CN113930070B - Preparation method and application of low-dielectric-constant bio-based high-temperature nylon - Google Patents
Preparation method and application of low-dielectric-constant bio-based high-temperature nylon Download PDFInfo
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Abstract
The invention discloses a preparation method and application of low-dielectric-constant bio-based high-temperature nylon. The method comprises the following steps: dispersing hollow mesoporous silica in butanol by ultrasonic treatment, adding the dispersed hollow mesoporous silica into a reaction kettle, adding pentanediamine, 4' -bis (4-amino-2-trifluoromethyl phenoxy) biphenyl and terephthalic acid to form salt, adding benzoic acid into the reaction kettle, heating the reaction kettle to reflux butanol, discharging and recovering butanol, reacting, and obtaining white solid powder after the reaction is finished; then adding alpha-olefin-maleic anhydride copolymer into the solid, and carrying out reaction extrusion and granulation in a double-screw extruder to obtain the low-dielectric-constant bio-based high-temperature nylon. The low-dielectric-constant bio-based high-temperature nylon material provided by the invention meets the requirements of bio-based environment-friendly renewable materials, has excellent dielectric properties, high impact strength and heat resistance, and is particularly suitable for application fields such as miniaturized and thinned 5G products.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a preparation method and application of low-dielectric-constant bio-based high-temperature nylon.
Background
With the accelerated deployment of fifth generation mobile communication technology (5G), 5G is getting closer to our lives. The 5G antenna is a gateway for signal transmission and reception, both at the base station and at the terminal. Due to the highly integrated and miniaturized nature of 5G antenna systems, the thermal load generated by data access has multiplied, plus the need to operate at higher processing speeds and frequencies (in the gigahertz range), all of which increase the operating temperature of the device, making it more difficult to disperse heat. Therefore, in order to achieve better signal emission efficiency and stability, the 5G antenna material needs to have excellent dielectric properties, long-term high temperature resistance, flame retardance and electrical properties. Currently, common plastic material options are Thermotropic Liquid Crystal Polymer (TLCP) and polyphenylene sulfide (PPS).
The TLCP material has the characteristics of excellent dielectric property, high dimensional stability, high temperature resistance, intrinsic flame retardance and the like. However, TLCP has the problems of anisotropy, low weld line strength, high requirements on injection molding technology, low comprehensive mechanical properties, difficult dyeing, specific gravity and the like, and limits the design of thin wall and light weight of the antenna. PPS has the advantages of low water absorption, low product shrinkage, good mechanical properties, good dielectric properties and the like. However, PPS has a low melting point (285 ℃) and is difficult to meet the SMT process temperature resistance requirement of plastic antenna manufacturing, with the development of 5G antenna technology, the antenna integration level is higher and the antenna is miniaturized, and more 5G antennas are required to be installed in a limited space, which tends to put higher requirements on the short-term high-temperature resistance and the long-term high-temperature resistance of the antenna. In addition, the molecular structure of the PPS material has poor mechanical toughness and large brittleness due to the existence of a large number of rigid benzene rings. When the PPS material is applied to the antenna and other complicated small-sized parts with thin walls and reinforcing ribs, the product is extremely easy to generate brittle failure in the injection molding and mounting processes, and the PPS material is also a disadvantageous factor for popularization and application of the antenna product.
The high-temperature nylon, which is used as special engineering plastic, has the excellent performance of aromatic polyamide and the processing performance of aliphatic polyamide, is a material with excellent performance, is widely applied to the fields of electronic appliances, LED illumination, automobile industry and the like, and has been gradually developed into a main product of the special engineering plastic. However, commercial high-temperature nylon materials generally have a relatively high dielectric constant, which is unfavorable for signal transmission and limits the expansion of the materials in the 5G field.
The Chinese patent application with publication number of CN111675900A (202010724060.3) discloses a glass fiber reinforced nylon composite material with low dielectric constant and a preparation method thereof, wherein the functionalized POSS is provided with a skeleton cavity structure, and is combined with a nylon matrix through a reactive group or a hydrogen bond to form a network structure with multiple cavities, and the special structure of the composite material endows the composite material with low dielectric constant. The composite material has excellent rigidity and toughness and low dielectric constant, and can be applied to the field of high-frequency communication. However, the above scheme adopts a physical blending mode, has high dispersion requirement on POSS, and has limited improvement on nylon dielectric properties by POSS.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method and application of low-dielectric-constant bio-based high-temperature nylon, and the low-dielectric-constant bio-based high-temperature nylon is polymerized by biomass source monomers, so that the polymerization process is simple, the energy consumption is low, and the obtained high-temperature nylon has excellent mechanical properties and dielectric properties.
The aim of the invention can be achieved by the following technical scheme:
the preparation method of the low-dielectric-constant bio-based high-temperature nylon comprises the following steps:
(1) Dispersing hollow mesoporous silica in butanol, adding the dispersed silica into a reactor, adding pentanediamine, 4' -bis (4-amino-2-trifluoromethyl phenoxy) biphenyl and terephthalic acid and adipic acid to form salts, adding benzoic acid into the reactor, heating the reactor to reflux butanol, discharging and recovering butanol, raising the temperature for reaction, and obtaining white solid powder after the reaction is finished;
(2) And (3) adding alpha-olefin maleic anhydride copolymer into the solid powder obtained in the step (1), and performing reaction extrusion and granulation in a double-screw extruder to obtain the low-dielectric-constant bio-based high-temperature nylon.
The low-dielectric-constant bio-based high-temperature nylon adopts terephthalic acid as diacid, and adopts pentanediamine and 4,4' -bis (4-amino-2-trifluoromethyl phenoxy) biphenyl as diamine, and the dielectric property of the hollow mesoporous silica regulating material is introduced in the polymerization process, so that the low-dielectric-constant bio-based high-temperature nylon is obtained. The chain extension is carried out by the alpha-olefin-maleic anhydride copolymer, so that the toughness of the material is improved and the good processability is maintained.
The preparation method of the low-dielectric-constant bio-based high-temperature nylon adopts the following raw materials in parts by weight:
in the step (1), the pore diameter of the hollow mesoporous silica is 2-10nm, the diameter is 100-300nm, and the specific surface area is more than or equal to 900m 2 /g。
And the air in the reactor is discharged by replacement of the protective gas. The protective gas is nitrogen.
The conditions for the elevated temperature reaction were: raising the reaction temperature to 230-260 ℃, continuously maintaining the reaction for 10-60 min, and continuously introducing nitrogen to remove water in the reaction process.
The reactor heating is by microwave means. The microwave heating power is 600w-1200w, most preferably 800w
The butanol reflux is maintained for 5-30min, most preferably 20min.
Butanol is then recovered by evacuation through a vacuum pump.
175-194 parts of pentanediamine in the step (1); 100-177 parts of 4,4' -bis (4-amino-2-trifluoromethyl phenoxy) biphenyl; 146-156 parts of terephthalic acid; 154-164 parts of adipic acid; 8-10 parts of benzoic acid; 1900-2100 parts of butanol;
23 to 60 parts of alpha-olefin maleic anhydride copolymer in the step (2).
The low-dielectric-constant bio-based high-temperature nylon prepared by the preparation method is applied to the field of 5G communication.
Compared with the prior art, the invention has the following advantages:
(1) The pentylene diamine selected by the invention is a biomass source, and accords with green and environment-friendly low-carbon sustainable development;
(2) According to the invention, the 4,4' -bis (4-amino-2-trifluoromethyl phenoxy) biphenyl is introduced into the nylon structure to reduce the fluorine element, so that the dielectric property of the high-temperature nylon is improved, and meanwhile, the biphenyl structure provides rigidity and heat resistance for the high-temperature nylon;
(3) According to the invention, hollow mesoporous silica is selected for in-situ polymerization, the dielectric property of the material is further improved by utilizing a porous structure of the silica, the crystallization of high-temperature nylon is promoted, and the heat resistance of the material is improved;
(4) The invention selects the alpha-olefin-maleic anhydride copolymer as a chain extender, so that the material has good toughness and good processability.
The low-dielectric-constant bio-based high-temperature nylon material provided by the invention meets the requirements of bio-based environment-friendly renewable materials, has excellent dielectric properties, high impact strength and heat resistance, and is particularly suitable for application fields such as miniaturized and thinned 5G products.
Detailed Description
The invention is further illustrated by the following examples:
pentanediamine (Kaiser), 4' -bis (4-amino-2-trifluoromethylphenoxy) biphenyl (Hunan Jia navigation pharmaceutical technology Co., ltd.), terephthalic acid (Ala Ding Shiji), hollow mesoporous silica (Jiangsu Xianfeng nanometer materials science Co., ltd.) with pore diameter of 2-10nm, diameter of 100-300nm, and specific surface area of more than or equal to 900m 2 Per g), butanol (Aba Ding Shiji), benzoic acid (Aba Ding Shiji), alpha-olefin maleic anhydride copolymer (Mitsubishi chemical Co., ltd., DIACARNA) TM )
TABLE 1 unit g
| Raw materials | Implementation of the embodimentsExample 1 | Example 2 | Example 3 | Comparative example 1 |
| Hollow mesoporous silica | 15 | 24 | 60 | 0 |
| Pentanediamine | 193.8 | 185.6 | 178.5 | 214.2 |
| 4,4' -bis (4-amino-2-trifluoromethylphenoxy) biphenyl | 100.8 | 141.1 | 176.4 | 0 |
| Terephthalic acid | 151.1 | 151.1 | 151.1 | 151.1 |
| Adipic acid | 159.1 | 159.1 | 159.1 | 159.1 |
| Benzoic acid | 9.1 | 9.5 | 8.7 | 5.2 |
| Butanol (Butanol) | 2000 | 2000 | 2000 | 2000 |
| Alpha-olefin maleic anhydride copolymer | 25 | 38 | 52 | 0 |
Example 1
The preparation method of the low dielectric constant bio-based high temperature nylon comprises the following steps of:
(1) Dispersing hollow mesoporous silica in butanol, adding the dispersed silica into a reaction kettle, introducing nitrogen to replace and discharge air in the kettle, then adding pentanediamine, 4' -bis (4-amino-2-trifluoromethyl phenoxy) biphenyl and terephthalic acid, and adipic acid to form salt, adding benzoic acid into the reaction kettle, heating the reaction kettle (800 w microwave heating) until butanol is refluxed, keeping butanol reflux for 20min, then discharging and recycling butanol, raising the reaction temperature to 240 ℃, continuously keeping the reaction for 20min, continuously introducing nitrogen to remove water in the reaction process, and obtaining white solid powder after the reaction is finished;
(2) And (3) adding alpha-olefin-maleic anhydride copolymer into the solid in the step (1), and performing reaction extrusion and granulation in a double-screw extruder to obtain the low-dielectric-constant bio-based high-temperature nylon.
The low dielectric constant high temperature Ni obtained in example 1 according to the inventionThe infrared spectrum of the dragon is obtained at 3350cm -1 And 1570cm -1 An amide group NH absorbance peak appears; at 1664cm -1 A structural peak belonging to the amide bond c=o appears; at 1340cm -1 The absorption peak belonging to C-N appears at 1100-1300cm -1 The appearance of C-O and C-F absorption peaks indicates that the final product was a fluoronylon.
Example 2
The preparation method of the low dielectric constant bio-based high temperature nylon comprises the following steps of:
(1) Dispersing hollow mesoporous silica in butanol, adding the dispersed silica into a reaction kettle, introducing nitrogen to replace and discharge air in the kettle, then adding pentanediamine, 4' -bis (4-amino-2-trifluoromethyl phenoxy) biphenyl and terephthalic acid, and adipic acid to form salt, adding benzoic acid into the reaction kettle, heating the reaction kettle (800 w microwave heating) until butanol is refluxed, keeping butanol reflux for 20min, then discharging and recycling butanol, raising the reaction temperature to 250 ℃, continuously keeping the reaction for 40min, continuously introducing nitrogen to remove water in the reaction process, and obtaining white solid powder after the reaction is finished;
(2) And (3) adding alpha-olefin-maleic anhydride copolymer into the solid in the step (1), and performing reaction extrusion and granulation in a double-screw extruder to obtain the low-dielectric-constant bio-based high-temperature nylon.
Example 3
The preparation method of the low dielectric constant bio-based high temperature nylon comprises the following steps of:
(1) Dispersing hollow mesoporous silica in butanol, adding the dispersed silica into a reaction kettle, introducing nitrogen to replace and discharge air in the kettle, then adding pentanediamine, 4' -bis (4-amino-2-trifluoromethyl phenoxy) biphenyl and terephthalic acid, and adipic acid to form salt, adding benzoic acid into the reaction kettle, heating the reaction kettle (800 w microwave heating) until butanol is refluxed, keeping butanol reflux for 20min, then discharging and recycling butanol, raising the reaction temperature to 260 ℃, continuously keeping the reaction for 60min, continuously introducing nitrogen to remove water in the reaction process, and obtaining white solid powder after the reaction is finished;
(2) And (3) adding alpha-olefin-maleic anhydride copolymer into the solid in the step (1), and performing reaction extrusion and granulation in a double-screw extruder to obtain the low-dielectric-constant bio-based high-temperature nylon.
Comparative example 1
The preparation method of the low dielectric constant bio-based high temperature nylon comprises the following steps of:
(1) Adding butanol into a reaction kettle, introducing nitrogen to replace and discharge air in the kettle, then adding pentylene diamine, terephthalic acid and adipic acid to form salt, adding benzoic acid into the reaction kettle, heating the reaction kettle (heating in a 800w microwave mode) until butanol flows back, keeping the butanol flow back for 20min, then discharging and recycling butanol, raising the reaction temperature to 240 ℃, continuously keeping the reaction for 40min, continuously introducing nitrogen to remove water in the reaction process, and obtaining white solid powder after the reaction is finished;
(2) And (3) carrying out reaction extrusion and granulation on the solid in the step (1) in a double-screw extruder to obtain the bio-based high-temperature nylon.
The testing method comprises the following steps:
(1) Relative viscosity of sulfuric acid
Relative viscosity of polyamide at a concentration of 0.1g/ml measured in concentrated sulfuric acid at 25 ℃
(2) Physical and mechanical Properties
According to the national standard, the tensile bending, bending strength, notched impact strength of a simply supported beam, heat distortion temperature, melt index, dielectric constant, loss factor and the like are tested.
(3) Thermal performance
The melting temperature and the crystallization temperature of the high-temperature nylon are characterized by DSC, the heating and cooling speed is 20 ℃/min, and the nitrogen atmosphere is adopted.
The results of the test are shown in table 2.
Examples 1 to 3 and comparative example 1
TABLE 2
The low dielectric constant bio-based high temperature nylons obtained in examples 1-3 have excellent dielectric and mechanical properties.
From examples 1, 2 and 3, comparative example 1 was superior to comparative example 1 in dielectric properties, thermal properties and toughness, and as the ratio of mesoporous silica to 4,4' -bis (4-amino-2-trifluoromethylphenoxy) biphenyl was increased, the dielectric constant and loss tangent of the material were gradually decreased, and the heat distortion temperature of the material was gradually increased. This is because the special structure of mesoporous silica effectively improves the dielectric properties of the material, and the introduction of fluorine reduces the polarity of the material, thereby improving the dielectric properties of the material. In addition, mesoporous silica plays a heterogeneous nucleation role in the material, so that the crystallization temperature and crystallization rate of the material are improved, and the thermal performance of the material is improved. When the alpha-olefin-maleic anhydride copolymer is introduced into the material, the notch impact strength of the material is obviously improved, and the melt index is basically kept unchanged.
The foregoing is merely illustrative of specific embodiments of the present invention, but the design concept of the present invention is not limited thereto, and any insubstantial modification of the present invention by using the design concept shall fall within the scope of the present invention.
Claims (9)
1. The preparation method of the low-dielectric-constant bio-based high-temperature nylon is characterized by comprising the following raw materials in parts by weight:
15-60 parts of hollow mesoporous silica;
175-194 parts of pentanediamine;
100-177 parts of 4,4' -bis (4-amino-2-trifluoromethyl phenoxy) biphenyl;
146-156 parts of terephthalic acid;
154-164 parts of adipic acid;
8-10 parts of benzoic acid;
1900-2100 parts of butanol;
23-60 parts of alpha-olefin and seed maleic anhydride copolymer;
the preparation method comprises the following steps:
(1) Dispersing hollow mesoporous silica in butanol, adding the dispersed silica into a reactor, adding pentanediamine, 4' -bis (4-amino-2-trifluoromethyl phenoxy) biphenyl and terephthalic acid and adipic acid to form salts, adding benzoic acid into the reactor, heating the reactor to reflux butanol, discharging and recovering butanol, raising the temperature to react, and obtaining solid powder after the reaction is finished;
(2) Adding alpha-olefin and maleic anhydride copolymer into the solid powder obtained in the step (1), and carrying out reaction extrusion and granulation in a double-screw extruder to obtain the low-dielectric-constant bio-based high-temperature nylon.
2. The method for preparing low dielectric constant bio-based high temperature nylon according to claim 1, wherein in the step (1), the pore diameter of the hollow mesoporous silica is 2-10nm, the diameter is 100-300nm, and the specific surface area is more than or equal to 900m 2 /g。
3. The method for producing a low dielectric constant bio-based high temperature nylon according to claim 1, wherein in the step (1), the air in the reactor is purged by a shielding gas.
4. The method for preparing low dielectric constant bio-based high temperature nylon according to claim 3, wherein the shielding gas is nitrogen.
5. The method for preparing low dielectric constant bio-based high temperature nylon according to claim 1, wherein in the step (1), the conditions of the reaction at the elevated temperature are: raising the reaction temperature to 230-260 ℃, continuously maintaining the reaction for 10-60 min, and continuously introducing nitrogen to remove water in the reaction process.
6. The method for preparing low dielectric constant bio-based high temperature nylon according to claim 1, wherein in the step (1), the reactor is heated by microwave.
7. The method for preparing low dielectric constant bio-based high temperature nylon according to claim 6, wherein in the step (1), the heating power by the microwave mode is 600w-1200w.
8. The method for preparing low dielectric constant bio-based high temperature nylon according to claim 1, wherein in the step (1), butanol is refluxed for 5 to 30min.
9. The application of the low-dielectric-constant bio-based high-temperature nylon prepared by the preparation method according to any one of claims 1-8 in the field of 5G communication.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20100216967A1 (en) * | 2009-02-20 | 2010-08-26 | International Business Machines Corporation | Interfacial polymerization methods for making fluoroalcohol-containing polyamides |
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| CN102471590A (en) * | 2009-07-14 | 2012-05-23 | 花王株式会社 | Low-permittivity resin composition |
| CN102627853A (en) * | 2012-04-17 | 2012-08-08 | 金发科技股份有限公司 | High-temperature elastomer nylon and preparation method thereof |
| CN110684190A (en) * | 2019-08-19 | 2020-01-14 | 浙江新力新材料股份有限公司 | Preparation method of bio-based high-temperature nylon |
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