CN113321932A - Heat-conducting nylon 66 material and preparation method thereof - Google Patents
Heat-conducting nylon 66 material and preparation method thereof Download PDFInfo
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- CN113321932A CN113321932A CN202010128564.9A CN202010128564A CN113321932A CN 113321932 A CN113321932 A CN 113321932A CN 202010128564 A CN202010128564 A CN 202010128564A CN 113321932 A CN113321932 A CN 113321932A
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- nylon
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- dihydroxybiphenyl
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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
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/48—Polymers modified by chemical after-treatment
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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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Abstract
The invention discloses a heat-conducting nylon 66 material and a preparation method thereof, wherein the heat-conducting nylon 66 material is prepared from 69.1-89.8% of nylon 66, 10-30% of heat-conducting modifier, 0.1-0.3% of lubricant and 0.1-0.6% of antioxidant according to weight percentage, wherein the heat-conducting modifier is 4,4' -dihydroxybiphenyl modified nylon, and the 4,4' -dihydroxybiphenyl modified nylon is prepared by carrying out reflux reaction on the nylon 66 and 4,4' -dihydroxybiphenyl in a DMF solution and potassium carbonate. The heat-conducting nylon 66 material has excellent mechanical properties while having heat-conducting property.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a heat-conducting nylon 66 material and a preparation method thereof.
Background
Nylon is one of engineering plastics and is widely applied. Because of the characteristics of good rigidity, impact resistance, self-lubricating property, oil resistance and the like, the composite material is widely applied to the fields of automobile parts, electronic and electric appliances, connectors and the like.
Because nylon is usually used at the component interface of electronic and electrical equipment and is connected with more electronic components, electrical equipment is easy to generate heat under working conditions, if the heat cannot be timely dissipated, electrical components can be aged if the heat is light, the service life of the electrical components is influenced, and fire disasters are easy to cause if the heat is heavy. So the heat dissipation function of the nylon material is very important.
The conventional common method for modifying the heat-conducting nylon is to add heat-conducting carbon black or metal filler into the material, so that the required addition amount is large, and the loss of the mechanical property of the material is obvious.
Disclosure of Invention
In view of the above, the invention needs to provide a heat-conducting nylon 66 material and a preparation method thereof, wherein 4,4' -dihydroxybiphenyl modified nylon is introduced into a nylon 66 system as a heat-conducting modifier, so that the nylon 66 material has better mechanical properties while realizing heat conduction, and the technical problem that the existing heat-conducting nylon cannot have both heat conduction and mechanical properties is solved.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention discloses a heat-conducting nylon 66 material, which is prepared from 69.1-89.8% of nylon 66, 10-30% of heat-conducting modifier, 0.1-0.3% of lubricant and 0.1-0.6% of antioxidant according to weight percentage, wherein the heat-conducting modifier is 4,4' -dihydroxybiphenyl modified nylon, and the 4,4' -dihydroxybiphenyl modified nylon is prepared by carrying out reflux reaction on the nylon 66 and 4,4' -dihydroxybiphenyl in a DMF solution and potassium carbonate.
Further, the lubricant in the present invention may be a conventional choice in the art, and in some embodiments of the present invention, the lubricant is selected from at least one of pentaerythritol, stearate.
Further, the antioxidant in the present invention may be conventionally selected in the art, and in some embodiments of the present invention, the antioxidant is at least one of hindered phenolic antioxidants, phosphite antioxidants.
Preferably, the hindered phenolic antioxidant is selected from N, N' -bis- (3(3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine and the phosphite antioxidant is selected from bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite.
Further, the specific preparation method of the 4,4' -dihydroxybiphenyl modified nylon comprises the following steps: adding nylon 66 and 4,4' -dihydroxybiphenyl into DMF solution, adding potassium carbonate, and reflux-reacting at 75-90 deg.C for 15-30 h.
Preferably, in the method for preparing the 4,4 '-dihydroxybiphenyl modified nylon, the mass ratio of the nylon 66 to the 4,4' -dihydroxybiphenyl is 1 (0.66-1.5);
2mL-5mL of the solution of the nylon 66 is needed for every 1g of the nylon 66 in the system, and 0.02-0.5g of potassium carbonate is needed for every 1g of the nylon 66.
The second aspect of the invention discloses a preparation method of the heat-conducting nylon 66 material according to the first aspect of the invention, which comprises the following steps:
fully mixing nylon 66, a heat conduction modifier, a lubricant and an antioxidant according to a ratio to obtain a uniform mixed material;
and adding the mixed material into a double-screw extruder, and carrying out melt extrusion, granulation and drying to obtain the heat-conducting nylon 66 material.
Further, the length-diameter ratio of the double-screw extruder is 36-42: 1, the temperature from the feed inlet to the machine head is as follows in sequence: 235-275 deg.C, 270-280 deg.C, 265-275 deg.C, 260-275 deg.C.
According to the invention, 4 '-dihydroxybiphenyl modified nylon is added into a nylon 66 system as a heat conduction modifier, 4' -dihydroxybiphenyl is introduced into a nylon molecular chain, and an adjacent double benzene ring structure is introduced between amide bonds of nylon 66 end groups. On the other hand, the large pi bond of the benzene ring can react with low-energy phonons, so that the average free path of main chain carbon and nitrogen phonons is reduced, the effect of lattice vibration is enhanced, and the heat conductivity can be realized. In addition, as the conductive filler is not used and the benzene ring structure with higher strength is introduced into the main chain, the heat-conducting nylon 66 material prepared by the method has better mechanical property while realizing heat conduction.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the specific embodiments illustrated. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
In the following examples, nylon 66: preferably EPR27 and EPR24 of the Henan Pingshan horse group, and Zhejiang Huafeng EP1107 and EP 1106;
lubricant: preferably calcium stearate of Shanghai New Material science and technology Limited and pentaerythritol of Shandong Ruijie New Material Limited;
antioxidant: irganox 1098 from CIBA, or THP-24, an antioxidant from Hubei ferry chemical Co.
Example 1
In this example, 79.5% of nylon 66EPR27, 20% of 4,4' -dihydroxybiphenyl modified nylon, 0.2% of lubricant calcium stearate, and 0.3% of antioxidant Irganox 1098 were mixed well by weight percentage, and then added with a mixture having an aspect ratio of 38: 1, and extruding, granulating and drying to obtain the heat-conducting nylon 66 material, wherein the temperature from a feed inlet to a machine head in the double-screw extruder is 240 ℃, 270 ℃, 275 ℃, 270 ℃, 275 ℃ and 275 ℃.
Wherein the preparation of the 4,4' -dihydroxy biphenyl modified nylon comprises the following steps: adding 50g of nylon 66 and 50g of 4,4 '-dihydroxybiphenyl into 150ml of DMF solution, adding 100g of potassium carbonate into the solution, and carrying out reflux reaction at 80 ℃ for 24 hours to obtain the 4,4' -dihydroxybiphenyl modified nylon.
Example 2
In this example, 84.35% nylon 66EPR24, 15% 4,4' -dihydroxybiphenyl modified nylon, 0.25% lubricant calcium stearate, and 0.4% antioxidant Irganox 1098 were mixed thoroughly and uniformly according to the weight percentage, and then the mixture was added with a ratio of length to diameter of 42: 1, and extruding, granulating and drying to obtain the heat-conducting nylon 66 material, wherein the temperature from a feed inlet to a machine head in the double-screw extruder is 240 ℃, 165 ℃, 270 ℃, 275 ℃, 270 ℃ and 265 ℃.
Wherein the preparation of the 4,4' -dihydroxy biphenyl modified nylon comprises the following steps: 50g of nylon 66 and 50g of 4,4 '-dihydroxybiphenyl are added into 200ml of the MF solution, potassium carbonate is added into the solution (20 g of potassium carbonate is added into every 1g of nylon 66), and the mixture is refluxed and reacted for 20 hours at the temperature of 85 ℃ to obtain the 4,4' -dihydroxybiphenyl modified nylon.
Example 3
In this example, 74.65% nylon 66EP1107, 25% 4,4' -dihydroxybiphenyl modified nylon, 0.15% lubricant pentaerythritol and 0.2% antioxidant THP-24 were mixed thoroughly and homogeneously in terms of weight percentage, and then the mixture was added with a ratio of length to diameter of 40: 1, and extruding, granulating and drying to obtain the heat-conducting nylon 66 material, wherein the temperature of the double-screw extruder from a feed inlet to a machine head is 240 ℃, 260 ℃, 270 ℃, 275 ℃, 265 ℃ and 260 ℃.
Wherein the preparation of the 4,4' -dihydroxy biphenyl modified nylon comprises the following steps: adding 125ml of the solution of the nylon 66 and 50g of the 4,4' -dihydroxybiphenyl into the solution of the nylon 66 and 50g of the solution of the 4,4' -dihydroxybiphenyl, adding 13g of potassium carbonate into the solution of the nylon, and carrying out reflux reaction for 24 hours at the temperature of 80 ℃ to obtain the 4,4' -dihydroxybiphenyl modified nylon.
Example 4
In this example, 89.8% nylon 66, 10% 4,4' -dihydroxybiphenyl modified nylon EP1106, 0.1% lubricant pentaerythritol, and 0.1% antioxidant THP-24 were mixed well by weight percentage, and then added with a mixture having a length-diameter ratio of 38: 1, and extruding, granulating and drying to obtain the heat-conducting nylon 66 material, wherein the temperatures from a feed inlet to a machine head in the double-screw extruder are 245 ℃, 275 ℃, 280 ℃, 270 ℃, 275 ℃, 270 ℃, 260 ℃ and 265 ℃.
Wherein the preparation of the 4,4' -dihydroxy biphenyl modified nylon comprises the following steps: adding 80ml of the mixed solution of nylon 66 (40 g) and 4,4 '-dihydroxybiphenyl (60 g), adding potassium carbonate (0.8 g), and carrying out reflux reaction at 75 ℃ for 15 hours to obtain the 4,4' -dihydroxybiphenyl modified nylon.
Example 5
In this example, 69.1% nylon 66EPR27, 30% 4,4' -dihydroxybiphenyl modified nylon, 0.3% lubricant calcium stearate and 0.6% antioxidant Irganox 1098 were mixed thoroughly and uniformly according to the weight percentage, and then the mixture was added with a length-diameter ratio of 36: 1, and extruding, granulating and drying to obtain the heat-conducting nylon 66 material, wherein the temperatures from a feed inlet to a machine head in the double-screw extruder are respectively 235 ℃, 265 ℃, 270 ℃, 275 ℃, 270 ℃, 265 ℃ and 260 ℃.
Wherein the preparation of the 4,4' -dihydroxy biphenyl modified nylon comprises the following steps: adding 60g of nylon 66 and 39.6g of 4,4 '-dihydroxybiphenyl into 300ml of DMF solution, adding 30g of potassium carbonate into the solution, and carrying out reflux reaction at 90 ℃ for 30 hours to obtain the 4,4' -dihydroxybiphenyl modified nylon.
Comparative example 1
In the comparative example, after 49.6 percent of nylon 66EPR27, 50 percent of conductive carbon black, 0.2 percent of lubricant calcium stearate and 0.2 percent of antioxidant Irganox 1098 are fully and uniformly mixed according to weight percentage, the mixture is added with the mixture with the length-diameter ratio of 36: 1, and extruding, granulating and drying to obtain the heat-conducting nylon 66 material, wherein the temperature from a feed inlet to a machine head in the double-screw extruder is 240 ℃, 270 ℃, 275 ℃, 270 ℃, 275 ℃ and 275 ℃.
Comparative example 2
In the comparative example, 69.1 percent of nylon 66EPR24, 30 percent of conductive carbon black, 0.3 percent of lubricant pentaerythritol and 0.6 percent of antioxidant Irganox 1098 are fully and uniformly mixed according to weight percentage, and then the mixture is added with the mixture with the length-diameter ratio of 36: 1, and extruding, granulating and drying to obtain the heat-conducting nylon 66 material, wherein the temperatures from a feed inlet to a machine head in the double-screw extruder are respectively 235 ℃, 265 ℃, 270 ℃, 275 ℃, 270 ℃, 265 ℃ and 260 ℃.
The thermally conductive nylon 66 materials prepared in the examples and comparative examples were subjected to the relevant performance tests, and the results are shown in table 1:
TABLE 1 Performance test results for thermally conductive Nylon 66 materials
As can be seen from the test results in table 1, the thermal conductive nylon 66 material of the present invention has excellent thermal conductivity, and maintains excellent mechanical properties.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (8)
1. A heat-conducting nylon 66 material is characterized by being prepared from 69.1-89.8% of nylon 66, 10-30% of heat-conducting modifier, 0.1-0.3% of lubricant and 0.1-0.6% of antioxidant according to weight percentage, wherein the heat-conducting modifier is 4,4' -dihydroxybiphenyl modified nylon, and the 4,4' -dihydroxybiphenyl modified nylon is prepared by carrying out reflux reaction on the nylon 66 and 4,4' -dihydroxybiphenyl in a DMF solution and potassium carbonate.
2. The thermally conductive nylon 66 material of claim 1, wherein the lubricant is selected from at least one of pentaerythritol and stearate.
3. The thermally conductive nylon 66 material of claim 1, wherein the antioxidant is at least one of a hindered phenolic antioxidant and a phosphite antioxidant.
4. The thermally conductive nylon 66 material of claim 3, wherein the hindered phenolic antioxidant is selected from N, N' -bis- (3(3, 5-di-t-butyl-4-hydroxyphenyl) propionyl) hexanediamine and the phosphite antioxidant is selected from bis (2, 4-di-t-butylphenyl) pentaerythritol diphosphite.
5. The heat-conducting nylon 66 material of claim 1, wherein the 4,4' -dihydroxybiphenyl modified nylon is prepared by the following specific steps: adding nylon 66 and 4,4' -dihydroxybiphenyl into DMF solution, adding potassium carbonate, and reflux-reacting at 75-90 deg.C for 15-30 h.
6. The thermally conductive nylon 66 material of claim 5, wherein in the preparation method of the 4,4 '-dihydroxybiphenyl modified nylon, the mass ratio of the nylon 66 to the 4,4' -dihydroxybiphenyl is 1 (0.66-1.5);
2mL-5mL of the solution of the nylon 66 is needed for every 1g of the nylon 66 in the system, and 0.02-0.5g of potassium carbonate is needed for every 1g of the nylon 66.
7. A method for preparing the heat-conducting nylon 66 material as claimed in any one of claims 1-6, which comprises the following steps:
fully mixing nylon 66, a heat conduction modifier, a lubricant and an antioxidant according to a ratio to obtain a uniform mixed material;
and adding the mixed material into a double-screw extruder, and carrying out melt extrusion, granulation and drying to obtain the heat-conducting nylon 66 material.
8. The method of claim 7, wherein the twin screw extruder has an aspect ratio of 36 to 42: 1, the temperature from the feed inlet to the machine head is as follows in sequence: 235-275 deg.C, 270-280 deg.C, 265-275 deg.C, 260-275 deg.C.
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| CN202010128564.9A CN113321932B (en) | 2020-02-28 | 2020-02-28 | Heat-conducting nylon 66 material and preparation method thereof |
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| CN202010128564.9A CN113321932B (en) | 2020-02-28 | 2020-02-28 | Heat-conducting nylon 66 material and preparation method thereof |
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| CN113321932B CN113321932B (en) | 2022-07-12 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103059565A (en) * | 2013-01-25 | 2013-04-24 | 本松工程塑料（杭州）有限公司 | Heat-conducting nylon composite material, preparation method and application thereof |
| CN103497508A (en) * | 2013-10-09 | 2014-01-08 | 深圳市沃尔核材股份有限公司 | Low-temperature-resistant illumination-resistant nylon binding tape |
| WO2014129805A1 (en) * | 2013-02-21 | 2014-08-28 | 제일모직주식회사 | Thermally conductive resin composition |
| CN104559159A (en) * | 2013-10-09 | 2015-04-29 | 上海杰事杰新材料(集团)股份有限公司 | Heat-conducting high-temperature-resistant nylon composite material and preparation method thereof |
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2020
- 2020-02-28 CN CN202010128564.9A patent/CN113321932B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103059565A (en) * | 2013-01-25 | 2013-04-24 | 本松工程塑料（杭州）有限公司 | Heat-conducting nylon composite material, preparation method and application thereof |
| WO2014129805A1 (en) * | 2013-02-21 | 2014-08-28 | 제일모직주식회사 | Thermally conductive resin composition |
| CN103497508A (en) * | 2013-10-09 | 2014-01-08 | 深圳市沃尔核材股份有限公司 | Low-temperature-resistant illumination-resistant nylon binding tape |
| CN104559159A (en) * | 2013-10-09 | 2015-04-29 | 上海杰事杰新材料(集团)股份有限公司 | Heat-conducting high-temperature-resistant nylon composite material and preparation method thereof |
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