CN114181518B - Nylon composite material with low dielectric constant and preparation method thereof - Google Patents
Nylon composite material with low dielectric constant and preparation method thereof Download PDFInfo
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- CN114181518B CN114181518B CN202111544754.XA CN202111544754A CN114181518B CN 114181518 B CN114181518 B CN 114181518B CN 202111544754 A CN202111544754 A CN 202111544754A CN 114181518 B CN114181518 B CN 114181518B
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- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
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 nanocrystalline, ethylene and octene copolymer grafted maleic anhydride, benzoic acid, toluene diisocyanate and antioxidant. The low-dielectric-constant nylon composite material has excellent mechanical property and processability, low water absorption and low dielectric constant, and can be applied to shells, cladding, 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 nylon composite material with a low dielectric constant and a preparation method thereof.
Background
With the development of the microelectronics industry, the circuit interconnection delay gradually increases. To accommodate the development of very large scale integrated circuits, it is important to develop high performance dielectric materials to reduce interconnect delay, power consumption, and cross-talk. The low-k dielectric material can reduce parasitic capacitance between metal lines, thereby achieving the above purpose. Conventional inorganic materials such as silicon dioxide and the like are increasingly unable to meet the high-speed development of integrated circuits due to excessive dielectric constants. Compared with inorganic dielectric materials, high-performance organic plastics are receiving attention because of the advantages of low dielectric constant, good processability, low cost, chemical resistance, heat resistance and the like. The 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, sensitive notch, large water absorption and high dielectric constant (the dielectric constant Dk of PA6 is 3.5, the test frequency is 5GHz, and the test is according to the GB/T5597-1999 standard).
In general, lowering the dielectric constant of a material can be achieved by lowering the molecular polarizability and reducing the number of polarizable molecules per unit volume. Current low dielectric constant plastics are mainly prepared by the following three ways, alone or in combination. Firstly, introducing a large-volume side group, a non-coplanar group or fluorine element to prepare the intrinsic low-dielectric-constant plastic. Secondly, air holes are introduced into the plastic, so that the number of polarizable molecules in unit volume is reduced, and the purpose of reducing dielectric constant is achieved. Thirdly, adding substances with low dielectric properties to prepare the composite low dielectric constant material.
Currently, some studies are made 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 its preparation method, which comprises the following raw materials (by weight portion): polyamide: 39-93.8 parts; wood powder: 5-30 parts; ionic polymer: 1-6 parts; microsphere foaming agent: 1-3 parts; reinforcing filler material: 0-20 parts; and (3) a lubricant: 0.1-1 parts; stabilizing agent: 0.1-1 part. Chinese patent CN 112175387a discloses a low dielectric nano injection-molded polyamide composite material, and its preparation method and application, the polyamide composite material comprises polyamide 10-95%, polysilsesquioxane 1-10%, antioxidant 0.05-0.5%, release agent 0.1-2%, flexibilizer 1-10%, polyolefin 1-15% and glass fiber 5-50%. Chinese patent CN 107573683a discloses a low dielectric constant glass fiber reinforced polyamide material and preparation method thereof, 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 parts. Chinese patent CN 111675900a discloses a low dielectric constant glass fiber reinforced nylon composite material, in which the functionalized POSS has 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 a low dielectric constant; the flow modifier is added to improve the processing fluidity of the nylon composite material, so that the composite material is suitable for thin-wall products; adding silicone lubricant to strengthen 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 prepared by adding substances with low dielectric properties through a blending method, or the dielectric constant of the materials is reduced through introducing air holes into plastics through the blending of microsphere foaming agents, and the mechanical properties of the nylon materials are easily degraded due to the problems that the addition amount of the substances with low dielectric properties is not low or the air holes are in a structure.
Disclosure of Invention
Based on this, it is an object of the present invention to provide a nylon composite material with 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:
the nylon composite material with 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 nanocrystalline is obtained by organizing zeolite nanocrystalline by 3-aminopropyl triethoxysilane; 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 (test frequency of 5GHz, according to GB/T5597-1999 standard), an intrinsic viscosity of 1.07 dL/g-1.70 dL/g (according to GB/T1632-2008 standard, concentrated sulfuric acid as solvent) and a melting temperature of 228-238 ℃ (according to GB/T19466.3-2004 standard).
In some of these embodiments, the ethylene and octene copolymer has a grafting ratio of maleic anhydride to maleic anhydride of 0.8% to 2.2%.
In some of these embodiments, the preparation method of the amino zeolite nanocrystals includes the steps of: tetraethyl orthosilicate, tetrabutyl ammonium hydroxide and deionized water are mixed according to a mole ratio of 1:0.1 to 0.4: 13-50 are added into a polymerization reaction kettle, stirred and prehydrolyzed for 10-20 hours at 30-40 ℃, then crystallized for 10-20 hours at 110-150 ℃, cooled to normal temperature to obtain zeolite nanocrystalline, and finally 3-aminopropyl triethoxysilane accounting for 1-3 wt% of the total mass of tetraethoxysilane and tetrabutylammonium hydroxide is added, stirred for 0.5-3.5 hours at 30-40 ℃, and vacuum dried to obtain the amino zeolite nanocrystalline.
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-hexamethylene-bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionamide ], and N, N' -bis (2, 6-tetramethyl-4-piperidyl) -1, 3-benzene dicarboxamide; the auxiliary antioxidant is one or more of tri (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 primary antioxidant is N, N' -bis (2, 6-tetramethyl-4-piperidinyl) -1, 3-benzenedicarboxamide, and the secondary antioxidant is bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate.
Another object of the present invention is to provide a method for preparing the low dielectric constant nylon composite material.
The specific technical scheme for realizing the aim of the invention is as follows:
the preparation method of the nylon composite material with low dielectric constant comprises the following steps:
(1) Adding the caprolactam subjected to vacuum drying into a stirring type polymerization reactor, and simultaneously adding 2,2' -di (trifluoromethyl) diaminobiphenyl, adipic acid, amino zeolite nanocrystalline, ethylene and 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, and circulating for 4-8 times, wherein the system pressure in the stirring type polymerization reactor is controlled to be 0.1-0.4 MPa;
(2) And (3) heating the stirring type polymerization reactor to 215-220 ℃ at a constant speed in a closed manner within 2-4 hours, regulating the stirring speed of the stirring type polymerization reactor to 30-50 r/min, deflating to 1.7MPa when the temperature of the stirring type polymerization reactor reaches 215 ℃, maintaining the pressure at 1.7MPa, deflating to normal pressure after reacting for 0.5-3 hours, simultaneously heating to 240-250 ℃ and continuing to react for 0.5-3 hours, continuously vacuumizing at constant temperature for 0.1-2 hours, ending the reaction, and supplementing nitrogen when discharging to obtain the catalyst.
In some of these embodiments, the method for preparing the low dielectric constant nylon composite comprises the steps of:
(1) Adding the caprolactam subjected to vacuum drying into a stirring type polymerization reactor, and simultaneously adding the 2,2' -di (trifluoromethyl) diaminobiphenyl, adipic acid, amino zeolite nanocrystalline, ethylene and 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 to ensure that reactants exist in an environment under the protection of nitrogen, wherein the system pressure in the stirring type polymerization reactor is controlled to be 0.2-0.3 MPa;
(2) And (3) heating the stirring type polymerization reactor to 215-220 ℃ at a constant speed in a closed manner within 2-4 hours, regulating 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 stirring type polymerization reactor is deflated to 1.7MPa, the pressure is maintained to be 1.7MPa, the stirring type polymerization reactor is deflated to normal pressure after reacting for 1-2 hours, the temperature is raised to 240-250 ℃ at the same time, the stirring type polymerization reactor is continuously vacuumized at constant temperature for 0.5-1.5 hours after continuously reacting for 1-2 hours, and the stirring type polymerization reactor is completed and is filled with nitrogen during discharging.
The low dielectric constant nylon composite material has the following functions of the raw materials:
2,2' -di (trifluoromethyl) diaminobiphenyl is introduced with fluorine-containing substituent groups and simultaneously with rigid benzene ring structural units, so as to ensure the thermal performance and mechanical performance of nylon materials. Because the main chain structure of nylon has diversity, different main chain structures have great influence on the performance of nylon, the introduction of fluorine-containing substituent groups into the main chain of nylon can effectively reduce the dielectric constant of the material, but the introduction of fluorine elements can lead to the reduction of the thermal performance and the mechanical performance of the material.
The amino zeolite nanocrystalline is obtained by organically modifying 3-aminopropyl triethoxysilane and introducing an organic functional group amino group on the surface of the amino zeolite nanocrystalline. The zeolite nanocrystalline is a highly crystalline porous SiO with micropores of uniform molecular size inside 2 Has the characteristics of extremely low theoretical dielectric constant (about 1.60), high hydrophobicity, high thermal conductivity, excellent mechanical strength and the like. Although zeolite nanocrystals have an intrinsically high hydrophobicity, small amounts of silicon hydroxyl groups remain on their 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 lower, 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 method 2 The method comprises the steps of carrying out a first treatment on the surface of the (3) Since the amino zeolite nanocrystals are essentiallyHydrophobic, can dispense with SiO prepared by sol-gel method 2 A process of surface hydrophobic treatment is needed; (4) The amino group carried on the surface of the amino zeolite nanocrystalline can react with the carboxyl end group of the nylon material after the amino zeolite nanocrystalline is organically modified, so that the interfacial adhesion and compatibility of the amino zeolite nanocrystalline and the nylon material are improved.
The ethylene and octene copolymer is grafted with maleic anhydride, the maleic anhydride group can react with the terminal amino group of the nylon, and the ethylene and octene copolymer can absorb a great amount of impact energy from the outside, so that the toughness of the nylon composite material can be improved.
Toluene diisocyanate, its isocyanate group can react with the terminal group of nylon, terminal amino group of amino zeolite nanocrystalline, thus can raise the compatibility between nylon material and amino zeolite nanocrystalline.
Benzoic acid, adjusts the intrinsic viscosity of polyamide material, thus improve the processability of nylon composite material.
The main antioxidant is N, N' -bis (2, 6-tetramethyl-4-piperidyl) -1, 3-benzene dicarboxamide, the melting point is 272 ℃, the boiling point is more than 360 ℃, the heat stability in the polymerization process of nylon materials is good, the amide group can react with the end group of the nylon materials to improve the compatibility, and the hindered piperidyl can provide the antioxidation effect 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, has a melting point of 239 ℃ and a thermal decomposition temperature of more than 350 ℃, has good heat resistance and hydrolysis resistance, can provide excellent color stability and melt stability for the polymerization process of nylon materials, can prevent the thermal degradation of the nylon materials in the high-temperature process, can inhibit the thermal oxidative discoloration caused by long time, and also provides the flame retardant for nitric oxide (NO x ) Color stability under gaseous environment prevents the chameleon from discolouring.
Compared with the prior art, the low dielectric constant nylon composite material and the preparation method thereof have the following beneficial effects:
1. the invention selects caprolactam, 2' -di (trifluoromethyl) diaminobiphenyl, adipic acid, amino zeolite nanocrystalline and other raw materials with specific proportion to prepare the composite nylon material with low dielectric constant, low water absorption, excellent mechanical property and processing property, 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 5G base stations, micro base station systems, data communication terminals, shells, coating and protecting materials of multimedia terminals and the like.
2. The preparation method of the composite nylon material adopts the method of introducing fluorine element and low dielectric substance to polymerize in situ, and overcomes the defects of poor mechanical property and high dielectric constant existing in the traditional preparation method of adding low dielectric substance by 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 the reaction, so that the probability of occurrence of side reaction is reduced; adding a proper amount of water before the reaction, so as to increase the pressure in the kettle and transfer mass and heat in the heating process; the vacuum is pumped in the reaction process, and the low-molecular extractables generated in the polymerization reaction process are removed, so that the forward polymerization reaction is facilitated, the residual low-molecular extractables cannot influence the performance of the low-dielectric-constant nylon composite material, and therefore, additional extraction equipment is not needed to separate the low-molecular extractables, and the time and 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 invention.
Detailed Description
In order that the invention may be understood more fully, the invention will be described with reference to the accompanying drawings. This 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. The term "and/or" as used herein 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 of the invention is as follows (the preparation process flow chart is shown in figure 1):
wherein a=100 to 300, b=5 to 50, c=5 to 50, and b=c, R is zeolite nanocrystal.
Reaction mechanism
From the reaction formula, caprolactam, 2' -di (trifluoromethyl) diaminobiphenyl and adipic acid can be subjected to condensation polymerization to obtain a nylon resin material, and the terminal amino group and the terminal carboxyl group of the nylon resin material can react with the isocyanate group of toluene diisocyanate and the terminal amino group of the amino zeolite nanocrystal, so that the compatibility of the nylon resin material and the amino zeolite nanocrystal is improved; the terminal amino group of the nylon resin material can react with the maleic anhydride group of the maleic anhydride grafted by the ethylene and octene copolymer, 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 the petrochemical company, basil, china.
2,2' -bis (trifluoromethyl) diaminobiphenyl, available from Hebei Junli Feng New Material Co.
Adipic acid, purchased from the company of China's god horse group, inc.
Ethyl orthosilicate, available from Shandong Wang Biotechnology Co., ltd.
Tetrabutylammonium hydroxide, available from Shanghai Kaiser chemical Co.
3-aminopropyl triethoxysilane, available from Nanjing Netherlands New Material technologies Co.
The ethylene and octene copolymer was grafted with maleic anhydride at a grafting ratio of 0.9% and was purchased from Shenyang Kotong plastics Co.
The ethylene and octene copolymer was grafted with maleic anhydride at a grafting ratio of 1.5% and was purchased from Shenyang Kotong plastics Co.
Benzoic acid, available from national pharmaceutical group chemical company, inc.
Toluene diisocyanate, available from national medicine group chemical Co., ltd.
N, N' -bis (2, 6-tetramethyl-4-piperidinyl) -1, 3-benzenedicarboxamide, available from Tokyo chemical Co.
Bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, available from Shanghai Yao Fine chemical Co., ltd.
Polyamide 6, purchased from the company baling division, a chinese petrochemical company, inc.
The preparation of the amino zeolite nanocrystals was as follows: 5mol of ethyl orthosilicate (1041 g), 1.25mol of tetrabutylammonium hydroxide (324 g) and 155mol of deionized water (2790 g) are added into a 10L polymerization reaction kettle, the mixture is stirred and pre-hydrolyzed for 15 hours at 35 ℃, then crystallized for 15 hours at 130 ℃, zeolite nanocrystalline is obtained after cooling to normal temperature, and finally 2wt% (calculated by the total mass of the ethyl orthosilicate and the tetrabutylammonium hydroxide, namely 27.3 g) of 3-aminopropyl triethoxysilane is added, the mixture is stirred for 2 hours at 35 ℃, and the amino zeolite nanocrystalline is obtained after vacuum drying.
Example 1 Low dielectric constant Nylon composite material and method for preparing 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 maleic anhydride in the maleic anhydride POE-g-MAH grafted by the ethylene and octene copolymer is 0.9 percent.
The preparation method of the low dielectric constant nylon composite material comprises the following steps:
(1) Adding the caprolactam subjected to vacuum drying into a stirring type polymerization reactor, and simultaneously adding the 2,2 '-bis (trifluoromethyl) diaminobiphenyl, adipic acid, amino zeolite nanocrystalline, ethylene and octene copolymer grafted maleic anhydride, benzoic acid, toluene diisocyanate, N' -bis (2, 6-tetramethyl-4-piperidinyl) -1, 3-benzenedicarboxamide, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate and a proper amount of water; then vacuumizing for 7min, introducing nitrogen for 7min, and circulating for 4 times, so that reactants exist in an environment under the protection of nitrogen, and controlling the system pressure in the stirring type polymerization reactor to be 0.4MPa;
(2) And (3) heating the stirring type polymerization reactor to 220 ℃ at a constant speed in a sealing manner within 4 hours, regulating 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 stirring type polymerization reactor is deflated to 1.7MPa, the pressure is maintained to be 1.7MPa, after the stirring type polymerization reactor reacts for 0.5 hour, the stirring type polymerization reactor is deflated to normal pressure, and is warmed to 250 ℃ at the same time, after the stirring type polymerization reactor continues to react for 0.5 hour at 250 ℃, the constant temperature is continuously vacuumized for 2 hours, the reaction is finished, and nitrogen is supplemented during discharging, so that the catalyst is obtained.
Example 2 Low dielectric constant Nylon composite material and method for preparing 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 maleic anhydride in the maleic anhydride POE-g-MAH grafted by the ethylene and octene copolymer is 1.5 percent.
The preparation method of the low dielectric constant nylon composite material comprises the following steps:
(1) Adding the caprolactam subjected to vacuum drying into a stirring type polymerization reactor, and simultaneously adding the 2,2 '-bis (trifluoromethyl) diaminobiphenyl, adipic acid, amino zeolite nanocrystalline, ethylene and octene copolymer grafted maleic anhydride, benzoic acid, toluene diisocyanate, N' -bis (2, 6-tetramethyl-4-piperidinyl) -1, 3-benzenedicarboxamide, 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 so that reactants exist in an environment under the protection of nitrogen, and controlling the system pressure in the stirring type polymerization reactor to be 0.1MPa;
(2) And heating the stirring type polymerization reactor to 215 ℃ at a constant speed in a closed manner within 2 hours, regulating 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 stirring type polymerization reactor is deflated to 1.7MPa, the pressure is maintained to be 1.7MPa, after the stirring type polymerization reactor reacts for 3 hours, the stirring type polymerization reactor is deflated to normal pressure, the temperature is raised to 240 ℃ at the same time, after the stirring type polymerization reactor continues to react for 3 hours at 240 ℃, the constant temperature is kept for vacuumizing for 0.1 hour, the reaction is finished, and nitrogen is supplemented during discharging, so that the nylon composite material with the low dielectric constant is obtained.
Example 3 Low dielectric constant Nylon composite material and method for preparing 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 maleic anhydride in the maleic anhydride POE-g-MAH grafted by the ethylene and octene copolymer is 1.5 percent.
The preparation method of the low dielectric constant nylon composite material comprises the following steps:
(1) Adding the caprolactam subjected to vacuum drying into a stirring type polymerization reactor, and simultaneously adding the 2,2 '-bis (trifluoromethyl) diaminobiphenyl, adipic acid, amino zeolite nanocrystalline, ethylene and octene copolymer grafted maleic anhydride, benzoic acid, toluene diisocyanate, N' -bis (2, 6-tetramethyl-4-piperidinyl) -1, 3-benzenedicarboxamide, 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 so that reactants exist in an environment under the protection of nitrogen, and controlling the system pressure in the stirring type polymerization reactor to be 0.3MPa;
(2) And heating the stirring type polymerization reactor to 220 ℃ at a constant speed in a closed manner within 4 hours, regulating 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 stirring type polymerization reactor is deflated to 1.7MPa, the pressure is maintained to be 1.7MPa, after the stirring type polymerization reactor reacts for 1 hour, the stirring type polymerization reactor is deflated to normal pressure, and is simultaneously warmed to 250 ℃, after the stirring type polymerization reactor continues to react for 1 hour at 250 ℃, the constant temperature is kept for vacuumizing for 1.5 hours, and after the reaction, nitrogen is supplemented during discharging, so that the nylon composite material with the low dielectric constant is obtained.
Example 4 Low dielectric constant Nylon composite material and method for preparing 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 maleic anhydride in the maleic anhydride POE-g-MAH grafted by the ethylene and octene copolymer is 1.5 percent.
The preparation method of the low dielectric constant nylon composite material comprises the following steps:
(1) Adding the caprolactam subjected to vacuum drying into a stirring type polymerization reactor, and simultaneously adding the 2,2 '-bis (trifluoromethyl) diaminobiphenyl, adipic acid, amino zeolite nanocrystalline, ethylene and octene copolymer grafted maleic anhydride, benzoic acid, toluene diisocyanate, N' -bis (2, 6-tetramethyl-4-piperidinyl) -1, 3-benzenedicarboxamide, 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, so that reactants exist in an environment under the protection of nitrogen, and controlling the system pressure in the stirring type polymerization reactor to be 0.2MPa;
(2) And heating the stirring type polymerization reactor to 215 ℃ at a constant speed in a closed manner within 2 hours, regulating 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 stirring type polymerization reactor is deflated to 1.7MPa, the pressure is maintained to be 1.7MPa, after the stirring type polymerization reactor reacts for 2 hours, the stirring type polymerization reactor is deflated to normal pressure, the temperature is raised to 240 ℃ at the same time, after the stirring type polymerization reactor continues to react for 2 hours at 240 ℃, the constant temperature is kept for vacuumizing for 0.5 hour, the reaction is finished, and nitrogen is supplemented during discharging, so that the nylon composite material with the low dielectric constant is obtained.
Example 5 Low dielectric constant Nylon composite material and method for preparing 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 maleic anhydride in the maleic anhydride POE-g-MAH grafted by the ethylene and octene copolymer is 1.5 percent.
The preparation method of the low dielectric constant nylon composite material comprises the following steps:
(1) Adding the caprolactam subjected to vacuum drying into a stirring type polymerization reactor, and simultaneously adding the 2,2 '-bis (trifluoromethyl) diaminobiphenyl, adipic acid, amino zeolite nanocrystalline, ethylene and octene copolymer grafted maleic anhydride, benzoic acid, toluene diisocyanate, N' -bis (2, 6-tetramethyl-4-piperidinyl) -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 so that reactants exist in an environment under the protection of nitrogen, and controlling the system pressure in the stirring type polymerization reactor to be 0.25MPa;
(2) And (3) heating the stirring type polymerization reactor to 218 ℃ at a constant speed in a sealing manner within 3 hours, regulating 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 stirring type polymerization reactor is deflated to 1.7MPa, the pressure is maintained to be 1.7MPa, after the stirring type polymerization reactor reacts for 1.5 hours, the stirring type polymerization reactor is deflated to normal pressure, the stirring type polymerization reactor is simultaneously warmed to 245 ℃, after the stirring type polymerization reactor continuously reacts for 1.5 hours at 245 ℃, the constant temperature is continuously vacuumized for 1 hour, the reaction is finished, and nitrogen is supplemented during discharging, so that the nylon composite material with the low dielectric constant is obtained.
Example 6 Low dielectric constant Nylon composite material and method for preparing 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 maleic anhydride in the maleic anhydride POE-g-MAH grafted by the ethylene and octene copolymer is 1.5 percent.
The preparation method of the low dielectric constant nylon composite material comprises the following steps:
(1) Adding the caprolactam subjected to vacuum drying into a stirring type polymerization reactor, and simultaneously adding the 2,2 '-bis (trifluoromethyl) diaminobiphenyl, adipic acid, amino zeolite nanocrystalline, ethylene and octene copolymer grafted maleic anhydride, benzoic acid, toluene diisocyanate, N' -bis (2, 6-tetramethyl-4-piperidinyl) -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 so that reactants exist in an environment under the protection of nitrogen, and controlling the system pressure in the stirring type polymerization reactor to be 0.25MPa;
(2) And (3) heating the stirring type polymerization reactor to 218 ℃ at a constant speed in a sealing manner within 3 hours, regulating 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 stirring type polymerization reactor is deflated to 1.7MPa, the pressure is maintained to be 1.7MPa, after the stirring type polymerization reactor reacts for 1.5 hours, the stirring type polymerization reactor is deflated to normal pressure, the stirring type polymerization reactor is simultaneously warmed to 245 ℃, after the stirring type polymerization reactor continuously reacts for 1.5 hours at 245 ℃, the constant temperature is continuously vacuumized for 1 hour, the reaction is finished, and nitrogen is supplemented during discharging, so that the nylon composite material with the low dielectric constant is obtained.
Example 7 Low dielectric constant Nylon composite material and method for preparing 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 maleic anhydride in the maleic anhydride POE-g-MAH grafted by the ethylene and octene copolymer is 1.5 percent.
The preparation method of the low dielectric constant nylon composite material comprises the following steps:
(1) Adding the caprolactam subjected to vacuum drying into a stirring type polymerization reactor, and simultaneously adding the 2,2 '-bis (trifluoromethyl) diaminobiphenyl, adipic acid, amino zeolite nanocrystalline, ethylene and octene copolymer grafted maleic anhydride, benzoic acid, toluene diisocyanate, N' -bis (2, 6-tetramethyl-4-piperidinyl) -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 so that reactants exist in an environment under the protection of nitrogen, and controlling the system pressure in the stirring type polymerization reactor to be 0.25MPa;
(2) And (3) heating the stirring type polymerization reactor to 218 ℃ at a constant speed in a sealing manner within 3 hours, regulating 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 stirring type polymerization reactor is deflated to 1.7MPa, the pressure is maintained to be 1.7MPa, after the stirring type polymerization reactor reacts for 1.5 hours, the stirring type polymerization reactor is deflated to normal pressure, the stirring type polymerization reactor is simultaneously warmed to 245 ℃, after the stirring type polymerization reactor continuously reacts for 1.5 hours at 245 ℃, the constant temperature is continuously vacuumized for 1 hour, the reaction is finished, and nitrogen is supplemented during discharging, so that the nylon composite material with the low dielectric constant is obtained.
Comparative example 1
The nylon composite material with the low dielectric constant is prepared from the following raw materials in parts by weight:
wherein, the grafting rate of maleic anhydride in the maleic anhydride POE-g-MAH grafted by the ethylene and octene copolymer is 1.5 percent.
The preparation method of the low dielectric constant nylon composite material comprises the following steps:
(1) Adding the caprolactam subjected to 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, 6-tetramethyl-4-piperidinyl) -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 so that reactants exist in an environment under the protection of nitrogen, and controlling the system pressure in the stirring type polymerization reactor to be 0.25MPa;
(2) And (3) heating the stirring type polymerization reactor to 218 ℃ at a constant speed in a sealing manner within 3 hours, regulating 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 stirring type polymerization reactor is deflated to 1.7MPa, the pressure is maintained to be 1.7MPa, after the stirring type polymerization reactor reacts for 1.5 hours, the stirring type polymerization reactor is deflated to normal pressure, the stirring type polymerization reactor is simultaneously warmed to 245 ℃, after the stirring type polymerization reactor continuously reacts for 1.5 hours at 245 ℃, the constant temperature is continuously vacuumized for 1 hour, the reaction is finished, and nitrogen is supplemented during discharging, so that the nylon composite material with the low dielectric constant is obtained.
Comparative example 2
The nylon composite material with the low dielectric constant is prepared from the following raw materials in parts by weight:
wherein, the grafting rate of maleic anhydride in the maleic anhydride POE-g-MAH grafted by the ethylene and octene copolymer is 1.5 percent.
The preparation method of the low dielectric constant nylon composite material comprises the following steps:
(1) Adding the caprolactam subjected to 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, 6-tetramethyl-4-piperidinyl) -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 so that reactants exist in an environment under the protection of nitrogen, and controlling the system pressure in the stirring type polymerization reactor to be 0.25MPa;
(2) And (3) heating the stirring type polymerization reactor to 218 ℃ at a constant speed in a sealing manner within 3 hours, regulating 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 stirring type polymerization reactor is deflated to 1.7MPa, the pressure is maintained to be 1.7MPa, after the stirring type polymerization reactor reacts for 1.5 hours, the stirring type polymerization reactor is deflated to normal pressure, the stirring type polymerization reactor is simultaneously warmed to 245 ℃, after the stirring type polymerization reactor continuously reacts for 1.5 hours at 245 ℃, the constant temperature is continuously vacuumized for 1 hour, the reaction is finished, and nitrogen is supplemented during discharging, so that the nylon composite material with the low dielectric constant is obtained.
Comparative example 3
The nylon composite material with the low dielectric constant 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 subjected to vacuum drying into a stirring type polymerization reactor, and simultaneously adding the 2,2 '-bis (trifluoromethyl) diaminobiphenyl, adipic acid, amino zeolite nanocrystalline, benzoic acid, toluene diisocyanate, N' -bis (2, 6-tetramethyl-4-piperidinyl) -1, 3-phthalamide, 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 so that reactants exist in an environment under the protection of nitrogen, and controlling the system pressure in the stirring type polymerization reactor to be 0.25MPa;
(2) And (3) heating the stirring type polymerization reactor to 218 ℃ at a constant speed in a sealing manner within 3 hours, regulating 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 stirring type polymerization reactor is deflated to 1.7MPa, the pressure is maintained to be 1.7MPa, after the stirring type polymerization reactor reacts for 1.5 hours, the stirring type polymerization reactor is deflated to normal pressure, the stirring type polymerization reactor is simultaneously warmed to 245 ℃, after the stirring type polymerization reactor continuously reacts for 1.5 hours at 245 ℃, the constant temperature is continuously vacuumized for 1 hour, the reaction is finished, and nitrogen is supplemented during discharging, so that the nylon composite material with the low dielectric constant is obtained.
Comparative example 4
The nylon composite material with the low dielectric constant is prepared from the following raw materials in parts by weight:
wherein, the grafting rate of maleic anhydride in the maleic anhydride POE-g-MAH grafted by the ethylene and octene copolymer is 1.5 percent.
The preparation method of the low dielectric constant nylon composite material comprises the following steps:
(1) Adding the caprolactam subjected to vacuum drying into a stirring type polymerization reactor, and simultaneously adding the 2,2 '-bis (trifluoromethyl) diaminobiphenyl, adipic acid, amino zeolite nanocrystalline, ethylene and octene copolymer grafted maleic anhydride, toluene diisocyanate, N' -bis (2, 6-tetramethyl-4-piperidinyl) -1, 3-benzene dicarboxamide, 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 so that reactants exist in an environment under the protection of nitrogen, and controlling the system pressure in the stirring type polymerization reactor to be 0.25MPa;
(2) And (3) heating the stirring type polymerization reactor to 218 ℃ at a constant speed in a sealing manner within 3 hours, regulating 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 stirring type polymerization reactor is deflated to 1.7MPa, the pressure is maintained to be 1.7MPa, after the stirring type polymerization reactor reacts for 1.5 hours, the stirring type polymerization reactor is deflated to normal pressure, the stirring type polymerization reactor is simultaneously warmed to 245 ℃, after the stirring type polymerization reactor continuously reacts for 1.5 hours at 245 ℃, the constant temperature is continuously vacuumized for 1 hour, the reaction is finished, and nitrogen is supplemented during discharging, so that the nylon composite material with the low dielectric constant is obtained.
Comparative example 5
The nylon composite material with the low dielectric constant is prepared from the following raw materials in parts by weight:
wherein, the grafting rate of maleic anhydride in the maleic anhydride POE-g-MAH grafted by the ethylene and octene copolymer is 1.5 percent.
The preparation method of the low dielectric constant nylon composite material comprises the following steps:
(1) Adding the caprolactam subjected to vacuum drying into a stirring type polymerization reactor, and simultaneously adding the 2,2 '-bis (trifluoromethyl) diaminobiphenyl, adipic acid, amino zeolite nanocrystalline, ethylene and octene copolymer grafted maleic anhydride, benzoic acid, N' -bis (2, 6-tetramethyl-4-piperidinyl) -1, 3-phthalamide, 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 so that reactants exist in an environment under the protection of nitrogen, and controlling the system pressure in the stirring type polymerization reactor to be 0.25MPa;
(2) And (3) heating the stirring type polymerization reactor to 218 ℃ at a constant speed in a sealing manner within 3 hours, regulating 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 stirring type polymerization reactor is deflated to 1.7MPa, the pressure is maintained to be 1.7MPa, after the stirring type polymerization reactor reacts for 1.5 hours, the stirring type polymerization reactor is deflated to normal pressure, the stirring type polymerization reactor is simultaneously warmed to 245 ℃, after the stirring type polymerization reactor continuously reacts for 1.5 hours at 245 ℃, the constant temperature is continuously vacuumized for 1 hour, the reaction is finished, and nitrogen is supplemented during discharging, so that the nylon composite material with the low dielectric constant is obtained.
Comparative example 6
The nylon composite material with the low dielectric constant is prepared from the following raw materials in parts by weight:
wherein, the grafting rate of maleic anhydride in the maleic anhydride POE-g-MAH grafted by the ethylene and octene copolymer 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 110 ℃ for 3 hours, cooling, and placing the cooled polyamide 6 for later use;
(2) Adding the amino zeolite nanocrystalline, ethylene and octene copolymer grafted maleic anhydride, toluene diisocyanate, N' -bis (2, 6-tetramethyl-4-piperidinyl) -1, 3-benzene dicarboxamide and bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate into another high-speed stirrer (with the rotating speed of 1000 rpm) for mixing;
(3) Feeding the polyamide 6 dried in the step (1) into a parallel double-screw extruder through a feeder, and adding the mixture mixed in the step (2) into the side direction (fourth zone) of the parallel double-screw extruder (total eight zones) for melt extrusion, and granulating, wherein the technological parameters are as follows: the first zone temperature is 210 ℃, the second zone temperature is 220 ℃, the third zone temperature is 225 ℃, the fourth zone temperature is 230 ℃, the fifth zone temperature is 230 ℃, the sixth zone temperature is 230 ℃, the seventh zone temperature is 230 ℃, the eighth zone temperature is 230 ℃, the die temperature is 225 ℃, and the screw rotating speed is 400rpm.
The following is a list of the raw material compositions of examples 1-7 and comparative examples 1-6.
Table 1 list of raw material compositions of examples 1 to 7 and comparative examples 1 to 6
Remarks: a, replacing the amino zeolite nanocrystalline with common zeolite (prepared by a sol-gel method); b, caprolactam is replaced by polyamide 6.
Wherein, the addition amount of N, N' -bis (2, 6-tetramethyl-4-piperidyl) -1, 3-benzene dicarboxamide (main antioxidant) and bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate (auxiliary antioxidant) of the above examples and comparative examples is 0.2 part.
Examples 1 to 7 were prepared by adjusting the addition amounts of 2,2' -bis (trifluoromethyl) diaminobiphenyl, adipic acid, aminozeolite nanocrystals, ethylene-octene copolymer grafted maleic anhydride (POE-g-MAH), benzoic acid, toluene diisocyanate, and low dielectric constant nylon composites, and comparative examples 1 to 6 were prepared by changing the aminozeolite nanocrystals to normal zeolite, ethylene-octene copolymer grafted maleic anhydride (POE-g-MAH), benzoic acid, toluene diisocyanate, and caprolactam to polyamide 6 resin based on 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 properties: the stretching rate was 50mm/min as tested according to GB/T1040-2006 standard.
Notched impact properties: tested according to GB/T1843-2008 standard.
Melt index: the test is carried out according to GB/T3682-2000 standard, the test temperature is 250 ℃, and the load is 2.16kg.
Balance water absorption: the test temperature was 25℃according to GB/T1034-2008 standard.
Dielectric constant: the test frequency was 5GHz according to GB/T5597-1999 standard test.
Intrinsic viscosity: according to GB/T1632-2008 standard test, the solvent is concentrated sulfuric acid.
Melting temperature: tested according to GB/T19466.3-2004 standard.
The results of the performance test are shown in Table 2.
Table 2 performance tables of low dielectric constant nylon composites of examples 1-7 and comparative examples 1-6
As can be seen from table 2:
with the increasing of the addition amount of 2,2' -di (trifluoromethyl) diaminobiphenyl, adipic acid, benzoic acid, amino zeolite nanocrystals, ethylene and octene copolymer grafted maleic anhydride (POE-g-MAH), the tensile strength and melt index of the low dielectric constant nylon composite material show a change trend of increasing and decreasing after increasing, which is mainly influenced by multiple factors: (1) 2,2' -di (trifluoromethyl) diaminobiphenyl contains rigid benzene ring structural units, so that the tensile strength of the material can be improved, but the relative movement of molecular chains can be blocked, and the melt index of the material is reduced; (2) Benzoic acid affects the intrinsic viscosity of the nylon composite material, and the lower the benzoic acid is, the higher the viscosity of the benzoic acid is, the higher the tensile strength of the nylon composite material is, and the lower the melt index of the nylon composite material is; (3) The amino zeolite nanocrystalline is a high-crystallinity porous SiO with micropores with uniform molecular size inside 2 The polymer has a reinforcing effect on the polymer, so that the tensile strength of the material can be improved; (4) The ethylene and octene copolymer grafted maleic anhydride (POE-g-MAH) has lower tensile strength and poorer fluidity, and has adverse effect on the tensile strength and melt index of the composite materialAnd (5) sounding. Under the influence of the common factors, when the addition amount of 2,2' -di (trifluoromethyl) diaminobiphenyl, adipic acid, benzoic acid, amino zeolite nanocrystalline and ethylene-octene copolymer grafted maleic anhydride (POE-g-MAH) is small, the influence of benzene ring on the tensile strength of the composite material is higher than that of other factors, and the influence of the intrinsic viscosity on the melt index of the composite material is higher than that of other factors; when the addition amount of 2,2' -di (trifluoromethyl) diaminobiphenyl, adipic acid, benzoic acid, amino zeolite nanocrystalline 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 benzene rings on the melt index of the composite material is higher than that of other factors.
With the reduction of the addition amount of the grafted maleic anhydride (POE-g-MAH) of the ethylene and octene copolymer, the notch impact performance of the composite material shows a reduced change trend, because the intervention of octene in a POE molecular chain damages the crystallization of part of polyethylene, the octene chain segment and the polyethylene chain segment with the destroyed crystallization jointly form an elastic soft segment, the crystallization part of the polyethylene forms a hard segment and plays a role of a physical crosslinking point, so that the POE has the property of an elastomer, and the addition amount of the POE-g-MAH is reduced, so that the capability of absorbing external impact is reduced when the composite material is impacted by external force, and the notch impact performance of the composite material is reduced.
With the increase of the addition amount of the 2,2' -di (trifluoromethyl) diaminobiphenyl, the water absorption rate of the 2,2' -di (trifluoromethyl) diaminobiphenyl shows a reduced change trend, and the melting temperature of the 2,2' -di (trifluoromethyl) diaminobiphenyl shows a raised change trend, because the more structural units of the 2,2' -di (trifluoromethyl) diaminobiphenyl are, the density of amide groups can be reduced, so that the water absorption rate is reduced, and the rigid benzene ring structural units in the 2,2' -di (trifluoromethyl) diaminobiphenyl prevent the relative sliding among molecular chains of the composite material, so that the composite material can slide at a higher temperature, and the melting temperature is improved.
As the addition amount of 2,2 '-bis (trifluoromethyl) diaminobiphenyl and the amino zeolite nanocrystals increases, the dielectric constant of the nylon composite material shows a decreasing trend of change because 2,2' -bis (trifluoromethyl) diaminobiphenyl contains fluorineThe element atoms, because the fluorine element atoms have strong attraction to the extra-nuclear electrons, the interaction force between the electrons and atomic nuclei is large, the electron cloud density is high, the polarization rate is low when the electrons are polarized by an external electric field, meanwhile, the fluorine-containing groups with larger volume are introduced into polymer molecules, the stacking density of the polymer can be reduced, the free volume of the polymer is increased, the dielectric constant of the polymer material is reduced, and the zeolite nanocrystalline is a high-crystallinity porous SiO with uniform molecular size micropores inside 2 Has extremely low theoretical dielectric constant (about 1.60), and can effectively reduce the dielectric constant of the nylon composite material under the combined action of 2,2' -di (trifluoromethyl) diaminobiphenyl and amino zeolite nanocrystalline.
Along with the reduction of the addition amount of the benzoic acid, the intrinsic viscosity of the nylon composite material shows an increasing change trend, because the monofunctional benzoic acid plays a role of a polymerization inhibitor, the intrinsic viscosity of the nylon composite material is effectively regulated, the processability is influenced when the intrinsic viscosity of the nylon composite material is too high, the mechanical properties are influenced when the intrinsic viscosity of the nylon composite material is too low, and therefore the nylon composite material with excellent mechanical properties and processability can be obtained only by the proper intrinsic viscosity.
In summary, by adjusting the addition amounts of 2,2' -di (trifluoromethyl) diaminobiphenyl, adipic acid, amino zeolite nanocrystals, ethylene and octene copolymer grafted maleic anhydride (POE-g-MAH), benzoic acid and toluene diisocyanate, under the synergistic cooperation of the auxiliary agents, the nylon composite material with low dielectric constant and excellent mechanical properties and processability can be obtained, wherein the nylon composite material prepared in example 7 has the best comprehensive properties.
In example 7, compared with comparative example 1, comparative example 1 was free of the addition of the amino zeolite nanocrystals, and the dielectric constant of comparative example 1 was higher than that of example 7 because the amino zeolite nanocrystals had a porous structure and the dielectric constant was about 1.6.
Example 7 compared with comparative example 2, comparative example 2 uses a general zeolite prepared by a sol-gel method, which has strong hydrophilicity, poor compatibility with nylon materials, and inferior mechanical properties to amino zeolite nanocrystals, so that the nylon composite prepared in comparative example 2 has lower tensile strength and notch impact properties than example 7, and has a higher dielectric constant than example 7.
Example 7 compared with comparative example 3, comparative example 3 was free of POE-g-MAH, since POE-g-MAH has very high notched impact property, its maleic anhydride group can react with terminal amino group of nylon material, interfacial adhesion and compatibility between the two were previously enhanced, and POE-g-MAH has lower dielectric constant (Dk of 2.4, test frequency of 5 GHz), thus the notched impact property of the nylon composite material prepared in comparative example 3 was lower than that of example 7, but the dielectric constant was higher than that of example 7.
In example 7, compared with comparative example 4, no benzoic acid was added in comparative example 4, and the melt index of comparative example 4 was much lower than that of example 7 because the monofunctional benzoic acid acts as a polymerization inhibitor, thereby effectively adjusting the intrinsic viscosity of the nylon composite, which is too high to affect the processability.
Example 7 compared with comparative example 5, comparative example 5 was free of toluene diisocyanate, and the tensile strength and notched impact strength of the nylon composite material prepared in comparative example 5 were lower than those of example 7 because the isocyanate group of toluene diisocyanate can react with the terminal groups of nylon and the terminal amino groups of the amino zeolite nanocrystals, thereby improving the compatibility therebetween.
Example 7 in comparison with comparative example 6, comparative example 6 was prepared by a general blending method using a polyamide 6 resin to obtain a low dielectric constant nylon composite material, and since the polyamide 6 resin of the general type has a high density of amide bonds, and lacks a rigid benzene ring and a fluorine-containing side group in the nylon structure of example 7, it is easy to absorb water vapor in daily use, its 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), the dielectric constant of comparative example 6 is higher than that of example 7.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (9)
1. The nylon composite material with the low dielectric constant is characterized by being prepared from the following raw materials in parts by weight:
caprolactam 100 parts
10.95 to 32.85 portions of 2,2' -bis (trifluoromethyl) diaminobiphenyl
Adipic acid 5-15 parts
5 to 15 portions of amino zeolite nanocrystalline
1 to 7 parts of maleic anhydride grafted by ethylene and octene copolymer
0.01 to 1 part of benzoic acid
Toluene diisocyanate 0.1-2 parts
0.1 to 0.6 part of antioxidant;
the 2,2' -bis (trifluoromethyl) diaminobiphenyl and adipic acid are in an equimolar ratio;
the amino zeolite nanocrystalline is obtained by organizing zeolite nanocrystalline by 3-aminopropyl triethoxysilane; the zeolite nanocrystalline is prepared from tetraethoxysilane and tetrabutylammonium hydroxide; the preparation method of the amino zeolite nanocrystalline comprises the following steps: tetraethyl orthosilicate, tetrabutyl ammonium hydroxide and deionized water are mixed according to a mole ratio of 1:0.1 to 0.4:13 to 50 are added into a polymerization reaction kettle, stirred and pre-hydrolyzed for 10 to 20 hours at the temperature of between 30 and 40 ℃, then crystallized for 10 to 20 hours at the temperature of between 110 and 150 ℃ and cooled to normal temperature to obtain zeolite nanocrystalline, and finally 3-aminopropyl triethoxysilane accounting for 1 to 3 weight percent of the total mass of the tetraethoxysilane and the tetrabutylammonium hydroxide is added, stirred for 0.5 to 3.5 hours at the temperature of between 30 and 40 ℃ and dried in vacuum to obtain the catalyst;
the preparation method of the low dielectric constant nylon composite material comprises the following steps:
(1) Adding the caprolactam subjected to vacuum drying into a stirring type polymerization reactor, and simultaneously adding 2,2' -di (trifluoromethyl) diaminobiphenyl, adipic acid, amino zeolite nanocrystalline, ethylene and 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, and circulating for 4-8 times, wherein the system pressure in the stirring type polymerization reactor is controlled to be 0.1-0.4 MPa;
(2) Regulating the stirring speed of the stirring type polymerization reactor to be 30-50 r/min, heating the stirring type polymerization reactor to 215-220 ℃ in a sealed and uniform manner within 2-4 hours, deflating to 1.7MPa when the temperature of the stirring type polymerization reactor reaches 215 ℃, maintaining the pressure at 1.7MPa, reacting for 0.5-3 hours, deflating to normal pressure, simultaneously heating to 240-250 ℃, continuously reacting for 0.5-3 hours at 240-250 ℃, continuously vacuumizing for 0.1-2 hours at constant temperature, finishing the reaction, and supplementing nitrogen when discharging to obtain the catalyst.
2. The low dielectric constant nylon composite material according to claim 1, which is characterized by being prepared from the following raw materials in parts by weight:
Caprolactam 100 parts
15.33 to 28.47 portions of 2,2' -bis (trifluoromethyl) diaminobiphenyl
Adipic acid 7-13 parts
7 to 13 portions of amino zeolite nanocrystalline
2-6 parts of maleic anhydride grafted by ethylene and octene copolymer
0.3 to 0.8 part of benzoic acid
Toluene diisocyanate 0.3-1.8 parts
0.2 to 0.5 part of antioxidant.
3. The low dielectric constant nylon composite material according to claim 2, which is characterized by being prepared from the following raw materials in parts by weight:
caprolactam 100 parts
19.71 to 24.09 parts of 2,2' -bis (trifluoromethyl) diaminobiphenyl
9 to 11 portions of adipic acid
9-11 parts of amino zeolite nanocrystalline
3-5 parts of maleic anhydride grafted by ethylene and octene copolymer
0.4 to 0.6 part of benzoic acid
Toluene diisocyanate 0.5-1.5 parts
0.3 to 0.5 part of antioxidant.
4. A low dielectric constant nylon composite as claimed in any one of claims 1 to 3, wherein the low dielectric constant nylon composite 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 of any one of claims 1-3, wherein the maleic anhydride grafting ratio of the ethylene and octene copolymer grafted maleic anhydride is 0.8% -2.2%.
6. The low dielectric constant nylon composite according to any one of claim 1 to 3, wherein,
the antioxidant comprises a main antioxidant and an auxiliary antioxidant; the main antioxidant is one or more of pentaerythritol tetra (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate), N '-1, 6-hexamethylene-bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionamide ], and N, N' -bis (2, 6-tetramethyl-4-piperidyl) -1, 3-benzene dicarboxamide; the auxiliary antioxidant is one or more of tri (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.
7. The method for preparing the low dielectric constant nylon composite material according to any one of claims 1 to 6, which is characterized by comprising the following steps:
(1) Adding the caprolactam subjected to vacuum drying into a stirring type polymerization reactor, and simultaneously adding 2,2' -di (trifluoromethyl) diaminobiphenyl, adipic acid, amino zeolite nanocrystalline, ethylene and 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, and circulating for 4-8 times, wherein the system pressure in the stirring type polymerization reactor is controlled to be 0.1-0.4 MPa;
(2) Regulating the stirring speed of the stirring type polymerization reactor to be 30-50 r/min, heating the stirring type polymerization reactor to 215-220 ℃ in a sealed and uniform manner within 2-4 hours, deflating to 1.7MPa when the temperature of the stirring type polymerization reactor reaches 215 ℃, maintaining the pressure at 1.7MPa, reacting for 0.5-3 hours, deflating to normal pressure, simultaneously heating to 240-250 ℃, continuously reacting for 0.5-3 hours at 240-250 ℃, continuously vacuumizing for 0.1-2 hours at constant temperature, finishing the reaction, and supplementing nitrogen when discharging to obtain the catalyst.
8. The method for preparing a nylon composite material with a low dielectric constant according to claim 7, wherein the vacuumizing time in the step (1) is 4-6 min, the nitrogen introducing time is 4-6 min, the steps are repeated for 5-7 times, and the system pressure in the stirring type polymerization reactor is controlled to be 0.2-0.3 MPa.
9. The method for preparing a nylon composite material with low dielectric constant according to claim 7, wherein the reaction is continued for 1 to 2 hours at 240 to 250 ℃ when the temperature in the step (2) reaches 215 ℃, and the constant temperature is continuously vacuumized for 0.5 to 1.5 hours.
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