, 2022,39 (6): 2599-2606. DOI:10.13801/J. Cnki. Fhclxb.20210819.005.
As can be seen from the comparison of the data in Table 1, the copolyester CP synthesized by using 1, 4-dithio-2, 5-di (methane mercaptan), 2, 5-thiophene dimethanol and 4, 4-thiodiphenol as raw materials in the invention 1 ～CP 8 The tensile breaking strength is 20-48 MPa higher than that of the epoxy resin (EP); the elongation at break of the epoxy resin (EP) was 291.1%, while the copolyester CP of the present invention was synthesized using 1, 4-dithio-2, 5-di (methanethiol), 2, 5-thiophenedimethanol and 4, 4-thiodiphenol as raw materials 1 ～CP 8 The elongation at break of (a) is slightly lower than that of the epoxy resin (EP); as can be seen from the comparison of the bending strength in Table 1, the degradable copolyester based on 4, 4-thiodiphenol synthesized by the invention can be suitable for more severe environment, and the service life is greatly prolonged, thereby reducing the cost. As can be seen from Table 2, the copolyester synthesized from 1, 4-dithio-2, 5-di (methane mercaptan), 2, 5-thiophene dimethanol and 4, 4-thiodiphenol as raw materials has better heat conduction performance with aluminum nitride, and as the aluminum nitride content in the composite heat conduction material increases, heat conductionThe better the effect. When the mass fraction of the aluminum nitride reaches 55%, the heat conduction performance reaches the best, and the thermal resistance value of the composite material is 5.97x10 -4 m 2 K/W, a thermal conductivity of 5.380W/mK, compared with document [5]]Silicone composite materials and literature [6]]The hBN/EP composite material is 2-10 times higher than that of the prior art.
In summary, the heat conducting material reported in the prior literature has the defects of poor mechanical property, narrow practical range, incapability of simultaneously considering thermal property, electrical property and the like, and is difficult to meet the requirements of various material properties in practical application. Aiming at the problems in the prior art, the invention prepares a novel heat conduction composite material CP/aluminum nitride composite heat conduction material, and the specific method is that 4, 4-thiodiphenol and methyl chloroacetate are subjected to phenolic hydroxyl esterification reaction to obtain a diester monomer M, and the diester monomer M is subjected to transesterification with a dihydric alcohol monomer 1, 4-disulfide-2, 5-di (methane mercaptan) and 2, 5-thiophene dimethanol to obtain a novel esterification product. Heating the esterification product to perform polycondensation reaction to obtain a crude product of the polycondensation product; finally, the copolyester CP is obtained through solvent extraction, precipitant precipitation, filtration and drying, and the obtained copolyester CP and aluminum nitride powder are crosslinked together through a high-energy ball milling method to obtain a target product. Therefore, the invention patent based on the degradable copolyester of 4, 4-thiodiphenol, the preparation method and the application has good market prospect.
The novel bio-based polyester monomer is synthesized by adopting 4, 4-thiodiphenol and methyl chloroacetate as reaction raw materials, and replaces polyester prepared by taking petroleum-based monomers as basic raw materials, thereby being beneficial to carbon emission reduction and carbon neutralization national policy implementation and having remarkable environmental protection characteristics.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the invention. It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (4)
1. The degradable copolyester based on 4, 4-thiodiphenol is characterized in that the structure is shown as formula 1:
x in the formula 1 is 40-116, Y is 58-144;
the preparation method comprises the following three steps:
1) Preparation of diester monomer M: dissolving 4-6 g of 4, 4-thiodiphenol with CAS number 2664-63-3 in 30-50 ml of acetonitrile, adding methyl chloroacetate, wherein the mass ratio of 4, 4-thiodiphenol to methyl chloroacetate is 1 (2-2.3), and adding K accounting for 1-5% of the mass of 4, 4-thiodiphenol 2 CO 3 Reacting for 3-4 h at 80-90 ℃ as a catalyst, filtering to obtain a clear solution after the reaction, evaporating acetonitrile, dissolving with 20-30 ml of chloroform, washing with water for 2-3 times, removing water phase, adding 2-3 g of Na into an organic phase 2 SO 4 Drying for 2 hours, filtering, and evaporating the filtrate to remove chloroform to obtain diester monomer M, wherein the structure is shown as formula 2:
2) Synthesis of polycondensation crude products: 1, 4-disulfide-2, 5-di (methane mercaptan) with CAS number of 136122-15-1 is used as a first alcohol source, 2, 5-thiophene dimethanol is used as a second alcohol source, the prepared monomer M, the first alcohol source and the second alcohol source are added into a reaction vessel according to the mass ratio of 10 (5.1-5.7) (4.3-4.9), a catalyst is added, nitrogen is introduced for protection, stirring reaction is carried out for 3-4 hours at 190-210 ℃ to obtain a new esterification product, the temperature of the new esterification product is continuously raised to 240-260 ℃, the absolute pressure in a reaction system is controlled to be 80-120 Pa, and polycondensation reaction is carried out for 3-4 hours under full stirring to obtain a polycondensation crude product;
3) Preparation of degradable copolyester: dissolving the polycondensation crude product with chloroform, filtering, taking clear liquid, adding lower alcohol into the clear liquid until precipitation is not increased, centrifugally separating, filtering, washing the obtained solid with ethanol, and drying the filtered solid at 60-70 ℃ for 2-3 hours to obtain the degradable copolyester based on 4, 4-thiodiphenol.
2. The degradable copolyester based on 4, 4-thiodiphenol according to claim 1, wherein the catalyst in the step 2) is one of potassium hexafluorotitanate, dibutyltin oxyhydroxide, methanesulfonic acid and antimony trioxide, and the catalyst is used in an amount of 0.05-0.15% of the amount of diester monomer M.
3. The degradable copolyester based on 4, 4-thiodiphenol according to claim 1, wherein the lower alcohol in the step 3) is one of methanol, ethanol, isopropanol, isobutanol and n-butanol.
4. Use of a degradable copolyester based on 4, 4-thiodiphenol according to any one of claims 1 to 3 for the preparation of a thermally conductive material, the preparation method comprising the steps of:
1) Mixing and banburying raw materials of the copolyester heat-conducting material: weighing 10 parts by mass of aluminum nitride powder, and drying in vacuum drying equipment at 100 ℃ for 1 hour for later use; weighing 100 parts by mass of the degradable copolyester according to any one of claims 1 to 3, uniformly mixing the degradable copolyester with 1 part by mass of the chain extender epoxy compound glycidyl acrylate, 0.5 part by mass of the antioxidant 1010 and 1 to 5 parts by mass of the liquid paraffin, extruding the mixture by using a double-screw extruder, granulating, drying, grinding the mixture into powder, mixing the powder with aluminum nitride powder by a high-energy ball milling method, and banburying the mixture by an internal mixer;
2) And (3) forming and processing a copolyester heat-conducting material: the raw materials of the copolyester heat-conducting material in the step 1) are mixed and banburying, and then are formed by hot-pressing; and obtaining the uniform and compact degradable copolyester/aluminum nitride composite heat-conducting material.
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