CN110964307A - Flame-retardant wear-resistant thermoplastic polyurethane composite material and preparation method thereof - Google Patents
Flame-retardant wear-resistant thermoplastic polyurethane composite material and preparation method thereof Download PDFInfo
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- CN110964307A CN110964307A CN201911265867.9A CN201911265867A CN110964307A CN 110964307 A CN110964307 A CN 110964307A CN 201911265867 A CN201911265867 A CN 201911265867A CN 110964307 A CN110964307 A CN 110964307A
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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
- C08K3/38—Boron-containing compounds
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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
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
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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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Abstract
The invention belongs to the technical field of functional polymer materials, and particularly relates to a flame-retardant wear-resistant thermoplastic polyurethane composite material and a preparation method thereof. The flame-retardant wear-resistant thermoplastic polyurethane composite material is prepared from the following raw materials in parts by mass: 40-70 parts of thermoplastic polyurethane, 2-7 parts of boron nitride nano powder and 0.5-1 part of boric acid. The flame-retardant wear-resistant thermoplastic polyurethane composite material solves the problems that thermoplastic polyurethane is difficult to be compatible with boron nitride and functional materials need to be prepared by adding excessive fillers through the ingenious structural design, the synthesis process is simple and efficient, the flame resistance of the prepared thermoplastic polyurethane composite material can reach V-0 level, and good mechanical properties are kept; and this method is suitable for thermoplastic polyurethane systems having a hardness of 70A to 60D.
Description
Technical Field
The invention belongs to the technical field of functional polymer materials, and particularly relates to a flame-retardant wear-resistant thermoplastic polyurethane composite material and a preparation method thereof.
Background
Thermoplastic polyurethane is widely applied to national economy because of its good properties of tear resistance, tensile resistance, toughness, repeated use and the like. However, with the gradual improvement of the living guarantee of people, the performance of a single-component material can not meet the current requirements, the use performance and safety requirements of various materials are more and more emphasized by people, and the factors promote the urgent need of the thermoplastic polyurethane to be changed into the aspect of functional composite materials.
Boron nitride nanopowders, which are white inorganic fillers, are called "white graphite" because they have a graphene-like structure. The boron nitride nanopowder has chemical and mechanical resistance, good oxidation resistance, and no oxidation at 1500 deg.C, and is a high-performance inorganic additive.
At present, people prepare functional composite materials mainly by compounding with boron nitride through the following methods:
chinese patent CN201711162591.2 discloses a wear-resistant reinforcing agent for aqueous polyurethane paint, which utilizes boron nitride as a lubricant and a reinforcing agent to prepare the aqueous polyurethane paint with high strength and friction resistance. Chinese patent CN201910012878.X discloses a normal temperature curing aqueous polyurethane/boron nitride nano composite coating and a preparation method of a coating film thereof, wherein boron nitride nano powder with amino and hydroxyl is directly added into aqueous polyurethane to improve the water resistance and mechanical properties of a composite material. Chinese patent CN201711456667.2 discloses a polyurethane with high flame retardant property and a preparation method thereof, which prepares a polyurethane composite material with high flame retardant property by using a large amount of polymers (such as polyurethane, polycaprolactone diol, alkyd resin, etc.) and inorganic fillers (such as boron nitride, mica iron oxide, antimony trioxide, etc.). Chinese patent CN201910565393.3 discloses a wear-resistant polyurethane elastomer material and a method for manufacturing pump parts, and the wear-resistant polyurethane composite material is prepared by utilizing elastic polyurethane, silicon carbide, boron nitride, aluminum oxide and the like.
Although many boron nitride/polyurethane functional composites have been prepared by the above methods, these methods all have a significant disadvantage in that boron nitride needs to be directly mixed with polyurethane, and the amount of boron nitride added is not too small to achieve functionality, so that the compatibility between the two seriously affects the performance of the composite. Meanwhile, the methods also have the problems that a large amount of other auxiliary additives need to be added into a polyurethane system, and the like, so that a process which is simple to operate, low in cost and efficient is urgently needed for improving the versatility of the polyurethane composite material.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the defects of the prior art are overcome, and the flame-retardant wear-resistant thermoplastic polyurethane composite material has good wear-resistant and flame-retardant characteristics, and cannot be decomposed to generate toxic gas; the invention also provides a preparation method with low cost, which is scientific, reasonable, simple and efficient.
The flame-retardant wear-resistant thermoplastic polyurethane composite material is prepared from the following raw materials in parts by mass:
40-70 parts of thermoplastic polyurethane,
2-7 parts of boron nitride nano powder,
0.5-1 part of boric acid.
Wherein:
the thermoplastic polyurethane is thermoplastic polyurethane with the hardness of 70A-60D.
The diameter of the boron nitride nanopowder is 1-50 μm.
Preferably, the diameter of the boron nitride nanopowder is 2 μm, 20 μm or 45 μm.
The flame-retardant wear-resistant thermoplastic polyurethane composite material has the flame-retardant grade reaching V-0 and the DIN abrasion reducing to 11mm3。
The preparation method of the flame-retardant wear-resistant thermoplastic polyurethane composite material comprises the following steps:
(1) adding boron nitride nanopowder into a mixed solution of deionized water and ethanol, performing ultrasonic treatment, introducing into a polytetrafluoroethylene reaction kettle, heating at 150-180 ℃ for 10-18 h, naturally cooling to room temperature, centrifuging at 3000-5000 r/min for 10-30 min, taking supernatant, filtering, and finally re-dispersing into an ethanol solution to obtain an ultrathin boron nitride nanopowder dispersion liquid;
(2) and (2) uniformly stirring and melting the thermoplastic polyurethane at 190-210 ℃, introducing the mixed melt into a polytetrafluoroethylene mold while the thermoplastic polyurethane is hot, spraying the ultrathin boron nitride nano powder dispersion liquid prepared in the step (1) before the melt is cooled and formed, finally spraying a 100-200 mg/mL boric acid solution, and drying under vacuum to obtain the flame-retardant wear-resistant thermoplastic polyurethane composite material.
In the step (1), the volume ratio of the deionized water to the ethanol is 1: 1-1: 5.
preferably, the preparation method of the flame-retardant wear-resistant thermoplastic polyurethane composite material specifically comprises the following steps:
(1) adding 2-7 parts of boron nitride nanopowder into a mixed solution of deionized water and ethanol, wherein the concentration is 0.5-2 mg/mL, carrying out ultrasonic treatment for 30min, then introducing into a polytetrafluoroethylene reaction kettle, heating at 150-180 ℃ for 10-18 h, then naturally cooling to room temperature, centrifuging at 3000r/min for 10min, taking supernatant, filtering, and finally re-dispersing into an ethanol solution to obtain an ultrathin boron nitride nanopowder dispersion liquid;
(2) rapidly stirring 40-70 parts of thermoplastic polyurethane at 190-210 ℃ to uniformly melt, and finally introducing the mixed melt into a polytetrafluoroethylene mold while the mixed melt is hot; spraying 2-7 parts of the ultra-thin boron nitride nano powder dispersion liquid prepared in the step (1) before cooling and forming the melt; and finally, spraying 0.5-1 part of 100mg/mL boric acid solution, and drying in a vacuum drying oven at 80 ℃ to obtain the layered polyurethane/boron nitride composite material.
According to the invention, the wear-resistant and flame-retardant layered polyurethane/boron nitride composite material is prepared by embedding boron nitride nanopowder with high mechanical property, oxidation resistance and high inertia into the surface of thermoplastic polyurethane and firmly crosslinking an upper layered structure and a lower layered structure together by using boric acid. The composite material still maintains good flame retardant properties even when heated to 1500 ℃, and does not decompose to produce toxic gases.
The invention deposits the high-strength, oxidation-resistant and ultrathin boron nitride nanopowder on the surface of the thermoplastic polyurethane, thereby avoiding the difficult problem that the direct mixing of the boron nitride and the thermoplastic polyurethane is difficult to be compatible. Because the top of the thermoplastic polyurethane contains a large amount of boron nitride nanopowder, when the polyurethane/boron nitride composite material is invaded by external force and fire, the boron nitride layered structure at the top can provide stronger protection effect than the traditional direct mixing, thereby improving the wear resistance and flame retardance of the polyurethane/boron nitride composite material.
Compared with the prior art, the invention has the following beneficial effects:
1) the invention utilizes a small amount of boron nitride nanopowder to prepare the thermoplastic polyurethane/boron nitride layered composite coating with a compact protection structure, and solves the problems that boron nitride is incompatible with polyurethane and nano-filler is enough to play the characteristics of wear resistance, flame retardance and the like in the traditional form.
2) The multi-level layered structure of the boron nitride nanopowder and the thermoplastic polyurethane, the effective binding force between the boron nitride nanopowder and the thermoplastic polyurethane, and the self-lubricating property of the boron nitride promote the efficient transmission of external force between the boron nitride nanopowder and the polyurethane, thereby enhancing the wear resistance of the polyurethane composite material.
3) The existence of pure boron nitride on the top of the thermoplastic polyurethane greatly enhances the flame-retardant protective performance of the polyurethane composite material, and harmful gas can not be released in the combustion process.
4) The preparation method provided by the invention is low in cost, scientific, reasonable, simple and efficient.
Drawings
Fig. 1 is a schematic structural diagram of a flame-retardant wear-resistant thermoplastic polyurethane composite (layered polyurethane/boron nitride composite) prepared by the invention.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the present invention is not limited thereto, and modifications of the technical solutions of the present invention by those skilled in the art should be within the scope of the present invention.
Example 1
The wear-resistant and flame-retardant thermoplastic polyurethane composite material comprises the following raw materials in parts by weight:
40 parts of Thermoplastic Polyurethane (TPU),
7 parts of boron nitride nano powder (2 mu m),
0.8 part of boric acid, namely,
the thermoplastic polyurethane is a polyester injection molding grade 70A product T3170 produced by Shandong-Nowegian polyurethane GmbH.
The preparation method comprises the following steps:
(1) adding 7 parts of boron nitride nanopowder into a mixed solution of deionized water and ethanol at a fixed ratio (volume ratio of 1: 1) to obtain a solution with a concentration of 0.5mg/mL, performing ultrasonic treatment for 30min, introducing the solution into a polytetrafluoroethylene reaction kettle, heating at 160 ℃ for 15h, naturally cooling to room temperature, centrifuging at 3000r/min for 10min, taking the supernatant, filtering, and finally re-dispersing into an ethanol solution (with a concentration of 0.05mg/mL) to obtain the ultrathin boron nitride nanopowder dispersion.
(2) Rapidly stirring 40 parts of thermoplastic polyurethane at 190 ℃ to uniformly melt, and finally introducing the mixed melt into a polytetrafluoroethylene mold while the mixed melt is hot; and (2) spraying 7 parts of the ultrathin boron nitride nano powder dispersion liquid prepared in the step (1) before cooling and forming the melt, finally spraying 0.8 part of 100mg/mL boric acid solution, and drying in a vacuum drying oven at the temperature of 80 ℃ to obtain the layered polyurethane/boron nitride composite material.
Example 2
The wear-resistant and flame-retardant thermoplastic polyurethane composite material comprises the following raw materials in parts by weight:
50 parts of Thermoplastic Polyurethane (TPU),
5 parts of boron nitride nano powder (20 mu m),
1 part of boric acid, namely 1 part of boric acid,
the thermoplastic polyurethane is a polyester extrusion grade 80A product E2180 produced by Shandong Nonwei polyurethane GmbH.
The preparation method comprises the following steps:
(1) adding 5 parts of boron nitride nanopowder into a mixed solution of deionized water and ethanol at a fixed ratio (volume ratio of 1: 5) to obtain a solution with a concentration of 1mg/mL, performing ultrasonic treatment for 30min, introducing the solution into a polytetrafluoroethylene reaction kettle, heating at 170 ℃ for 12h, naturally cooling to room temperature, centrifuging at 3000r/min for 30min, taking the supernatant, filtering, and finally re-dispersing into an ethanol solution (with a concentration of 0.05mg/mL) to obtain the ultrathin boron nitride nanopowder dispersion.
(2) 50 parts of thermoplastic polyurethane is rapidly stirred at 200 ℃ to be uniformly melted, and finally the mixed melt is introduced into a polytetrafluoroethylene mold while the mixed melt is hot; and (2) spraying 5 parts of the ultrathin boron nitride nano powder dispersion prepared in the step (1) before cooling and forming the melt, finally spraying 1 part of 100mg/mL boric acid solution, and drying in a vacuum drying oven at 80 ℃ to obtain the layered polyurethane/boron nitride composite material.
Example 3
The wear-resistant and flame-retardant thermoplastic polyurethane composite material comprises the following raw materials in parts by weight:
60 parts of Thermoplastic Polyurethane (TPU),
3 parts of boron nitride nano powder (45 mu m),
0.5 part of boric acid, namely,
the thermoplastic polyurethane is a polyester injection molding grade 85A product T3185 produced by Shandong-Nowegian polyurethane GmbH.
The preparation method comprises the following steps:
(1) adding 3 parts of boron nitride nanopowder into a mixed solution of deionized water and ethanol at a fixed ratio (volume ratio of 1: 3) to obtain a 1.5mg/mL solution, performing ultrasonic treatment for 30min, introducing the solution into a polytetrafluoroethylene reaction kettle, heating at 150 ℃ for 18h, naturally cooling to room temperature, centrifuging at 5000r/min for 10min, taking the supernatant, filtering, and finally re-dispersing into an ethanol solution (concentration of 0.05mg/mL) to obtain the ultrathin boron nitride nanopowder dispersion.
(2) 60 parts of thermoplastic polyurethane is rapidly stirred at 200 ℃ to be uniformly melted, and finally the mixed melt is introduced into a polytetrafluoroethylene mold while the mixed melt is hot; and (2) spraying 3 parts of the ultrathin boron nitride nano powder dispersion liquid prepared in the step (1) before cooling and forming the melt, finally spraying 0.5 part of 150mg/mL boric acid solution, and drying in a vacuum drying oven at the temperature of 80 ℃ to obtain the layered polyurethane/boron nitride composite material.
Example 4
The wear-resistant and flame-retardant thermoplastic polyurethane composite material comprises the following raw materials in parts by weight:
70 parts of Thermoplastic Polyurethane (TPU),
7 parts of boron nitride nano powder (2 mu m),
1 part of boric acid, namely 1 part of boric acid,
the thermoplastic polyurethane is 360DU (Du) of a polyester injection molding grade 60D product produced by Shandong-Nowei polyurethane GmbH.
The preparation method comprises the following steps:
(1) adding 7 parts of boron nitride nanopowder into a mixed solution of deionized water and ethanol at a fixed ratio (volume ratio of 1: 2) to obtain a 2mg/mL solution, performing ultrasonic treatment for 30min, introducing the solution into a polytetrafluoroethylene reaction kettle, heating at 180 ℃ for 10h, naturally cooling to room temperature, centrifuging at 3000r/min for 10min, taking the supernatant, filtering, and finally re-dispersing into an ethanol solution (concentration of 0.05mg/mL) to obtain the ultrathin boron nitride nanopowder dispersion.
(2) Rapidly stirring 70 parts of thermoplastic polyurethane at 210 ℃ to be uniformly melted, and finally introducing the mixed melt into a polytetrafluoroethylene mold while the mixed melt is hot; and (2) spraying 7 parts of the ultrathin boron nitride nano powder dispersion prepared in the step (1) before cooling and forming the melt, finally spraying 1 part of 200mg/mL boric acid solution, and drying in a vacuum drying oven at 80 ℃ to obtain the layered polyurethane/boron nitride composite material.
Comparative example 1
40 parts of thermoplastic polyurethane (polyester injection grade 70A product T3170 produced by Shandong-Nowegian polyurethane Co., Ltd.) is rapidly stirred at 190 ℃ to be uniformly melted, the mixed melt is introduced into a polytetrafluoroethylene mold while the mixture is hot, and the polytetrafluoroethylene mold is dried in a vacuum drying oven at 80 ℃ to obtain the thermoplastic polyurethane.
Comparative example 2
50 parts of thermoplastic polyurethane (a polyester extrusion grade 80A product E2180 produced by Shandong-Nowei polyurethane Co., Ltd.) is rapidly stirred at 200 ℃ to be uniformly melted, the mixed melt is introduced into a polytetrafluoroethylene mold while the mixture is hot, and the polytetrafluoroethylene mold is dried in a vacuum drying oven at 80 ℃ to obtain the thermoplastic polyurethane.
Comparative example 3
60 parts of thermoplastic polyurethane (polyester injection grade 85A product T3185 produced by Shandong-Nowegian polyurethane Co., Ltd.) is rapidly stirred at 200 ℃ to be melted uniformly, the mixed melt is introduced into a polytetrafluoroethylene mold while the mixture is hot, and the polytetrafluoroethylene mold is dried in a vacuum drying oven at 80 ℃ to obtain the thermoplastic polyurethane.
Comparative example 4
70 parts of thermoplastic polyurethane (360 DU which is a polyester type injection molding grade 60D product produced by Shandong-Nowei polyurethane Co., Ltd.) is rapidly stirred at 210 ℃ to be uniformly melted, the mixed melt is introduced into a polytetrafluoroethylene mold while the mixed melt is hot, and the mixed melt is dried in a vacuum drying oven at 80 ℃ to obtain the thermoplastic polyurethane.
The materials of examples 1-4 and comparative examples 1-4 were tested for performance by the following methods:
(1) flame retardant property: the flame retardant property of the composite material is studied according to GB/T2408-2008 vertical burning test.
(2) DIN abrasion Performance: DIN abrasion was determined according to GB/T9867-2008.
The test results are shown in table 1.
TABLE 1 results of material Property test of examples 1 to 4 and comparative examples 1 to 4
| Item | Example 1 | Example 2 | Example 3 | Example 4 |
| Flame retardant rating | V-0 | V-0 | V-0 | V-0 |
| DIN abrasion/mm3 | 20 | 16 | 11 | 19 |
| Item | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 |
| Flame retardant rating | * | * | * | * |
| DIN abrasion/mm3 | 130 | 52 | 83 | 60 |
In the above table, represents combustibles.
As can be seen from fig. 1 and table 1, through the structural design, the stripped boron nitride nanopowder is deposited on the surface of the thermoplastic polyurethane, so that the thermoplastic polyurethane has the ultra-strong wear-resistant property, and due to the protective effect of the oxidation-resistant boron nitride nanopowder, the polyurethane/boron nitride composite material shows the huge flame-retardant potential in the flame-retardant test, the safety upper limit of the polyurethane material in use is improved, and the larger the size of the embedded boron nitride is, the more obvious the wear-resistant and flame-retardant properties are. Importantly, the flame-retardant and insulating protective layer material can be safely used as a flame-retardant and insulating protective layer material because no toxic gas is generated in the combustion process.
Claims (9)
1. A flame-retardant wear-resistant thermoplastic polyurethane composite material is characterized in that: the feed is prepared from the following raw materials in parts by mass:
40-70 parts of thermoplastic polyurethane,
2-7 parts of boron nitride nano powder,
0.5-1 part of boric acid.
2. The flame retardant, abrasion resistant thermoplastic polyurethane composite of claim 1 wherein: the thermoplastic polyurethane is thermoplastic polyurethane with the hardness of 70A-60D.
3. The flame retardant, abrasion resistant thermoplastic polyurethane composite of claim 1 wherein: the diameter of the boron nitride nanopowder is 1-50 μm.
4. The flame retardant, abrasion resistant thermoplastic polyurethane composite of claim 3 wherein: the diameter of the boron nitride nanopowder is 2 μm.
5. The flame retardant, abrasion resistant thermoplastic polyurethane composite of claim 3 wherein: the diameter of the boron nitride nanopowder is 20 μm.
6. The flame retardant, abrasion resistant thermoplastic polyurethane composite of claim 3 wherein: the diameter of the boron nitride nanopowder is 45 μm.
7. The flame retardant, abrasion resistant thermoplastic polyurethane composite of claim 1 wherein: the flame-retardant wear-resistant thermoplastic polyurethane composite material has the flame-retardant grade reaching V-0 and the DIN abrasion reducing to 11mm3。
8. A method of preparing a flame retardant abrasion resistant thermoplastic polyurethane composite material according to any one of claims 1 to 7, characterized in that: the method comprises the following steps:
(1) adding boron nitride nanopowder into a mixed solution of deionized water and ethanol, performing ultrasonic treatment, introducing into a polytetrafluoroethylene reaction kettle, heating at 150-180 ℃ for 10-18 h, cooling to room temperature, centrifuging at 3000-5000 r/min for 10-30 min, taking supernatant, filtering, and finally re-dispersing into an ethanol solution to obtain an ultrathin boron nitride nanopowder dispersion liquid;
(2) and (2) uniformly stirring and melting the thermoplastic polyurethane at 190-210 ℃, introducing the mixed melt into a polytetrafluoroethylene mold while the thermoplastic polyurethane is hot, spraying the ultrathin boron nitride nano powder dispersion liquid prepared in the step (1) before the melt is cooled and formed, finally spraying a 100-200 mg/mL boric acid solution, and drying under vacuum to obtain the flame-retardant wear-resistant thermoplastic polyurethane composite material.
9. The method of claim 8, wherein: in the step (1), the volume ratio of the deionized water to the ethanol is 1: 1-1: 5.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111875764A (en) * | 2020-08-03 | 2020-11-03 | 合肥万力轮胎有限公司 | Novel nanometer hybrid flame-retardant polyurethane elastomer and preparation method thereof |
| CN112341796A (en) * | 2020-11-27 | 2021-02-09 | 浙江长鸿纺织科技有限公司 | TPU membrane with corrosion resistance |
| CN113337103A (en) * | 2021-06-03 | 2021-09-03 | 上海交通大学 | Low-dielectric and high-thermal-conductivity polymer-based composite material and preparation method thereof |
| CN113831733A (en) * | 2021-09-28 | 2021-12-24 | 长春工业大学 | High-temperature shape memory, flame-retardant and environment-friendly composite material |
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2019
- 2019-12-11 CN CN201911265867.9A patent/CN110964307A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111875764A (en) * | 2020-08-03 | 2020-11-03 | 合肥万力轮胎有限公司 | Novel nanometer hybrid flame-retardant polyurethane elastomer and preparation method thereof |
| CN112341796A (en) * | 2020-11-27 | 2021-02-09 | 浙江长鸿纺织科技有限公司 | TPU membrane with corrosion resistance |
| CN113337103A (en) * | 2021-06-03 | 2021-09-03 | 上海交通大学 | Low-dielectric and high-thermal-conductivity polymer-based composite material and preparation method thereof |
| CN113831733A (en) * | 2021-09-28 | 2021-12-24 | 长春工业大学 | High-temperature shape memory, flame-retardant and environment-friendly composite material |
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