CN103819895A - Epoxy group modified graphite, heat-conduction nylon composite and preparation of modified graphite and composite - Google Patents
Epoxy group modified graphite, heat-conduction nylon composite and preparation of modified graphite and composite Download PDFInfo
- Publication number
- CN103819895A CN103819895A CN201410088216.8A CN201410088216A CN103819895A CN 103819895 A CN103819895 A CN 103819895A CN 201410088216 A CN201410088216 A CN 201410088216A CN 103819895 A CN103819895 A CN 103819895A
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- Prior art keywords
- graphite
- nylon
- modified graphite
- epoxide group
- group modified
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- 239000004677 Nylon Substances 0.000 title claims abstract description 51
- 229920001778 nylon Polymers 0.000 title claims abstract description 51
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000002131 composite material Substances 0.000 title claims abstract description 18
- -1 Epoxy group modified graphite Chemical class 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000010439 graphite Substances 0.000 claims abstract description 32
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 32
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 29
- 239000004593 Epoxy Substances 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 14
- 239000003112 inhibitor Substances 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 claims description 3
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 229940125904 compound 1 Drugs 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 abstract description 8
- 239000011159 matrix material Substances 0.000 abstract description 7
- 238000005453 pelletization Methods 0.000 abstract description 6
- 150000002118 epoxides Chemical class 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 238000011049 filling Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 abstract description 2
- 125000003700 epoxy group Chemical group 0.000 abstract 2
- 239000003963 antioxidant agent Substances 0.000 abstract 1
- 230000003078 antioxidant effect Effects 0.000 abstract 1
- 230000002925 chemical effect Effects 0.000 abstract 1
- 230000000704 physical effect Effects 0.000 abstract 1
- 230000009257 reactivity Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 6
- 238000011284 combination treatment Methods 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229920002292 Nylon 6 Polymers 0.000 description 4
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 description 3
- 239000011231 conductive filler Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- 241000024287 Areas Species 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
Abstract
The invention discloses epoxy group modified graphite, a heat-conduction nylon composite and preparation methods of the modified graphite and the composite. The heat-conduction nylon composite comprises components in parts by mass as follows: 25-50 parts of nylon, 50-75 parts of bifunctional epoxide modified graphite and 0.1-0.5 part of an antioxidant. The components are mixed by a high-speed mixer and subjected to extrusion pelletization, and a product is obtained. According to the invention, the bifunctional epoxide with low molecular weight is used for performing surface modification on heat-conduction graphite powder, and an epoxy group with reactivity is grafted to the graphite surface due to physical and chemical effects; and besides, the bulk density of the graphite is increased remarkably, and high filling in a nylon matrix can be achieved. The epoxy group on the graphite surface has a chain extension function on nylon in an extrusion process, so that not only is the nylon endowed with good heat conduction performance, but also the mechanical property of the nylon is improved.
Description
Technical field
The present invention relates to a kind of epoxide group modified graphite and heat conduction nylon composite materials that adopts this modified graphite to prepare and preparation method thereof, belong to field of high polymer material processing.
Background technology
Nylon is as the most frequently used engineering plastics, there is excellent over-all properties, but thermal conductivity is low, only has 0.2-0.3 W/mK, in Application Areass such as LED illumination, automobile, electronic products, material heat transfer heat dispersion is had to higher requirement, and the low use that limits to a great extent nylon material of thermal conductivity.
Graphite wide material sources, cheap, be a kind of multifunctional inorganic filler, there is excellent heat conductivility, fill it in nylon, can significantly improve the heat conductivility of nylon.But, in order further to improve the heat conductivility of nylon, need to strengthen the addition of graphite, but because graphite tap density is little, content of graphite increase can cause filling difficulty, is difficult to disperse well in nylon matrix, can cause the mechanical property of nylon significantly to decline.Therefore, improve the tap density of graphite, increase the loading level of graphite in nylon matrix, when improving nylon material thermal conductivity, can keep or improve the intensity of material, become particularly important.
The nylon composite materials of a kind of high heat conduction described in patent CN102775767A, its high comprehensive performance, but rare earth element yttrium is unstable in air, easily cause nylon composite materials mechanical properties decrease, simultaneously, the treatment condition of rare earth element yttrium need very strict condition, are unfavorable for scale operation; The treatment process of heat conductive filler described in patent CN102408710A is to add heat conductive filler after nylon is dissolved, and after mixing, dries multi-program through drying crushing washing again, is unfavorable for suitability for industrialized production.
Summary of the invention
The heat conduction nylon composite materials that the object of the present invention is to provide a kind of epoxide group modified graphite and adopt this modified graphite to prepare, this heat conduction nylon composite materials has good mechanical property and higher thermal conductivity.
A kind of epoxide group modified graphite of the present invention, it is graphite and bifunctional epoxy compound 1, the combination of 6-hexanediol diglycidyl ether or BDDE or ethylene glycol diglycidylether; Described bifunctional epoxy compound's quality is the 8%-10% of graphite quality.
Above-mentioned graphite median size is good at 1-13 μ m.
The preparation method of epoxide group modified graphite of the present invention, it is at 80-85 ℃, and graphite and bifunctional epoxy compound's high-speed mixing processing 30-50min are made to bifunctional epoxy compound's modified graphite.
Before high-speed mixing is processed, described graphite being put in to 110-120 ℃ of baking oven inner drying 6-8h is advisable.
Heat conduction nylon composite materials provided by the invention, mainly made by the raw material of following mass parts:
Nylon 25-50 part;
Epoxide group modified graphite 50-75 part described above;
Oxidation inhibitor 0.1-0.5 part.
Described nylon is preferably PA6 or PA66.
Described oxidation inhibitor is that antioxidant 1010 and irgasfos 168 are used in conjunction with according to mass ratio 1:1.
The preparation method of heat conduction nylon composite materials of the present invention, comprises the steps:
(1) by following component and mass parts content raw materials weighing, nylon 25-50 part, epoxide group modified graphite 50-75 part, oxidation inhibitor 0.1-0.5 part;
(2) raw materials weighing is added to high-speed mixer mixing 3-5min;
(3) will join twin screw extruder through the mixed raw material of step (2), extruder temperature is 195-265 ℃, and screw speed 200-350rpm, through extruding, traction, granulation make product.
Step (2) is before high-speed mixing, and it is good that nylon is dried to 7-8h at 100-105 ℃ in vacuum drying oven.
The present invention uses bifunctional epoxy compound to carry out surface modification to graphite, an one epoxide group and graphite surface generation physics chemical action, make to have in graphite surface grafting the epoxide group of reactive behavior, in extrusion production process, the epoxide group on bifunctional epoxy compound's modified graphite surface can react with nylon molecular chain-end amino or carboxyl, nylon molecular chain can be coupled together, nylon is played to chain extension effect to a certain extent, the mechanical property of nylon is promoted, and the tensile strength of its matrix material is greater than 50MPa; The surface of bifunctional epoxy compound's modified graphite has become hydrophobicity from wetting ability in addition, has greatly improved the consistency of graphite and matrix, and graphite can be dispersed in nylon matrix well; Through bifunctional epoxy compound, graphite is carried out after surface modification, the tap density of graphite increases considerably, and this has improved the loading level of graphite in nylon matrix greatly, thereby the thermal conductivity of nylon material is greatly improved, more than thermal conductivity 2.3W/mK.
Embodiment
Following embodiment is further illustrating using the explaination as to the technology of the present invention content for content of the present invention; but flesh and blood of the present invention is not limited in described in following embodiment, those of ordinary skill in the art can and should know any simple change or replacement based on connotation of the present invention all should belong to protection domain of the presently claimed invention.
embodiment 1
Take median size 2.5 μ m graphite 1000g at 110-120 ℃, after baking oven inner drying 6-8h, take out and add high-speed mixer, at 80-85 ℃, add 80g bifunctional epoxy compound 1,6-hexanediol diglycidyl ether, makes bifunctional epoxy compound's modified graphite after combination treatment 45-50min.
Nylon 6 is dried to 7-8h at 100-105 ℃ in vacuum drying oven, get 30 parts of dry 6,70 parts of above-mentioned gained bifunctional epoxy compound modified graphites of nylon, (antioxidant 1010 and irgasfos 168 are used in conjunction with according to mass ratio 1:1 0.2 part of oxidation inhibitor, add high-speed mixer mixing 3-5min down together), after taking-up, add forcing machine, make product through extruding pelletization.Extrusion temperature 195-245 ℃, engine speed 260rmp.After product is injection molded into standard batten, test performance is as follows: thermal conductivity 3.4W/mK, tensile strength 50.8MPa.
embodiment 2
Take median size 5 μ m graphite 1000g at 110-120 ℃, after baking oven inner drying 6-8h, take out and add high-speed mixer, at 80-85 ℃, add 100g bifunctional epoxy compound 1,4-butanediol diglycidyl ether, makes bifunctional epoxy compound's modified graphite after combination treatment 45-50min.
Nylon 66 is dried to 7-8h at 100-105 ℃ in vacuum drying oven, get 40 parts of dry nylon 66,60 parts, 0.2 part oxidation inhibitor of above-mentioned bifunctional epoxy compound's modified graphite and add high-speed mixer mixing 3-5min, after taking-up, add forcing machine, make product through extruding pelletization.Extrusion temperature 235-265 ℃, engine speed 245rmp.It is as follows that product is injection molded into standard batten test performance: thermal conductivity 2.9W/mK, tensile strength 80.0MPa.
embodiment 3
Take median size 10 μ m graphite 1000g at 110-120 ℃, after baking oven inner drying 6-8h, take out and add high-speed mixer, at 80-85 ℃, add 100g bifunctional epoxy compound 1,6-hexanediol diglycidyl ether, makes bifunctional epoxy compound's modified graphite after combination treatment 45-50min.
Nylon 66 is dried to 7-8h at 100-105 ℃ in vacuum drying oven, get 50 parts of dry nylon 66,50 parts, 0.3 part oxidation inhibitor of above-mentioned bifunctional epoxy compound's modified graphite and add high-speed mixer mixing 3-5min, after taking-up, add forcing machine, make product through extruding pelletization.Extrusion temperature 235-260 ℃, engine speed 250rmp.It is as follows that product is injection molded into standard batten test performance: thermal conductivity 2.4W/mK, tensile strength 87.7MPa.
embodiment 4
Take median size 10 μ m graphite 1000g at 110-120 ℃, after baking oven inner drying 6-8h, take out and add high-speed mixer, at 80-85 ℃, add 100g bifunctional epoxy compound ethylene glycol diglycidylether, after combination treatment 45-50min, make bifunctional epoxy compound's modified graphite.
Nylon 6 is dried to 7-8h at 100-105 ℃ in vacuum drying oven, get 50 parts of dry nylon 6,50 parts, 0.2 part oxidation inhibitor of above-mentioned bifunctional epoxy compound's modified graphite and add high-speed mixer mixing 3-5min, after taking-up, add forcing machine, make product through extruding pelletization.Extrusion temperature 195-250 ℃, engine speed 275rmp.It is as follows that product is injection molded into standard batten test performance: thermal conductivity 2.3W/mK, tensile strength 67.5MPa.
embodiment 5
Take median size 8 μ m graphite 1000g at 110-120 ℃, after baking oven inner drying 6-8h, take out and add high-speed mixer, at 80-85 ℃, add 80g bifunctional epoxy compound 1,6-hexanediol diglycidyl ether, makes bifunctional epoxy compound's modified graphite after combination treatment 45-50min.
Nylon 6 is dried to 7-8h at 100-105 ℃ in vacuum drying oven, get 45 parts of dry nylon 6,55 parts, 0.2 part oxidation inhibitor of above-mentioned bifunctional epoxy compound's modified graphite and add high-speed mixer mixing 3-5min, after taking-up, add forcing machine, make product through extruding pelletization.Extrusion temperature 195-250 ℃, engine speed 275rmp.It is as follows that product is injection molded into standard batten test performance: thermal conductivity 2.4W/mK, tensile strength 65.0MPa.
Claims (9)
1. an epoxide group modified graphite, it is graphite and bifunctional epoxy compound 1, the combination of 6-hexanediol diglycidyl ether or BDDE or ethylene glycol diglycidylether; Described bifunctional epoxy compound's quality is the 8%-10% of graphite quality.
2. epoxide group modified graphite as claimed in claim 1, is characterized in that, described graphite median size is 1-13 μ m.
3. the preparation method of epoxide group modified graphite described in claim 1, is characterized in that, at 80-85 ℃, graphite and bifunctional epoxy compound's high-speed mixing processing 30-50min is made to bifunctional epoxy compound's modified graphite.
4. the preparation method of epoxide group modified graphite as claimed in claim 3, is characterized in that, high-speed mixing is put in 110-120 ℃ of baking oven inner drying 6-8h by described graphite before processing.
5. the heat conduction nylon composite materials based on epoxide group modified graphite described in claim 1-4 any one, mainly made by the raw material of following mass parts:
Nylon 25-50 part;
Epoxide group modified graphite 50-75 part;
Oxidation inhibitor 0.1-0.5 part.
6. described in claim 1-4 any one
Heat conduction nylon composite materials, is characterized in that as claimed in claim 5, and described nylon is PA6 or PA66.
7. heat conduction nylon composite materials as claimed in claim 5, is characterized in that, described oxidation inhibitor is that antioxidant 1010 and irgasfos 168 are used in conjunction with according to mass ratio 1:1.
8. the preparation method of heat conduction nylon composite materials described in claim 5, is characterized in that, comprises the steps:
(1) by following component and mass parts content raw materials weighing, nylon 25-50 part, epoxide group modified graphite 50-75 part, oxidation inhibitor 0.1-0.5 part;
(2) raw materials weighing is added to high-speed mixer mixing 3-5min;
(3) will join twin screw extruder through the mixed raw material of step (2), extruder temperature is 195-265 ℃, and screw speed 200-350rpm, through extruding, traction, granulation make product.
9. the preparation method of heat conduction nylon composite materials as claimed in claim 8, is characterized in that, step (2), before high-speed mixing, is dried 7-8h at 100-105 ℃ in vacuum drying oven by nylon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410088216.8A CN103819895B (en) | 2014-03-11 | 2014-03-11 | A kind of epoxide group modified graphite and heat conduction nylon composite materials and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410088216.8A CN103819895B (en) | 2014-03-11 | 2014-03-11 | A kind of epoxide group modified graphite and heat conduction nylon composite materials and preparation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103819895A true CN103819895A (en) | 2014-05-28 |
| CN103819895B CN103819895B (en) | 2016-05-04 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410088216.8A Expired - Fee Related CN103819895B (en) | 2014-03-11 | 2014-03-11 | A kind of epoxide group modified graphite and heat conduction nylon composite materials and preparation thereof |
Country Status (1)
| Country | Link |
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| CN (1) | CN103819895B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104629496A (en) * | 2015-03-05 | 2015-05-20 | 贵州一当科技有限公司 | Treatment method of modified graphene |
| CN111020739A (en) * | 2019-12-24 | 2020-04-17 | 广州市中诚新型材料科技有限公司 | Functional acid-oxidation-resistant polyamide fiber and preparation method thereof |
| CN112724661A (en) * | 2020-12-29 | 2021-04-30 | 河北亿正线缆有限公司 | High flame-retardant insulation type wire and cable |
| CN115322721A (en) * | 2022-10-11 | 2022-11-11 | 拓迪新材料(苏州)有限公司 | Room-temperature-cured epoxy heat-conducting adhesive for lithium battery, heat-conducting shell and preparation method of heat-conducting shell |
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| CN101781597A (en) * | 2010-02-24 | 2010-07-21 | 合肥工业大学 | Active lubricant for wear-resistant material and high-strength wear-resistant nylon material |
| CN102102001A (en) * | 2010-12-03 | 2011-06-22 | 烟台德邦科技有限公司 | High thermal conductivity graphene-based epoxy resin adhesive and preparation method thereof |
| CN102408710A (en) * | 2011-10-14 | 2012-04-11 | 中国工程物理研究院化工材料研究所 | Nylon 66 composite material with high heat conductivity and preparation method thereof |
| CN102775767A (en) * | 2012-05-21 | 2012-11-14 | 宁波泛龙塑料新材料有限公司 | High-heat-conduction nylon composite material and preparation method thereof |
| KR20140005398A (en) * | 2012-06-27 | 2014-01-15 | 롯데케미칼 주식회사 | Poly-amide resin composition |
-
2014
- 2014-03-11 CN CN201410088216.8A patent/CN103819895B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101781597A (en) * | 2010-02-24 | 2010-07-21 | 合肥工业大学 | Active lubricant for wear-resistant material and high-strength wear-resistant nylon material |
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| CN102408710A (en) * | 2011-10-14 | 2012-04-11 | 中国工程物理研究院化工材料研究所 | Nylon 66 composite material with high heat conductivity and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104629496A (en) * | 2015-03-05 | 2015-05-20 | 贵州一当科技有限公司 | Treatment method of modified graphene |
| CN111020739A (en) * | 2019-12-24 | 2020-04-17 | 广州市中诚新型材料科技有限公司 | Functional acid-oxidation-resistant polyamide fiber and preparation method thereof |
| CN111020739B (en) * | 2019-12-24 | 2022-10-14 | 广州市中诚新型材料科技有限公司 | Functional acid-oxidation-resistant polyamide fiber and preparation method thereof |
| CN112724661A (en) * | 2020-12-29 | 2021-04-30 | 河北亿正线缆有限公司 | High flame-retardant insulation type wire and cable |
| CN115322721A (en) * | 2022-10-11 | 2022-11-11 | 拓迪新材料(苏州)有限公司 | Room-temperature-cured epoxy heat-conducting adhesive for lithium battery, heat-conducting shell and preparation method of heat-conducting shell |
| CN115322721B (en) * | 2022-10-11 | 2023-01-13 | 拓迪化学(上海)有限公司 | Room-temperature-cured epoxy heat-conducting adhesive for lithium battery, heat-conducting shell and preparation method of heat-conducting shell |
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| Publication number | Publication date |
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| CN103819895B (en) | 2016-05-04 |
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