CN114181518A - Low dielectric constant nylon composite material and preparation method thereof - Google Patents
Low dielectric constant nylon composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a low dielectric constant nylon composite material and a preparation method thereof, wherein the low dielectric constant nylon composite material is synthesized by the following raw materials: caprolactam, 2' -bis (trifluoromethyl) diaminobiphenyl, adipic acid, amino zeolite nanocrystal, ethylene and octene copolymer grafted maleic anhydride, benzoic acid, toluene diisocyanate and an antioxidant. The low dielectric constant nylon composite material has excellent mechanical property and processing property, low water absorption and low dielectric constant, and can be applied to shells, coating materials, protective materials and the like of 5G base stations, micro base station systems, data communication terminals and multimedia terminals.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to a low-dielectric-constant nylon composite material and a preparation method thereof.
Background
With the development of the microelectronic industry, the circuit interconnection delay time is gradually increased. In order to adapt to the development of very large scale integrated circuits, it is important to develop high performance dielectric materials to reduce interconnect delay, power consumption and crosstalk. The low dielectric constant dielectric material can reduce the parasitic capacitance between metal lines, thereby achieving the purpose. Conventional inorganic materials such as silicon dioxide have become unsatisfactory for integrated circuits that are being developed at a high rate due to their dielectric constant being too large. Compared with inorganic dielectric materials, high-performance organic plastics are receiving wide attention due to the advantages of low dielectric constant, good processability, low cost, chemical and heat resistance and the like. Polyamide (PA) has the advantages of wear resistance, impact resistance, fatigue resistance, oil resistance, corrosion resistance, wide application temperature range and the like, is the earliest and most widely applied thermoplastic engineering plastic, but has the defects of poor impact toughness, notch sensitivity, high water absorption and high dielectric constant (the dielectric constant Dk of PA6 is 3.5, the test frequency is 5GHz, and the test is carried out according to the GB/T5597-.
In general, lowering the dielectric constant of a material can be achieved by lowering the polarizability of the molecules as well as reducing the number of polarizable molecules per unit volume. Low dielectric constant plastics are currently mainly prepared by the following three ways alone or in combination of several. Firstly, a large-volume side group, a non-coplanar group or fluorine element is introduced to prepare the intrinsic low-dielectric-constant plastic. And secondly, air holes are introduced into the plastic to reduce the number of polarizable molecules in unit volume, so that the aim of reducing the dielectric constant is fulfilled. Thirdly, adding substances with low dielectric property to prepare the composite low-dielectric constant material.
Currently, some research is being done in the prior art on low dielectric polyamide materials, such as: chinese patent CN 112341808A discloses a wood flour reinforced micro-foaming polyamide compound with low dielectric constant and high dielectric strength and a preparation method thereof, wherein the wood flour reinforced micro-foaming polyamide compound is composed of the following raw materials in parts by weight: polyamide: 39-93.8 parts; wood powder: 5-30 parts; ionic polymer: 1-6 parts; microsphere foaming agent: 1-3 parts; reinforcing and filling materials: 0-20 parts of a solvent; lubricant: 0.1-1 part; a stabilizer: 0.1-1 part. Chinese patent CN 112175387A discloses a polyamide composite material for low dielectric nano injection molding and a preparation method and application thereof, wherein the polyamide composite material comprises 10-95% of polyamide, 1-10% of polysilsesquioxane, 0.05-0.5% of antioxidant, 0.1-2% of release agent, 1-10% of toughening agent, 1-15% of polyolefin and 5-50% of glass fiber. Chinese patent CN 107573683A discloses a glass fiber reinforced polyamide material with low dielectric constant and a preparation method thereof, wherein the material comprises the following components in parts by weight: PA6610-70 parts, PA6I/6T copolymer 5-20 parts, glass fiber 20-60 parts, zeolite 5-10 parts, antioxidant 0.8-1.2 parts, and lubricant 0.5-1 part. Chinese patent CN 111675900A discloses a glass fiber reinforced nylon composite material with low dielectric constant, in the composite material, functionalized POSS has a skeleton cavity structure, and is combined with a nylon matrix through reactive groups or hydrogen bonds to form a net structure with multiple cavities, and the special structure of the composite material endows the composite material with low dielectric constant; the processing fluidity of the nylon composite material is improved by adding the flow modifier, so that the composite material is suitable for thin-wall products; silicone lubricant is added to enhance the comprehensive mechanical property of the composite material; the use of the antioxidant and the light stabilizer improves the light stability of the composite material, so that the composite material is suitable for outdoor high-temperature occasions. Chinese patent CN 108410167a discloses a glass fiber reinforced low dielectric nylon material mainly composed of: nylon resin, quartz glass fiber, nucleating agent, lubricant, thermal oxygen stabilizer and the like.
Therefore, the low dielectric constant nylon materials disclosed in the prior art are all prepared by adding substances with low dielectric property through a blending method, or the dielectric constant of the materials is reduced by blending and adding a microsphere foaming agent to introduce air holes into plastics.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a nylon composite material with a low dielectric constant, low water absorption, excellent mechanical properties and processability.
The specific technical scheme for realizing the aim of the invention is as follows:
a nylon composite material with a low dielectric constant is prepared from the following raw materials in parts by weight:
the 2,2' -bis (trifluoromethyl) diaminobiphenyl and adipic acid are in an equimolar ratio;
the amino zeolite nanocrystal is obtained by organizing zeolite nanocrystals by 3-aminopropyltriethoxysilane; the zeolite nanocrystals are prepared from ethyl orthosilicate and tetrabutylammonium hydroxide.
In some embodiments, the low dielectric constant nylon composite material is prepared from the following raw materials in parts by weight:
in some embodiments, the low dielectric constant nylon composite material is prepared from the following raw materials in parts by weight:
the low-dielectric-constant nylon composite material has a dielectric constant of 2.88-2.97 (the test frequency is 5GHz according to the test of GB/T5597-1999 standard), an intrinsic viscosity of 1.07 dL/g-1.70 dL/g (according to the test of GB/T1632-2008 standard, the solvent is concentrated sulfuric acid), and a melting temperature of 228-238 ℃ (according to the test of GB/T19466.3-2004 standard).
In some embodiments, the graft ratio of the maleic anhydride in the ethylene-octene copolymer grafted maleic anhydride is 0.8% to 2.2%.
In some of these embodiments, the method for preparing the amino zeolite nanocrystals comprises the steps of: ethyl orthosilicate, tetrabutylammonium hydroxide and deionized water in a molar ratio of 1: 0.1-0.4: 13-50, stirring and pre-hydrolyzing for 10-20 hours at 30-40 ℃, crystallizing for 10-20 hours at 110-150 ℃, cooling to normal temperature to obtain zeolite nanocrystals, finally adding 3-aminopropyltriethoxysilane accounting for 1-3 wt% of the total mass of the tetraethoxysilane and the tetrabutylammonium hydroxide, stirring for 0.5-3.5 hours at 30-40 ℃, and vacuum drying to obtain the amino zeolite nanocrystals.
In some of these embodiments, the antioxidant consists of a primary antioxidant and a secondary antioxidant; the main antioxidant is one or more of pentaerythritol tetra (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate), N '-1, 6-hexylene-bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionamide ], N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide; the auxiliary antioxidant is one or more of tris (2, 4-di-tert-butylphenyl) phosphite, bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite, bis (2, 4-di-tert-butyl) pentaerythritol diphosphite and bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite. Preferably, the main antioxidant is N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide, and the auxiliary antioxidant is bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate.
The invention also aims to provide a preparation method of the low-dielectric-constant nylon composite material.
The specific technical scheme for realizing the aim of the invention is as follows:
a preparation method of a low dielectric constant nylon composite material comprises the following steps:
(1) adding caprolactam after vacuum drying into a stirring type polymerization reactor, and simultaneously adding 2,2' -bis (trifluoromethyl) diaminobiphenyl, adipic acid, amino zeolite nanocrystalline, ethylene-octene copolymer grafted maleic anhydride, benzoic acid, toluene diisocyanate, an antioxidant and a proper amount of water; then vacuumizing for 3-7 min, introducing nitrogen for 3-7 min, circulating for 4-8 times in the way, and controlling the system pressure in the stirring type polymerization reactor to be 0.1-0.4 MPa;
(2) sealing the stirring type polymerization reactor within 2-4 hours, heating to 215-220 ℃ at a constant speed, adjusting the stirring speed of the stirring type polymerization reactor to 30-50 r/min, discharging gas to 1.7MPa when the temperature of the stirring type polymerization reactor reaches 215 ℃, maintaining the pressure at 1.7MPa, discharging gas to normal pressure after reacting for 0.5-3 hours, simultaneously heating to 240-250 ℃, continuously reacting for 0.5-3 hours, continuously vacuumizing for 0.1-2 hours at constant temperature, finishing the reaction, and supplementing nitrogen gas during discharging to obtain the catalyst.
In some embodiments, the preparation method of the low dielectric constant nylon composite material comprises the following steps:
(1) adding the caprolactam after vacuum drying into a stirring type polymerization reactor, and simultaneously adding the 2,2' -bis (trifluoromethyl) diaminobiphenyl, adipic acid, amino zeolite nanocrystalline, ethylene-octene copolymer grafted maleic anhydride, benzoic acid, toluene diisocyanate, an antioxidant and a proper amount of water; then vacuumizing for 4-6 min, introducing nitrogen for 4-6 min, and circulating for 5-7 times in such a way, so that reactants exist in the environment under the protection of nitrogen, and controlling the system pressure in the stirring type polymerization reactor to be 0.2-0.3 MPa;
(2) heating the stirring type polymerization reactor to 215-220 ℃ within 2-4 hours in a sealed manner at a constant speed, adjusting the stirring speed of the stirring type polymerization reactor to 30-50 r/min, wherein when the temperature of the stirring type polymerization reactor reaches 215 ℃, the gas is discharged to 1.7MPa, the pressure is maintained at 1.7MPa, after the reaction is carried out for 1-2 hours, the gas is discharged to normal pressure, meanwhile, the temperature is increased to 240-250 ℃, after the reaction is continued for 1-2 hours, the constant temperature is continuously vacuumized for 0.5-1.5 hours, the reaction is finished, and nitrogen is supplemented during discharging, so that the catalyst is obtained.
The low dielectric constant nylon composite material has the following functions:
the 2,2' -bis (trifluoromethyl) diaminobiphenyl introduces a fluorine-containing substituent and also introduces a rigid benzene ring structural unit so as to ensure the thermal property and the mechanical property of the nylon material. Because the main chain structure of nylon has diversity, different main chain structures have great influence on the performance of nylon, and the introduction of a fluorine-containing substituent in the main chain of nylon can effectively reduce the dielectric constant of the material, but the introduction of fluorine can cause the reduction of the thermal performance and the mechanical performance of the material.
The amino zeolite nanocrystalline is obtained by organically modifying 3-aminopropyltriethoxysilane and introducing an organic functional group amino on the surface of the amino zeolite nanocrystalline. The zeolite nanocrystal is high-crystallinity porous SiO with micropores with uniform molecular size in the interior2Has the characteristics of extremely low theoretical dielectric constant (about 1.60), high water repellency, high thermal conductivity, excellent mechanical strength and the like. Although the zeolite nanocrystals have intrinsic high hydrophobicity, a small amount of silicon hydroxyl groups still exist on the surface. The amino zeolite nanocrystals used in the present invention have four advantages: uniform microporous structure, high crystallinity, hydrophobicity and organic activity. (1) Because the amino zeolite nanocrystalline has a pore structure, the theoretical dielectric constant is low, the pore size is smaller than 2nm and obviously smaller than the size of an integrated circuit, and the problem of electronic breakdown is avoided; (2) because the amino zeolite nanocrystalline has a crystalline structure, the thermal conductivity and the mechanical strength are obviously higher than those of SiO prepared by a sol-gel method2(ii) a (3) Because the amino zeolite nano-crystal is hydrophobic in nature, the SiO prepared by a sol-gel method can be avoided2A process requiring surface hydrophobic treatment; (4) after the amino zeolite nanocrystalline is organically modified, amino carried on the surface of the amino zeolite nanocrystalline can react with terminal carboxyl of a nylon material, so that the interface binding power and compatibility of the amino zeolite nanocrystalline and the nylon material are improved.
The ethylene-octene copolymer is grafted with maleic anhydride, the maleic anhydride group can react with the terminal amino group of the nylon, and the ethylene-octene copolymer can absorb a large amount of external impact energy, so that the toughness of the nylon composite material can be improved.
The isocyanate group of the toluene diisocyanate can react with the terminal group of the nylon and the terminal amino group of the amino zeolite nanocrystal, so that the compatibility between the nylon material and the amino zeolite nanocrystal can be improved.
Benzoic acid is used for adjusting the intrinsic viscosity of the polyamide material, so that the processing performance of the nylon composite material is improved.
The main antioxidant is N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzeneThe melting point of the dimethylamide is 272 ℃, the boiling point is more than 360 ℃, the thermal stability in the polymerization process of the nylon material is good, the amide group of the dimethylamide can react with the end group of the nylon material to improve the compatibility, and the hindered piperidyl can provide the antioxidation and improve the dyeing property of the copolymer. The auxiliary antioxidant adopted by the invention is bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, the melting point is 239 ℃, the thermal decomposition temperature exceeds 350 ℃, the auxiliary antioxidant has good heat resistance and hydrolysis resistance, excellent color stability and melt stability can be provided for the polymerization process of the nylon material, meanwhile, the thermal degradation of the nylon material in the high-temperature process can be prevented, the thermal oxidative discoloration caused by long time is inhibited, and the auxiliary antioxidant also provides Nitrogen Oxide (NO)x) Color stability in gas environment, and prevention of discoloration of fumigant.
Compared with the prior art, the low dielectric constant nylon composite material and the preparation method thereof provided by the invention have the following beneficial effects:
1. the composite nylon material with low dielectric constant, low water absorption, excellent mechanical property and processability is prepared by selecting raw materials such as caprolactam, 2' -bis (trifluoromethyl) diaminobiphenyl, adipic acid, amino zeolite nanocrystalline and the like in a specific ratio, the dielectric constant is 2.88-2.97, the intrinsic viscosity is 1.07 dL/G-1.70 dL/G, the melting temperature is 228-238 ℃, and the composite nylon material can be applied to shells, coating materials, protective materials and the like of 5G base stations, micro base station systems, data communication terminals and multimedia terminals.
2. The preparation method of the composite nylon material provided by the invention is only carried out by adopting a method of introducing fluorine elements and low dielectric substances for in-situ polymerization, and overcomes the defects of poor mechanical property and high dielectric constant in the traditional preparation method of adding low dielectric substances through a blending method. The preparation method is simple, all reactions do not need to be carried out in a solvent, and the complex process of removing the solvent subsequently is omitted.
3. According to the preparation method of the composite nylon material, nitrogen is introduced before reaction, so that the probability of side reaction is reduced; adding a proper amount of water before reaction, thereby increasing the pressure in the kettle and the mass and heat transfer in the heating process; the reaction process is vacuumized, the low-molecular extractables generated in the polymerization reaction process are removed, the forward progress of the polymerization reaction is facilitated, and the performance of the low-dielectric-constant nylon composite material is not affected by the residual low-molecular extractables, so that the low-molecular extractables are separated without adopting additional extraction equipment, the time can be saved, and the energy can be saved.
Drawings
FIG. 1 is a flow chart of the preparation process of the low dielectric constant nylon composite material of the present invention.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. The present invention may be embodied in many different forms and is not limited to the embodiments described 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 in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The reaction mechanism of the low dielectric constant nylon composite material is as follows (see the preparation process flow chart in figure 1):
wherein a is 100-300, b is 5-50, c is 5-50, and b is c, R is zeolite nanocrystal.
Mechanism of reaction
From the above reaction formula, it can be seen that a nylon resin material can be obtained by condensation polymerization of caprolactam, 2' -bis (trifluoromethyl) diaminobiphenyl and adipic acid, and the terminal amino groups and terminal carboxyl groups of the nylon resin material can react with isocyanate groups of toluene diisocyanate and terminal amino groups of amino zeolite nanocrystals, thereby improving the compatibility of the nylon resin material and the amino zeolite nanocrystals; the terminal amino group of the nylon resin material can react with the maleic anhydride group of the ethylene-octene copolymer grafted maleic anhydride, thereby improving the toughness of the nylon resin material.
The raw materials used in the embodiment of the invention are as follows:
caprolactam available from Zhongpetrochemical Balng petrochemical Co.
2,2' -bis (trifluoromethyl) diaminobiphenyl, purchased from new materials of Junrez, Hebei.
Adipic acid, available from llc of the samara group, china.
Ethyl orthosilicate, purchased from Shandong King brand Biotech Co., Ltd.
Tetrabutylammonium hydroxide, available from Kjessah chemical Co., Ltd.
3-aminopropyltriethoxysilane, available from Nanjing Nentede New Material technology, Inc.
The copolymer of ethylene and octene was grafted with maleic anhydride at a grafting rate of 0.9% and was obtained from Shenyangtotong plastics Co.
The copolymer of ethylene and octene was grafted with maleic anhydride at a grafting rate of 1.5% and was obtained from Shenyangtotong plastics Co.
Benzoic acid, available from national pharmaceutical group chemical reagents, ltd.
Toluene diisocyanate, available from national pharmaceutical group chemical agents, ltd.
N, N' -bis (2,2,6, 6-tetramethyl-4-piperidinyl) -1, 3-benzenedicarboxamide, available from Toxongitai chemical Co., Ltd.
Bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, available from Shanghai Yaozao Fine chemical Co., Ltd.
Polyamide 6, available from the Balingdivision of petrochemical Co., Ltd, China.
The preparation of the amino zeolite nanocrystals was as follows: adding 5mol of tetraethoxysilane (1041g), 1.25mol of tetrabutylammonium hydroxide (324g) and 155mol of deionized water (2790g) into a 10L polymerization reaction kettle, stirring at 35 ℃ for prehydrolysis for 15 hours, crystallizing at 130 ℃ for 15 hours, cooling to normal temperature to obtain zeolite nanocrystals, finally adding 2 wt% (calculated by the total mass of tetraethoxysilane and tetrabutylammonium hydroxide, namely 27.3g) of 3-aminopropyltriethoxysilane, stirring at 35 ℃ for 2 hours, and vacuum drying to obtain the amino zeolite nanocrystals.
Example 1 Low dielectric constant Nylon composite and method for preparing the same
The low dielectric constant nylon composite material of the embodiment is prepared from the following raw materials in parts by weight:
wherein, the grafting rate of the maleic anhydride in the ethylene-octene copolymer grafted maleic anhydride POE-g-MAH is 0.9 percent.
The preparation method of the low dielectric constant nylon composite material comprises the following steps:
(1) adding the caprolactam after vacuum drying into a stirring type polymerization reactor, and simultaneously adding the 2,2 '-bis (trifluoromethyl) diaminobiphenyl, adipic acid, amino zeolite nanocrystals, ethylene-octene copolymer grafted maleic anhydride, benzoic acid, toluene diisocyanate, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-phthalic amide, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate and a proper amount of water; vacuumizing for 7min, introducing nitrogen for 7min, and circulating for 4 times in such a way, so that reactants exist in the environment under the protection of nitrogen, and controlling the system pressure in the stirring type polymerization reactor to be 0.4 MPa;
(2) and (2) sealing the stirring type polymerization reactor within 4 hours, heating to 220 ℃ at a constant speed, adjusting the stirring speed of the stirring type polymerization reactor to 40r/min, wherein when the temperature of the stirring type polymerization reactor reaches 215 ℃, gas is discharged to 1.7MPa, the pressure is maintained at 1.7MPa, after 0.5 hour of reaction, gas is discharged to normal pressure, meanwhile, the temperature is increased to 250 ℃, after 0.5 hour of continuous reaction at 250 ℃, vacuumizing is continuously performed at a constant temperature for 2 hours, the reaction is finished, and nitrogen is supplemented during discharging to obtain the catalyst.
Example 2 Low dielectric constant Nylon composite and method for preparing the same
The low dielectric constant nylon composite material of the embodiment is prepared from the following raw materials in parts by weight:
wherein, the grafting rate of the maleic anhydride in the ethylene-octene copolymer grafted maleic anhydride POE-g-MAH is 1.5 percent.
The preparation method of the low dielectric constant nylon composite material comprises the following steps:
(1) adding the caprolactam after vacuum drying into a stirring type polymerization reactor, and simultaneously adding the 2,2 '-bis (trifluoromethyl) diaminobiphenyl, adipic acid, amino zeolite nanocrystals, ethylene-octene copolymer grafted maleic anhydride, benzoic acid, toluene diisocyanate, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-phthalic amide, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate and a proper amount of water; then vacuumizing for 3min, introducing nitrogen for 3min, and circulating for 8 times in such a way, so that reactants exist in the environment under the protection of nitrogen, and controlling the system pressure in the stirring type polymerization reactor to be 0.1 MPa;
(2) and (2) sealing the stirring type polymerization reactor within 2 hours, heating to 215 ℃ at a constant speed, adjusting the stirring speed of the stirring type polymerization reactor to 40r/min, wherein when the temperature of the stirring type polymerization reactor reaches 215 ℃, gas is released to 1.7MPa, the pressure is maintained at 1.7MPa, after the reaction is carried out for 3 hours, gas is released to normal pressure, the temperature is increased to 240 ℃, after the reaction is continued for 3 hours at 240 ℃, the constant temperature is continuously vacuumized for 0.1 hour, after the reaction is finished, nitrogen is supplemented during discharging, and the low-dielectric-constant nylon composite material is obtained.
Example 3 Low dielectric constant Nylon composite and method for preparing the same
The low dielectric constant nylon composite material of the embodiment is prepared from the following raw materials in parts by weight:
wherein, the grafting rate of the maleic anhydride in the ethylene-octene copolymer grafted maleic anhydride POE-g-MAH is 1.5 percent.
The preparation method of the low dielectric constant nylon composite material comprises the following steps:
(1) adding the caprolactam after vacuum drying into a stirring type polymerization reactor, and simultaneously adding the 2,2 '-bis (trifluoromethyl) diaminobiphenyl, adipic acid, amino zeolite nanocrystals, ethylene-octene copolymer grafted maleic anhydride, benzoic acid, toluene diisocyanate, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-phthalic amide, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate and a proper amount of water; then vacuumizing for 6min, introducing nitrogen for 6min, and circulating for 5 times in such a way, so that reactants exist in the environment under the protection of nitrogen, and controlling the system pressure in the stirring type polymerization reactor to be 0.3 MPa;
(2) and (2) sealing the stirring type polymerization reactor within 4 hours, heating to 220 ℃ at a constant speed, adjusting the stirring speed of the stirring type polymerization reactor to 40r/min, wherein when the temperature of the stirring type polymerization reactor reaches 215 ℃, the gas is released to 1.7MPa, the pressure is maintained at 1.7MPa, after the reaction is carried out for 1 hour, the gas is released to normal pressure, the temperature is increased to 250 ℃, after the reaction is continued for 1 hour at 250 ℃, the constant temperature is continuously vacuumized for 1.5 hours, after the reaction is finished, nitrogen is supplemented during discharging, and the low dielectric constant nylon composite material is obtained.
Example 4 Low dielectric constant Nylon composite and method for preparing the same
The low dielectric constant nylon composite material of the embodiment is prepared from the following raw materials in parts by weight:
wherein, the grafting rate of the maleic anhydride in the ethylene-octene copolymer grafted maleic anhydride POE-g-MAH is 1.5 percent.
The preparation method of the low dielectric constant nylon composite material comprises the following steps:
(1) adding the caprolactam after vacuum drying into a stirring type polymerization reactor, and simultaneously adding the 2,2 '-bis (trifluoromethyl) diaminobiphenyl, adipic acid, amino zeolite nanocrystals, ethylene-octene copolymer grafted maleic anhydride, benzoic acid, toluene diisocyanate, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-phthalic amide, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate and a proper amount of water; then vacuumizing for 4min, introducing nitrogen for 4min, and circulating for 7 times in such a way, so that reactants exist in the environment under the protection of nitrogen, and controlling the system pressure in the stirring type polymerization reactor to be 0.2 MPa;
(2) and (2) sealing the stirring type polymerization reactor within 2 hours, heating to 215 ℃ at a constant speed, adjusting the stirring speed of the stirring type polymerization reactor to 40r/min, wherein when the temperature of the stirring type polymerization reactor reaches 215 ℃, the gas is released to 1.7MPa, the pressure is maintained at 1.7MPa, after 2 hours of reaction, the gas is released to normal pressure, the temperature is increased to 240 ℃, after 2 hours of continuous reaction at 240 ℃, the constant temperature is continuously vacuumized for 0.5 hour, after the reaction is finished, nitrogen is supplemented during discharging, and the low-dielectric-constant nylon composite material is obtained.
Example 5 Low dielectric constant Nylon composite and method of making the same
The low dielectric constant nylon composite material of the embodiment is prepared from the following raw materials in parts by weight:
wherein, the grafting rate of the maleic anhydride in the ethylene-octene copolymer grafted maleic anhydride POE-g-MAH is 1.5 percent.
The preparation method of the low dielectric constant nylon composite material comprises the following steps:
(1) adding the caprolactam after vacuum drying into a stirring type polymerization reactor, and simultaneously adding the 2,2 '-bis (trifluoromethyl) diaminobiphenyl, adipic acid, amino zeolite nanocrystals, ethylene-octene copolymer grafted maleic anhydride, benzoic acid, toluene diisocyanate, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-phthalic amide, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate and a proper amount of water; then vacuumizing for 5min, introducing nitrogen for 5min, and circulating for 6 times in such a way, so that reactants exist in the environment under the protection of nitrogen, and controlling the system pressure in the stirring type polymerization reactor to be 0.25 MPa;
(2) and (2) sealing the stirring type polymerization reactor within 3 hours, heating to 218 ℃ at a constant speed, adjusting the stirring speed of the stirring type polymerization reactor to 40r/min, wherein when the temperature of the stirring type polymerization reactor reaches 215 ℃, gas is discharged to 1.7MPa, the pressure is maintained at 1.7MPa, after the reaction is carried out for 1.5 hours, gas is discharged to normal pressure, the temperature is raised to 245 ℃, after the reaction is continued for 1.5 hours at 245 ℃, vacuumizing is continuously carried out for 1 hour at a constant temperature, the reaction is finished, and nitrogen is supplemented during discharging, so that the low-dielectric-constant nylon composite material is obtained.
Example 6 Low dielectric constant Nylon composite and method of making the same
The low dielectric constant nylon composite material of the embodiment is prepared from the following raw materials in parts by weight:
wherein, the grafting rate of the maleic anhydride in the ethylene-octene copolymer grafted maleic anhydride POE-g-MAH is 1.5 percent.
The preparation method of the low dielectric constant nylon composite material comprises the following steps:
(1) adding the caprolactam after vacuum drying into a stirring type polymerization reactor, and simultaneously adding the 2,2 '-bis (trifluoromethyl) diaminobiphenyl, adipic acid, amino zeolite nanocrystals, ethylene-octene copolymer grafted maleic anhydride, benzoic acid, toluene diisocyanate, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-phthalic amide, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate and a proper amount of water; then vacuumizing for 5min, introducing nitrogen for 5min, and circulating for 6 times in such a way, so that reactants exist in the environment under the protection of nitrogen, and controlling the system pressure in the stirring type polymerization reactor to be 0.25 MPa;
(2) and (2) sealing the stirring type polymerization reactor within 3 hours, heating to 218 ℃ at a constant speed, adjusting the stirring speed of the stirring type polymerization reactor to 40r/min, wherein when the temperature of the stirring type polymerization reactor reaches 215 ℃, gas is discharged to 1.7MPa, the pressure is maintained at 1.7MPa, after the reaction is carried out for 1.5 hours, gas is discharged to normal pressure, the temperature is raised to 245 ℃, after the reaction is continued for 1.5 hours at 245 ℃, vacuumizing is continuously carried out for 1 hour at a constant temperature, the reaction is finished, and nitrogen is supplemented during discharging, so that the low-dielectric-constant nylon composite material is obtained.
Example 7 Low dielectric constant Nylon composite and method of making the same
The low dielectric constant nylon composite material of the embodiment is prepared from the following raw materials in parts by weight:
wherein, the grafting rate of the maleic anhydride in the ethylene-octene copolymer grafted maleic anhydride POE-g-MAH is 1.5 percent.
The preparation method of the low dielectric constant nylon composite material comprises the following steps:
(1) adding the caprolactam after vacuum drying into a stirring type polymerization reactor, and simultaneously adding the 2,2 '-bis (trifluoromethyl) diaminobiphenyl, adipic acid, amino zeolite nanocrystals, ethylene-octene copolymer grafted maleic anhydride, benzoic acid, toluene diisocyanate, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-phthalic amide, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate and a proper amount of water; then vacuumizing for 5min, introducing nitrogen for 5min, and circulating for 6 times in such a way, so that reactants exist in the environment under the protection of nitrogen, and controlling the system pressure in the stirring type polymerization reactor to be 0.25 MPa;
(2) and (2) sealing the stirring type polymerization reactor within 3 hours, heating to 218 ℃ at a constant speed, adjusting the stirring speed of the stirring type polymerization reactor to 40r/min, wherein when the temperature of the stirring type polymerization reactor reaches 215 ℃, gas is discharged to 1.7MPa, the pressure is maintained at 1.7MPa, after the reaction is carried out for 1.5 hours, gas is discharged to normal pressure, the temperature is raised to 245 ℃, after the reaction is continued for 1.5 hours at 245 ℃, vacuumizing is continuously carried out for 1 hour at a constant temperature, the reaction is finished, and nitrogen is supplemented during discharging, so that the low-dielectric-constant nylon composite material is obtained.
Comparative example 1
The low dielectric constant nylon composite material is prepared from the following raw materials in parts by weight:
wherein, the grafting rate of the maleic anhydride in the ethylene-octene copolymer grafted maleic anhydride POE-g-MAH is 1.5 percent.
The preparation method of the low dielectric constant nylon composite material comprises the following steps:
(1) adding the caprolactam after vacuum drying into a stirring type polymerization reactor, and simultaneously adding the 2,2 '-bis (trifluoromethyl) diaminobiphenyl, adipic acid, ethylene-octene copolymer grafted maleic anhydride, benzoic acid, toluene diisocyanate, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate and a proper amount of water; then vacuumizing for 5min, introducing nitrogen for 5min, and circulating for 6 times in such a way, so that reactants exist in the environment under the protection of nitrogen, and controlling the system pressure in the stirring type polymerization reactor to be 0.25 MPa;
(2) and (2) sealing the stirring type polymerization reactor within 3 hours, heating to 218 ℃ at a constant speed, adjusting the stirring speed of the stirring type polymerization reactor to 40r/min, wherein when the temperature of the stirring type polymerization reactor reaches 215 ℃, gas is discharged to 1.7MPa, the pressure is maintained at 1.7MPa, after the reaction is carried out for 1.5 hours, gas is discharged to normal pressure, the temperature is raised to 245 ℃, after the reaction is continued for 1.5 hours at 245 ℃, vacuumizing is continuously carried out for 1 hour at a constant temperature, the reaction is finished, and nitrogen is supplemented during discharging, so that the low-dielectric-constant nylon composite material is obtained.
Comparative example 2
The low dielectric constant nylon composite material is prepared from the following raw materials in parts by weight:
wherein, the grafting rate of the maleic anhydride in the ethylene-octene copolymer grafted maleic anhydride POE-g-MAH is 1.5 percent.
The preparation method of the low dielectric constant nylon composite material comprises the following steps:
(1) adding the caprolactam after vacuum drying into a stirring type polymerization reactor, and simultaneously adding the 2,2 '-bis (trifluoromethyl) diaminobiphenyl, adipic acid, common zeolite, ethylene-octene copolymer grafted maleic anhydride, benzoic acid, toluene diisocyanate, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate and a proper amount of water; then vacuumizing for 5min, introducing nitrogen for 5min, and circulating for 6 times in such a way, so that reactants exist in the environment under the protection of nitrogen, and controlling the system pressure in the stirring type polymerization reactor to be 0.25 MPa;
(2) and (2) sealing the stirring type polymerization reactor within 3 hours, heating to 218 ℃ at a constant speed, adjusting the stirring speed of the stirring type polymerization reactor to 40r/min, wherein when the temperature of the stirring type polymerization reactor reaches 215 ℃, gas is discharged to 1.7MPa, the pressure is maintained at 1.7MPa, after the reaction is carried out for 1.5 hours, gas is discharged to normal pressure, the temperature is raised to 245 ℃, after the reaction is continued for 1.5 hours at 245 ℃, vacuumizing is continuously carried out for 1 hour at a constant temperature, the reaction is finished, and nitrogen is supplemented during discharging, so that the low-dielectric-constant nylon composite material is obtained.
Comparative example 3
The low dielectric constant nylon composite material is prepared from the following raw materials in parts by weight:
the preparation method of the low dielectric constant nylon composite material comprises the following steps:
(1) adding the caprolactam after vacuum drying into a stirring type polymerization reactor, and simultaneously adding the 2,2 '-bis (trifluoromethyl) diaminobiphenyl, adipic acid, amino zeolite nanocrystals, benzoic acid, toluene diisocyanate, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate and a proper amount of water; then vacuumizing for 5min, introducing nitrogen for 5min, and circulating for 6 times in such a way, so that reactants exist in the environment under the protection of nitrogen, and controlling the system pressure in the stirring type polymerization reactor to be 0.25 MPa;
(2) and (2) sealing the stirring type polymerization reactor within 3 hours, heating to 218 ℃ at a constant speed, adjusting the stirring speed of the stirring type polymerization reactor to 40r/min, wherein when the temperature of the stirring type polymerization reactor reaches 215 ℃, gas is discharged to 1.7MPa, the pressure is maintained at 1.7MPa, after the reaction is carried out for 1.5 hours, gas is discharged to normal pressure, the temperature is raised to 245 ℃, after the reaction is continued for 1.5 hours at 245 ℃, vacuumizing is continuously carried out for 1 hour at a constant temperature, the reaction is finished, and nitrogen is supplemented during discharging, so that the low-dielectric-constant nylon composite material is obtained.
Comparative example 4
The low dielectric constant nylon composite material is prepared from the following raw materials in parts by weight:
wherein, the grafting rate of the maleic anhydride in the ethylene-octene copolymer grafted maleic anhydride POE-g-MAH is 1.5 percent.
The preparation method of the low dielectric constant nylon composite material comprises the following steps:
(1) adding the caprolactam after vacuum drying into a stirring type polymerization reactor, and simultaneously adding the 2,2 '-bis (trifluoromethyl) diaminobiphenyl, adipic acid, amino zeolite nanocrystals, ethylene-octene copolymer grafted maleic anhydride, toluene diisocyanate, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate and a proper amount of water; then vacuumizing for 5min, introducing nitrogen for 5min, and circulating for 6 times in such a way, so that reactants exist in the environment under the protection of nitrogen, and controlling the system pressure in the stirring type polymerization reactor to be 0.25 MPa;
(2) and (2) sealing the stirring type polymerization reactor within 3 hours, heating to 218 ℃ at a constant speed, adjusting the stirring speed of the stirring type polymerization reactor to 40r/min, wherein when the temperature of the stirring type polymerization reactor reaches 215 ℃, gas is discharged to 1.7MPa, the pressure is maintained at 1.7MPa, after the reaction is carried out for 1.5 hours, gas is discharged to normal pressure, the temperature is raised to 245 ℃, after the reaction is continued for 1.5 hours at 245 ℃, vacuumizing is continuously carried out for 1 hour at a constant temperature, the reaction is finished, and nitrogen is supplemented during discharging, so that the low-dielectric-constant nylon composite material is obtained.
Comparative example 5
The low dielectric constant nylon composite material is prepared from the following raw materials in parts by weight:
wherein, the grafting rate of the maleic anhydride in the ethylene-octene copolymer grafted maleic anhydride POE-g-MAH is 1.5 percent.
The preparation method of the low dielectric constant nylon composite material comprises the following steps:
(1) adding the caprolactam after vacuum drying into a stirring type polymerization reactor, and simultaneously adding the 2,2 '-bis (trifluoromethyl) diaminobiphenyl, adipic acid, amino zeolite nanocrystals, ethylene-octene copolymer grafted maleic anhydride, benzoic acid, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate and a proper amount of water; then vacuumizing for 5min, introducing nitrogen for 5min, and circulating for 6 times in such a way, so that reactants exist in the environment under the protection of nitrogen, and controlling the system pressure in the stirring type polymerization reactor to be 0.25 MPa;
(2) and (2) sealing the stirring type polymerization reactor within 3 hours, heating to 218 ℃ at a constant speed, adjusting the stirring speed of the stirring type polymerization reactor to 40r/min, wherein when the temperature of the stirring type polymerization reactor reaches 215 ℃, gas is discharged to 1.7MPa, the pressure is maintained at 1.7MPa, after the reaction is carried out for 1.5 hours, gas is discharged to normal pressure, the temperature is raised to 245 ℃, after the reaction is continued for 1.5 hours at 245 ℃, vacuumizing is continuously carried out for 1 hour at a constant temperature, the reaction is finished, and nitrogen is supplemented during discharging, so that the low-dielectric-constant nylon composite material is obtained.
Comparative example 6
The low dielectric constant nylon composite material is prepared from the following raw materials in parts by weight:
wherein, the grafting rate of the maleic anhydride in the ethylene-octene copolymer grafted maleic anhydride POE-g-MAH is 1.5 percent.
The preparation method of the low dielectric constant nylon composite material comprises the following steps:
(1) drying the polyamide 6 at the temperature of 110 ℃ for 3 hours, cooling, and placing the cooled polyamide 6 for later use;
(2) adding the amino zeolite nanocrystal, ethylene-octene copolymer grafted maleic anhydride, toluene diisocyanate, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide and bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate into another high-speed stirrer (the rotating speed is 1000 rpm) for mixing;
(3) adding the polyamide 6 dried in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into the parallel double-screw extruder (totally eight zones) in the lateral direction (fourth zone) for melt extrusion, and granulating, wherein the process parameters are as follows: the temperature in the first zone was 210 ℃, the temperature in the second zone was 220 ℃, the temperature in the third zone was 225 ℃, the temperature in the fourth zone was 230 ℃, the temperature in the fifth zone was 230 ℃, the temperature in the sixth zone was 230 ℃, the temperature in the seventh zone was 230 ℃, the temperature in the eighth zone was 230 ℃, the temperature in the die head was 225 ℃ and the screw speed was 400 rpm.
The following is a summary of the raw material compositions of examples 1-7 and comparative examples 1-6.
TABLE 1 summary of the raw material compositions of examples 1-7 and comparative examples 1-6
Remarking: replacing amino zeolite nanocrystalline with common zeolite (prepared by a sol-gel method); b, replacing caprolactam with polyamide 6.
Wherein, the addition amounts of N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide (main antioxidant) and bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate (auxiliary antioxidant) of the above examples and comparative examples are all 0.2 part.
Examples 1 to 7 were conducted to prepare low dielectric constant nylon composite materials by adjusting the amounts of 2,2' -bis (trifluoromethyl) diaminobiphenyl, adipic acid, amino zeolite nanocrystals, ethylene-octene copolymer grafted maleic anhydride (POE-g-MAH), benzoic acid, and toluene diisocyanate, and comparative examples 1 to 6 were conducted to prepare low dielectric constant nylon composite materials by changing amino zeolite nanocrystals to ordinary zeolite, ethylene-octene copolymer grafted maleic anhydride (POE-g-MAH), benzoic acid, and toluene diisocyanate, and changing caprolactam to polyamide 6 resin, without adding amino zeolite nanocrystals, on the basis of the raw materials of example 7. The low dielectric constant nylon composite materials prepared in the above examples and comparative examples were subjected to the following performance tests:
tensile property: the tensile rate is 50mm/min according to the test of GB/T1040-2006 standard.
Notched impact strength: testing according to GB/T1843-2008 standard.
Melt index: the test temperature is 250 ℃ and the load is 2.16kg according to the test of GB/T3682-2000-plus-2000 standard.
Balance water absorption: the test temperature is 25 ℃ according to the GB/T1034-2008 standard.
Dielectric constant: the frequency was tested at 5GHz according to GB/T5597-1999 Standard.
Intrinsic viscosity: tested according to GB/T1632-2008 standard, the solvent is concentrated sulfuric acid.
Melting temperature: testing according to GB/T19466.3-2004 standard.
The results of the performance tests are shown in table 2.
TABLE 2 Performance of the Low dielectric constant Nylon composites of examples 1-7 and comparative examples 1-6
As can be seen from table 2:
with the increase of the addition amount of 2,2' -bis (trifluoromethyl) diaminobiphenyl, adipic acid, benzoic acid, amino zeolite nanocrystals and ethylene-octene copolymer grafted maleic anhydride (POE-g-MAH), the tensile strength and melt index of the low dielectric constant nylon composite material show a trend of increasing and then decreasing, which is mainly influenced by multiple factors: (1)2,2' -bis (trifluoromethyl) diaminobiphenyl contains rigid benzene ring structural units, can improve the tensile strength of the material, but also can block the relative movement of molecular chains, thereby reducing the melt index of the material; (2) the benzoic acid influences the intrinsic viscosity of the nylon composite material, the less the benzoic acid is, the higher the viscosity is, the higher the tensile strength of the nylon composite material is, and the lower the melt index is; (3) the amino zeolite nanocrystal is high-crystallinity porous SiO with micropores with uniform molecular sizes inside2It has reinforcing effect on polymer and can raise the tensile strength of material; (4) the ethylene-octene copolymer grafted maleic anhydride (POE-g-MAH) itself has a low tensile strength and poor flow properties, which have an adverse effect on the tensile strength and melt index of the composite. Under the influence of the common factors, when the addition amount of 2,2' -bis (trifluoromethyl) diaminobiphenyl, adipic acid, benzoic acid, amino zeolite nanocrystals and ethylene-octene copolymer grafted maleic anhydride (POE-g-MAH) is less, the influence of a benzene ring on the tensile strength of the composite material is higher than that of other factors, and the influence of intrinsic viscosity on the melt index of the composite material is higher than that of other factors; when the addition amount of 2,2' -bis (trifluoromethyl) diaminobiphenyl, adipic acid, benzoic acid, amino zeolite nanocrystal and ethylene-octene copolymer grafted maleic anhydride (POE-g-MAH) is more, the influence of the intrinsic viscosity on the tensile strength of the composite material is higher than that of other factors, and the influence of a benzene ring on the melt index of the composite material is higher than that of other factors.
As the addition of ethylene and octene copolymer grafted maleic anhydride (POE-g-MAH) is reduced, the notch impact performance of the copolymer is reduced and the change trend is reduced, because the introduction of octene in a POE molecular chain destroys part of polyethylene crystals, an octene chain segment and the polyethylene chain segment damaged by the crystals jointly form an elastic soft segment, and the crystal part of the polyethylene forms a hard segment which plays a role of a physical cross-linking point, so that the POE has the property of an elastomer, and the addition of the POE-g-MAH is reduced, so that the composite material has reduced external impact absorption capacity when being impacted by external force, and the notch impact performance of the composite material is reduced.
As the addition amount of 2,2' -bis (trifluoromethyl) diaminobiphenyl increases, the water absorption rate of the compound tends to decrease, and the melting temperature of the compound tends to increase, because the more structural units of 2,2' -bis (trifluoromethyl) diaminobiphenyl decrease the density of amide groups, thereby decreasing the water absorption rate, while the more rigid structural units of benzene rings in 2,2' -bis (trifluoromethyl) diaminobiphenyl hinder the relative slippage between the molecular chains of the composite material, so that the slippage can occur at a higher temperature, thereby increasing the melting temperature.
The dielectric constant of the nylon composite material shows a tendency of decreasing change as the addition amount of 2,2 '-bis (trifluoromethyl) diaminobiphenyl and amino zeolite nanocrystal increases, because 2,2' -bis (trifluoromethyl) diaminobiphenyl contains fluorine atom, the attraction of fluorine atom core to electron outside the nucleus is strong, the interaction force between electron and atom nucleus is large, so the electron cloud density is high, the polarizability when polarized by external electric field is low, at the same time, the fluorine-containing group with larger volume is introduced into the polymer molecule, the stacking density of the polymer can be decreased, the free volume of the polymer can be increased, thereby the dielectric constant of the polymer material is decreased, and the zeolite nanocrystal is a highly crystalline porous SiO with uniform molecular size micropores inside2The composite material has extremely low theoretical dielectric constant (about 1.60), and the dielectric constant of the nylon composite material can be effectively reduced by compounding 2,2' -bis (trifluoromethyl) diaminobiphenyl and amino zeolite nanocrystals under the combined action of the two.
With the reduction of the addition amount of benzoic acid, the intrinsic viscosity of the nylon composite material shows an increasing change trend, because the benzoic acid with single functional groups plays a role of a polymerization inhibitor, so that the intrinsic viscosity of the nylon composite material is effectively adjusted, the processing performance is influenced when the intrinsic viscosity of the nylon composite material is too high, the mechanical performance is influenced when the intrinsic viscosity of the nylon composite material is too low, and therefore the nylon composite material with good mechanical performance and processing performance can be obtained only by proper intrinsic viscosity.
In summary, by adjusting the addition amounts of 2,2' -bis (trifluoromethyl) diaminobiphenyl, adipic acid, amino zeolite nanocrystals, ethylene-octene copolymer grafted maleic anhydride (POE-g-MAH), benzoic acid, and toluene diisocyanate, the nylon composite material of the present invention with low dielectric constant, excellent mechanical properties, and excellent processability can be obtained under the synergistic cooperation of the additives, wherein the nylon composite material prepared in example 7 has the best combination properties.
Example 7 in comparison with comparative example 1, comparative example 1 has no added amino zeolite nanocrystals, and the dielectric constant of comparative example 1 is higher than example 7 because the amino zeolite nanocrystals have a porous structure and have a dielectric constant of about 1.6.
Example 7 compared with comparative example 2, comparative example 2 used a common zeolite prepared by a sol-gel method, which had strong hydrophilicity, poor compatibility with nylon materials, and inferior mechanical properties to those of amino zeolite nanocrystals, so that the nylon composite material prepared by comparative example 2 had tensile strength and notched impact properties lower than those of example 7, and had a dielectric constant higher than that of example 7.
Example 7 in comparison with comparative example 3, comparative example 3 was not added with POE-g-MAH, and since POE-g-MAH has very high notched impact properties, the maleic anhydride group of POE-g-MAH can react with the terminal amino group of nylon material, previously enhancing interfacial adhesion and compatibility between the two, and POE-g-MAH has a low dielectric constant (Dk of 2.4, test frequency 5GHz), the notched impact properties of the nylon composite prepared in comparative example 3 were lower than those of example 7, and the dielectric constant was higher than that of example 7.
Example 7 compared with comparative example 4, comparative example 4 has no benzoic acid added, and the melt index of comparative example 4 is much lower than that of example 7 because monofunctional benzoic acid acts as a polymerization inhibitor, thereby effectively adjusting the intrinsic viscosity of the nylon composite, and too high an intrinsic viscosity of the nylon composite affects processability.
Example 7 compared with comparative example 5, comparative example 5 has no toluene diisocyanate added, and the nylon composite material prepared in comparative example 5 has lower tensile strength and notched impact strength than example 7 because the isocyanate group of toluene diisocyanate can react with the terminal group of nylon and the terminal amino group of the amino zeolite nanocrystal to improve the compatibility between the two.
Example 7 compared with comparative example 6, comparative example 6 prepared by a common blending method using a polyamide 6 resin to obtain a low dielectric constant nylon composite material has a higher dielectric constant than example 7 because of the high amide bond density of the common polyamide 6 resin and the lack of rigid benzene rings and fluorine-containing pendant groups in the nylon structure of example 7, and thus absorbs moisture easily in daily use, the equilibrium water absorption rate reaches 1.65%, and the dielectric constant of water is 78.5 (test frequency 1kHz according to GB/T5597-1999 standard), which is higher than that of example 7.
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 (10)
1. The low-dielectric-constant nylon composite material is characterized by being prepared from the following raw materials in parts by weight:
the 2,2' -bis (trifluoromethyl) diaminobiphenyl and adipic acid are in an equimolar ratio;
the amino zeolite nanocrystal is obtained by organizing zeolite nanocrystals by 3-aminopropyltriethoxysilane; the zeolite nanocrystals are prepared from ethyl orthosilicate and tetrabutylammonium hydroxide.
2. The low dielectric constant nylon composite material as claimed in claim 1, which is prepared from the following raw materials in parts by weight:
3. the low dielectric constant nylon composite material as claimed in claim 2, which is prepared from the following raw materials in parts by weight:
4. the low dielectric constant nylon composite material of any one of claims 1 to 3, wherein the low dielectric constant nylon composite material has a dielectric constant of 2.88 to 2.97, an intrinsic viscosity of 1.07dL/g to 1.70dL/g, and a melting temperature of 228 ℃ to 238 ℃.
5. The low dielectric constant nylon composite material of any one of claims 1 to 3, wherein the maleic anhydride grafting ratio of the ethylene-octene copolymer grafted maleic anhydride is 0.8% to 2.2%.
6. The low dielectric constant nylon composite material of any one of claims 1 to 3, wherein the preparation method of the amino zeolite nanocrystal comprises the following steps: ethyl orthosilicate, tetrabutylammonium hydroxide and deionized water in a molar ratio of 1: 0.1-0.4: 13-50, stirring and pre-hydrolyzing for 10-20 hours at 30-40 ℃, crystallizing for 10-20 hours at 110-150 ℃, cooling to normal temperature to obtain zeolite nanocrystals, finally adding 3-aminopropyltriethoxysilane accounting for 1-3 wt% of the total mass of the tetraethoxysilane and the tetrabutylammonium hydroxide, stirring for 0.5-3.5 hours at 30-40 ℃, and vacuum drying to obtain the catalyst.
7. The low dielectric constant nylon composite material of any one of claims 1 to 3, wherein the antioxidant comprises a primary antioxidant and a secondary antioxidant; the main antioxidant is one or more of pentaerythritol tetra (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate), N '-1, 6-hexylene-bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionamide ], N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide; the auxiliary antioxidant is one or more of tris (2, 4-di-tert-butylphenyl) phosphite, bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite, bis (2, 4-di-tert-butyl) pentaerythritol diphosphite and bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite.
8. The method for preparing the low dielectric constant nylon composite material as claimed in any one of claims 1 to 7, comprising the steps of:
(1) adding the caprolactam after vacuum drying into a stirring type polymerization reactor, and simultaneously adding 2,2' -bis (trifluoromethyl) diaminobiphenyl, adipic acid, amino zeolite nanocrystalline, ethylene-octene copolymer grafted maleic anhydride, benzoic acid, toluene diisocyanate, an antioxidant and a proper amount of water; then vacuumizing for 3-7 min, introducing nitrogen for 3-7 min, circulating for 4-8 times in the way, and controlling the system pressure in the stirring type polymerization reactor to be 0.1-0.4 MPa;
(2) adjusting the stirring speed of the stirring type polymerization reactor to be 30 r/min-50 r/min, heating the stirring type polymerization reactor to 215-220 ℃ in a sealed and uniform manner within 2-4 hours, discharging gas to 1.7MPa when the temperature of the stirring type polymerization reactor reaches 215 ℃, maintaining the pressure at 1.7MPa, discharging gas to normal pressure after reacting for 0.5-3 hours, simultaneously heating to 240-250 ℃, continuing to react for 0.5-3 hours at 240-250 ℃, continuously vacuumizing for 0.1-2 hours at constant temperature, finishing the reaction, and supplementing nitrogen gas during discharging to obtain the catalyst.
9. The method for preparing the nylon composite material with low dielectric constant as claimed in claim 8, wherein in the step (1), the vacuumizing time is 4-6 min, the nitrogen introducing time is 4-6 min, the circulation is performed for 5-7 times, and the system pressure in the stirring type polymerization reactor is controlled to be 0.2-0.3 MPa.
10. The preparation method of the nylon composite material with low dielectric constant as claimed in claim 8, wherein the reaction is carried out for 1 to 2 hours when the temperature in the step (2) reaches 215 ℃, the reaction is continued for 1 to 2 hours at 240 to 250 ℃, and the constant temperature is continuously vacuumized for 0.5 to 1.5 hours.
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| CN115011108A (en) * | 2022-06-30 | 2022-09-06 | 江西中塑新材料科技有限公司 | Luminous transparent nylon resin and synthesis method thereof |
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| CN114181518B (en) | 2023-06-16 |
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