CN111675900A - Low-dielectric-constant glass fiber reinforced nylon composite material and preparation method thereof - Google Patents

Low-dielectric-constant glass fiber reinforced nylon composite material and preparation method thereof Download PDF

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Publication number
CN111675900A
CN111675900A CN202010724060.3A CN202010724060A CN111675900A CN 111675900 A CN111675900 A CN 111675900A CN 202010724060 A CN202010724060 A CN 202010724060A CN 111675900 A CN111675900 A CN 111675900A
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glass fiber
antioxidant
composite material
fiber reinforced
reinforced nylon
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廖正福
陈庆华
陈征
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Guangdong University of Technology
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Guangdong University of Technology
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Priority to CN202010724060.3A priority Critical patent/CN111675900A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
    • C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2400/00—Characterised by the use of unspecified polymers
    • C08J2400/20—Polymers characterized by their physical structure
    • C08J2400/202—Dendritic macromolecules, e.g. dendrimers or hyperbranched polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2477/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
    • C08J2483/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
    • C08J2483/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen

Abstract

The invention relates to the technical field of nylon materials, in particular to a glass fiber reinforced nylon composite material with a low dielectric constant and a preparation method thereof. The invention discloses a glass fiber reinforced nylon composite material with low dielectric constant, wherein in the composite material, 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 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. The composite material has excellent rigidity and toughness, has low dielectric constant, can be applied to the field of high-frequency communication, has excellent fluidity and can meet the injection molding requirement of thin-wall products.

Description

Low-dielectric-constant glass fiber reinforced nylon composite material and preparation method thereof
Technical Field
The invention relates to the technical field of nylon materials, in particular to a glass fiber reinforced nylon composite material with a low dielectric constant and a preparation method thereof.
Background
Engineering plastics generally have excellent mechanical strength, high temperature resistance, corrosion resistance and abrasion resistance, are easy to process, and often replace metals to manufacture mechanical parts. The thermoplastic engineering material comprises polyamide, polyester, ABS, polyformaldehyde, polycarbonate and other materials, and is widely applied to the industries of electronics, electrics, automobiles, buildings, office equipment, machinery, aerospace and the like. In recent years, the feature size of integrated circuits (especially high frequency circuits) is gradually reduced, and resistance, capacitance-induced delay, crosstalk and power consumption of interconnection parasitics become bottleneck problems to be solved for developing high-speed, high-density, low-power consumption and multifunctional integrated circuits, so that the requirements on the electrical and thermal properties of materials are more stringent, and the requirements on low-dielectric-constant and low-loss materials are more and more urgent.
The thermoplastic high molecular polymer polyamide, commonly called nylon, has excellent mechanical property, chemical resistance, good electrical property, self-lubricating property and wide application. With the advent of the era of high-frequency communications (the era of 5G and 6G), the dielectric constant of plastic materials for communications equipment has received considerable attention as to signal loss. The material with low dielectric constant has less damage to signals and better meets the performance requirement of high-frequency communication on the material. However, the dielectric constant of the plastic materials frequently used at present is large (about greater than 4), and the signal loss is also large, so that the dielectric constant of the materials is urgently needed to be reduced.
Disclosure of Invention
The invention provides a glass fiber reinforced nylon composite material with a low dielectric constant and a preparation method thereof, which solve the problem of large dielectric constant of the existing nylon material.
The specific technical scheme is as follows:
the invention provides a low-dielectric-constant glass fiber reinforced nylon composite material which is prepared from the following components in parts by weight:
PA 6660-80 shares;
20-40 parts of glass fiber;
1-5 parts of functionalized POSS;
0.1-0.5 part of flow modifier;
0.2-3 parts of antioxidant;
0.5-2 parts of light stabilizer;
0.3-1 part of lubricant.
In the invention, 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 net structure with multiple cavities, and the composite material with a special structure has a low dielectric constant so as to meet the requirement of high-frequency communication electronics on the dielectric constant of the material; 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 can be suitable for outdoor high-temperature occasions. The composite material has excellent rigidity and toughness, can be applied to various high-frequency communication fields, has excellent fluidity and can meet the injection molding requirement of thin-wall products.
In the invention, the PA66 is composed of a new material PA66 and a reclaimed material, and the preparation cost of the composite material can be properly reduced by adding the reclaimed PA 66. Wherein the melt index of the new material PA66 is 230 ℃ and 2.16kg load is 25-65g/10 min; PA66 reclaimed material: 2 to 10 percent of ash content and 5 to 30g/10min of 2.16kg load with the melt index of 230 ℃.
In the present invention, the antioxidant includes: antioxidant A and antioxidant B;
the antioxidant A is one or more than two of antioxidant 1098, antioxidant 1010, antioxidant 1076, antioxidant 1024, antioxidant 264, antioxidant 3125, antioxidant 3114 and antioxidant KY-586;
the antioxidant B is bis (3, 5-di-tert-butylphenyl) pentaerythritol diphosphite, tris (2, 4-di-tert-butylphenyl) phosphite, ethyl 2-methyl-4, 6- (1,1 '-dimethylethyl) phenol ] phosphate, tetrakis (2, 4-di-tert-butyloctaalkoxy-4, 4-biphenyl) phosphate, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, (2,4, 6-tri-tert-butylphenyl, 2-butyl-2-ethyl) -1, 3-propanediol phosphite, bis (2, 4-di-p-isopropylphenyl) pentaerythritol diphosphite, 2' -ethylenebis (4, 6-di-tert-butylphenyl) fluorophosphite and tetrakis (2, 4-di-tert-butylphenyl-4, 4-biphenylyl) bisphosphate.
The antioxidant A and the antioxidant B are compounded with the light stabilizer, so that the photo-thermal stability of the composite material is further improved, and the antioxidant effect and the antioxidant cost are considered.
In the invention, the mass ratio of the antioxidant A to the antioxidant B is 1: (1 to 10), preferably 1: (5-6).
In the invention, the glass fiber is alkali-free glass fiber. The glass fiber mainly has the function of mechanical reinforcement, and the alkali-free glass fiber has better effects of corrosion resistance, electrical insulation, mechanical reinforcement and the like than common glass fiber.
The preparation method of the alkali-free glass fiber comprises the following steps:
and (3) placing the glass fiber in a silane coupling agent solution for hydrolysis condensation reaction to obtain the alkali-free glass fiber. The silane coupling agent is a KH series silane coupling agent, preferably KH-550, KH-560, KH-570, KH580, KH590 or KH 602; the time of the hydrolysis condensation reaction is 10-30 hours, and preferably 20 hours.
After the surface of the glass fiber is treated, the compatibility of the glass fiber and matrix resin is increased, and meanwhile, the treated surface of the glass fiber has structural defects POSS formed by hydrolysis and condensation of a silane coupling agent, so that the dielectric constant of the composite material is further reduced.
In the invention, the lubricant is a silicone lubricant, more preferably KJ silicone lubricant KJ-A103, the silicone lubricant contains 30-80% by mass of siloxane, preferably 55-75% by mass of siloxane, and the silicone lubricant and the glass fiber after surface treatment are used together to enhance the comprehensive mechanical property of the composite material;
the light stabilizer is tris (1,2,2,6, 6-pentamethyl-4-hydroxypiperidine) phosphite, benzoic acid (2,2,6, 6-tetramethyl-4-hydroxypiperidine) ester, N-bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 6-hexanediamine, N-allyltetramethylpiperidinol, bis (1-octyloxy-2, 2,6, 6-tetramethyl-4-piperidyl) sebacate and 1,5,8, 12-tetrakis [4, 6-bis (N-butyl-N-1, 2,2,6, 6-pentamethyl-4-piperidylamino) -1,3, 5-triazin-2-yl ] -1, one or more than two of 5,8, 12-tetraazadodecane;
the functionalized POSS is one or more than two of amino POSS monomer, carboxylic group POSS monomer, epoxy group POSS monomer and hydroxyl POSS monomer, and the number of functional group substitution in the functionalized POSS is 2-8, preferably 4-6;
the flow modifier is CYD 701C, and the CYD 701C is a special dendritic polymer for nylon resin, so that the resin flowability can be effectively improved, the processing performance is improved, and the thickness uniformity and the size accuracy of a product are improved.
The invention also provides a preparation method of the glass fiber reinforced nylon composite material with the low dielectric constant, which comprises the following steps:
and melting and blending the PA66, the glass fiber, the functionalized POSS, the flow modifier, the antioxidant, the light stabilizer and the lubricant, and extruding to obtain the low-dielectric-constant glass fiber reinforced nylon composite material.
In the present invention, the melt blending is preferably carried out using a twin-screw extruder;
the preparation method is preferably as follows: mixing the dried new material PA66, the dried recovered PA66, the functionalized POSS, the flow modifier, the antioxidant, the light stabilizer and the lubricant to obtain a mixed material, adding the obtained mixed material into a double-screw extruder from a main feeding port of the double-screw extruder, adding the glass fiber into the double-screw extruder from a side feeding port, carrying out melt blending, extruding and granulating to obtain the low-dielectric-constant glass fiber reinforced nylon composite material;
the method for drying the new material PA66 and the recovered PA66 comprises the following steps: drying the new material PA66 and the recovered PA66 at 100 ℃ for 3h respectively; the mixing is preferably carried out in a high speed mixer; the mixing time is 3-5 min; the extrusion temperature of the melt blending is 240-275 ℃, and preferably, the extrusion temperature is as follows: the head temperatures of the first zone, the second zone, the third zone, the fourth zone, the fifth zone, the sixth zone, the seventh zone, the eighth zone and the ninth zone are respectively 245 ℃, 255 ℃, 260 ℃, 265 ℃, 275 ℃, 265 ℃, 260 ℃, 255 ℃, 240 ℃ and the rotation speed of the screw is 150-230 r/min, preferably 180 r/min.
The preparation method of the low-dielectric-constant glass fiber reinforced nylon composite material provided by the invention is simple to operate, easy to control the process steps, and suitable for industrial production.
According to the technical scheme, the invention has the following advantages:
the invention provides a low-dielectric-constant glass fiber reinforced nylon composite material, wherein in the composite material, 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 net structure with multiple cavities, and the special structure of the composite material endows the nylon composite material with a low dielectric constant so as to meet the requirement of high-frequency communication electronics and electricity on the dielectric constant of the material; 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 can be suitable for outdoor high-temperature occasions. The low-dielectric-constant glass fiber reinforced nylon composite material provided by the invention has excellent rigidity and toughness, has a low dielectric constant, can be applied to various high-frequency communication fields, has excellent fluidity and can meet the injection molding requirement of thin-wall products.
Detailed Description
In order to make the objects, features and advantages of the present invention more obvious and understandable, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it should be apparent that the embodiments described below are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the embodiment of the invention, all raw materials and reagents including recovered PA66 and new material PA66 are commercially available; the melt index of the new material PA66 is 230 ℃ and 2.16kg load is 25-65g/10min, the recovered PA66 ash content is 2-10%, and the melt index is 230 ℃ and 2.16kg load is 5-30g/10 min.
Example l
A low-dielectric-constant glass fiber reinforced nylon composite material is prepared from the following components in parts by weight:
new material PA 6670 shares;
recovering the PA 6630 part;
35 parts of glass fiber;
2 parts of functionalized POSS;
0.2 part of a flow modifier CYD 701C;
0.1 part of antioxidant A;
0.5 part of antioxidant B;
0.8 part of light stabilizer;
0.5 part of lubricant.
(1) Placing the glass fiber in 40-60 wt% of silane coupling agent KH550 hydroalcoholic solution at room temperature to perform hydrolytic condensation reaction for 20h to obtain treated glass fiber;
(2) respectively drying a new material PA66 and a recovered PA66 at 100 ℃ for 3 hours, and putting the dried PA66, the recovered PA66, a flow modifier CYD 701C, amino functionalized POSS, an antioxidant 1098, an antioxidant bis (3, 5-di-tert-butylphenyl) pentaerythritol diphosphite, a light stabilizer tris (1,2,2,6, 6-pentamethyl-4-hydroxypiperidine) phosphite and a lubricant KJ-A103 into a high-speed mixer for mixing for 3-5 minutes to obtain a mixed material;
(3) and (2) adding the mixed material into a double-screw extruder from a main feeding port of the double-screw extruder, adding the glass fiber treated in the step (1) into the double-screw extruder from a side feeding port, and performing melt blending, extrusion and granulation to obtain the low-dielectric-constant glass fiber reinforced nylon composite material.
Wherein the barrel temperature of the extruder is set to 245 ℃, 255 ℃, 260 ℃, 265 ℃, 275 ℃, 265 ℃, 260 ℃, 255 ℃, 240 ℃ and the screw rotation speed is 180 r/min.
Example 2
A low-dielectric-constant glass fiber reinforced nylon composite material is prepared from the following components in parts by weight:
new material PA 6670 shares;
recovering the PA 6630 part;
35 parts of glass fiber;
2.5 parts of functionalized POSS;
0.3 part of a flow modifier CYD 701C;
0.1 part of antioxidant A;
0.5 part of antioxidant B;
0.8 part of light stabilizer;
0.6 part of lubricant.
(1) Placing the glass fiber in 40-60 wt% KH550 silane coupling agent solution at room temperature for hydrolysis condensation reaction for 20 hours to obtain treated glass fiber;
(2) respectively drying a new material PA66 and a recovered PA66 at 100 ℃ for 3 hours, and putting the dried PA66, the recovered PA66, a flow modifier CYD 701C, amino functionalized POSS, an antioxidant 1098, an antioxidant bis (3, 5-di-tert-butylphenyl) pentaerythritol diphosphite, a light stabilizer tris (1,2,2,6, 6-pentamethyl-4-hydroxypiperidine) phosphite and a lubricant KJ-A103 into a high-speed mixer for mixing for 3-5 minutes to obtain a mixed material;
(3) adding the mixed material into a double-screw extruder from a main feeding port of the double-screw extruder, and adding the glass fiber treated by the silane coupling agent into the double-screw extruder from a side feeding port; and carrying out melt blending, extrusion and granulation to obtain the low-dielectric-constant glass fiber reinforced nylon composite material.
Wherein the barrel temperature of the extruder is set to 245 ℃, 255 ℃, 260 ℃, 265 ℃, 275 ℃, 265 ℃, 260 ℃, 255 ℃, 240 ℃ and the screw rotation speed is 180 r/min.
Example 3
A low-dielectric-constant glass fiber reinforced nylon composite material is prepared from the following components in parts by weight:
new material PA 6670 shares;
recovering the PA 6630 part;
35 parts of glass fiber;
2.5 parts of functionalized POSS;
0.3 part of a flow modifier CYD 701C;
0.1 part of antioxidant A;
0.5 part of antioxidant B;
0.8 part of light stabilizer;
0.6 part of lubricant.
(1) Placing the glass fiber in 40-60 wt% KH560 silane coupling agent alcohol water solution at room temperature for hydrolysis condensation reaction for 20 hours to obtain treated glass fiber;
(2) respectively drying a new material PA66 and a recovered PA66 at 100 ℃ for 3 hours, and putting the dried PA66, the recovered PA66, a flow modifier CYD 701C, epoxy group functionalized POSS, an antioxidant 1098, an antioxidant bis (3, 5-di-tert-butylphenyl) pentaerythritol diphosphite, a light stabilizer tris (1,2,2,6, 6-pentamethyl-4-hydroxypiperidine) phosphite and a lubricant KJ-A103 into a high-speed mixer for mixing for 3-5 minutes to obtain a mixed material;
(3) adding the mixed material into a double-screw extruder from a main feeding port of the double-screw extruder, and adding the glass fiber treated by the silane coupling agent into the double-screw extruder from a side feeding port; and carrying out melt blending, extrusion and granulation to obtain the low-dielectric-constant glass fiber reinforced nylon composite material.
Wherein the barrel temperature of the extruder is set to 245 ℃, 255 ℃, 260 ℃, 265 ℃, 275 ℃, 265 ℃, 260 ℃, 255 ℃, 240 ℃ and the screw rotation speed is 180 r/min.
Example 4
A low-dielectric-constant glass fiber reinforced nylon composite material is prepared from the following components in parts by weight:
new material PA 6670 shares;
recovering the PA 6630 part;
20 parts of glass fiber;
2.5 parts of functionalized POSS;
0.2 part of a flow modifier CYD 701C;
0.1 part of antioxidant A;
0.5 part of antioxidant B;
0.8 part of light stabilizer;
0.5 part of lubricant.
(1) Placing the glass fiber in 40-60 wt% KH550 silane coupling agent alcohol water solution at room temperature for hydrolysis condensation reaction for 20 hours to obtain treated glass fiber;
(2) respectively drying a new material PA66 and a recovered PA66 at 100 ℃ for 3 hours, and putting the dried PA66, the recovered PA66, a flow modifier CYD 701C, amino functionalized POSS, an antioxidant 1098, an antioxidant bis (3, 5-di-tert-butylphenyl) pentaerythritol diphosphite, a light stabilizer tris (1,2,2,6, 6-pentamethyl-4-hydroxypiperidine) phosphite and a lubricant KJ-A103 into a high-speed mixer for mixing for 3-5 minutes to obtain a mixed material;
(3) adding the mixed material into a double-screw extruder from a main feeding port of the double-screw extruder, and adding the glass fiber treated by the silane coupling agent into the double-screw extruder from a side feeding port; and carrying out melt blending, extrusion and granulation to obtain the low-dielectric-constant glass fiber reinforced nylon composite material.
Wherein the barrel temperature of the extruder is set to 245 ℃, 255 ℃, 260 ℃, 265 ℃, 275 ℃, 265 ℃, 260 ℃, 255 ℃, 240 ℃ and the screw rotation speed is 180 r/min.
Example 5
A low-dielectric-constant glass fiber reinforced nylon composite material is prepared from the following components in parts by weight:
new material PA 6670 shares;
recovering the PA 6630 part;
35 parts of glass fiber;
3.0 parts of functionalized POSS;
0.2 part of a flow modifier CYD 701C;
0.1 part of antioxidant A;
0.5 part of antioxidant B;
0.8 part of light stabilizer;
0.5 part of lubricant.
(1) Placing the glass fiber in 40-60 wt% KH550 silane coupling agent alcohol water solution at room temperature for hydrolysis condensation reaction for 20 hours to obtain treated glass fiber;
(2) respectively drying a new material PA66 and a recovered PA66 at 100 ℃ for 3 hours, and putting the dried PA66, the recovered PA66, a flow modifier CYD 701C, amino functionalized POSS, an antioxidant 1098, an antioxidant bis (3, 5-di-tert-butylphenyl) pentaerythritol diphosphite, a light stabilizer tris (1,2,2,6, 6-pentamethyl-4-hydroxypiperidine) phosphite and a lubricant KJ-A103 into a high-speed mixer for mixing for 3-5 minutes to obtain a mixed material;
(3) adding the mixed material into a double-screw extruder from a main feeding port of the double-screw extruder, and adding the glass fiber treated by the silane coupling agent into the double-screw extruder from a side feeding port; and carrying out melt blending, extrusion and granulation to obtain the low-dielectric-constant glass fiber reinforced nylon composite material.
Wherein the barrel temperature of the extruder is set to 245 ℃, 255 ℃, 260 ℃, 265 ℃, 275 ℃, 265 ℃, 260 ℃, 255 ℃, 240 ℃ and the screw rotation speed is 180 r/min.
Example 6
A low-dielectric-constant glass fiber reinforced nylon composite material is prepared from the following components in parts by weight:
new material PA 6670 shares;
recovering the PA 6630 part;
35 parts of glass fiber;
3.5 parts of functionalized POSS;
0.25 part of a flow modifier CYD 701C;
0.1 part of antioxidant A;
0.6 part of antioxidant B;
0.8 part of light stabilizer;
0.4 part of lubricant.
(1) Placing the glass fiber in 40-60 wt% KH550 silane coupling agent alcohol water solution at room temperature for hydrolysis condensation reaction for 20 hours to obtain treated glass fiber;
(2) respectively drying a new material PA66 and a recovered PA66 at 100 ℃ for 3 hours, and putting the dried PA66, the recovered PA66, a flow modifier CYD 701C, amino functionalized POSS, an antioxidant 1098, an antioxidant bis (3, 5-di-tert-butylphenyl) pentaerythritol diphosphite, a light stabilizer tris (1,2,2,6, 6-pentamethyl-4-hydroxypiperidine) phosphite and a lubricant KJ-A103 into a high-speed mixer for mixing for 3-5 minutes to obtain a mixed material;
(3) adding the mixed material into a double-screw extruder from a main feeding port of the double-screw extruder, and adding the glass fiber treated by the silane coupling agent into the double-screw extruder from a side feeding port; and carrying out melt blending, extrusion and granulation to obtain the low-dielectric-constant glass fiber reinforced nylon composite material.
Wherein the barrel temperature of the extruder is set to 245 ℃, 255 ℃, 260 ℃, 265 ℃, 275 ℃, 265 ℃, 260 ℃, 255 ℃, 240 ℃ and the screw rotation speed is 180 r/min.
Comparative example 1
A low-dielectric-constant glass fiber reinforced nylon composite material is prepared from the following components in parts by weight:
new material PA 6670 shares;
recovering the PA 6630 part;
35 parts of glass fiber;
0.25 part of a flow modifier CYD 701C;
0.1 part of antioxidant A;
0.6 part of antioxidant B;
0.8 part of light stabilizer;
0.4 part of lubricant.
(1) Placing the glass fiber in 40-60 wt% KH550 silane coupling agent alcohol water solution at room temperature for hydrolysis condensation reaction for 20 hours to obtain treated glass fiber;
(2) respectively drying a new material PA66 and a recovered PA66 at 100 ℃ for 3 hours, and putting the dried PA66, the recovered PA66, a flow modifier CYD 701C, an antioxidant 1098, an antioxidant bis (3, 5-di-tert-butylphenyl) pentaerythritol diphosphite, a light stabilizer tris (1,2,2,6, 6-pentamethyl-4-hydroxypiperidine) phosphite and a lubricant KJ-A103 into a high-speed mixer for mixing for 3-5 minutes to obtain a mixed material;
(3) and adding the mixed material into the double-screw extruder from a main feeding port of the double-screw extruder, adding the glass fiber treated by the silane coupling agent into the double-screw extruder from a side feeding port, and performing melt blending, extrusion and granulation to obtain the low-dielectric-constant glass fiber reinforced nylon composite material.
Wherein the barrel temperature of the extruder is set to 245 ℃, 255 ℃, 260 ℃, 265 ℃, 275 ℃, 265 ℃, 260 ℃, 255 ℃, 240 ℃ and the screw rotation speed is 180 r/min.
Comparative example 2
A low-dielectric-constant glass fiber reinforced nylon composite material is prepared from the following components in parts by weight:
new material PA 6670 shares;
recovering the PA 6630 part;
35 parts of glass fiber;
0.25 part of a flow modifier CYD 701C;
0.1 part of antioxidant A;
0.6 part of antioxidant B;
0.8 part of light stabilizer;
0.4 part of lubricant.
(1) Spraying a 40-60 wt% KH550 silane coupling agent solution on the surface of the glass fiber under stirring at room temperature, and drying at 100 ℃ to obtain the treated glass fiber;
(2) respectively drying a new material PA66 and a recovered PA66 at 100 ℃ for 3 hours, and putting the dried PA66, the recovered PA66, a flow modifier CYD 701C, an antioxidant 1098, an antioxidant bis (3, 5-di-tert-butylphenyl) pentaerythritol diphosphite, a light stabilizer tris (1,2,2,6, 6-pentamethyl-4-hydroxypiperidine) phosphite and a lubricant KJ-A103 into a high-speed mixer for mixing for 3-5 minutes to obtain a mixed material; (ii) a
(3) And (2) adding the mixed material into a double-screw extruder from a main feeding port of the double-screw extruder, adding the glass fiber treated in the step (1) into the double-screw extruder from a side feeding port, and performing melt blending, extrusion and granulation to obtain the low-dielectric-constant glass fiber reinforced nylon composite material.
Wherein the barrel temperature of the extruder is set to 245 ℃, 255 ℃, 260 ℃, 265 ℃, 275 ℃, 265 ℃, 260 ℃, 255 ℃, 240 ℃ and the screw rotation speed is 180 r/min.
Comparative example 3
A low-dielectric-constant glass fiber reinforced nylon composite material is prepared from the following components in parts by weight:
new material PA 6670 shares;
recovering the PA 6630 part;
35 parts of glass fiber;
3.5 parts of functionalized POSS;
0.25 part of a flow modifier CYD 701C;
0.1 part of antioxidant A;
0.6 part of antioxidant B;
0.8 part of light stabilizer;
0.4 part of lubricant.
(1) Spraying a 40-60 wt% KH550 silane coupling agent solution on the surface of the glass fiber under stirring at room temperature, and drying at 100 ℃ to obtain the treated glass fiber;
(2) respectively drying a new material PA66 and a recovered PA66 at 100 ℃ for 3 hours, and putting the dried PA66, the recovered PA66, a flow modifier CYD 701C, amino functionalized POSS, an antioxidant 1098, an antioxidant bis (3, 5-di-tert-butylphenyl) pentaerythritol diphosphite, a light stabilizer tris (1,2,2,6, 6-pentamethyl-4-hydroxypiperidine) phosphite and a lubricant KJ-A103 into a high-speed mixer for mixing for 3-5 minutes to obtain a mixed material;
(3) and (2) adding the mixed material into a double-screw extruder from a main feeding port of the double-screw extruder, adding the glass fiber treated in the step (1) into the double-screw extruder from a side feeding port, and performing melt blending, extrusion and granulation to obtain the low-dielectric-constant glass fiber reinforced nylon composite material.
Wherein the barrel temperature of the extruder is set to 245 ℃, 255 ℃, 260 ℃, 265 ℃, 275 ℃, 265 ℃, 260 ℃, 255 ℃, 240 ℃ and the screw rotation speed is 180 r/min.
In order to verify the effects of the present invention, the tensile strength, the bending modulus, the impact strength of the simple beam notch, the melt index, the dielectric constant, and the loss factor of the samples prepared in examples 1 to 6 and comparative examples 1 to 3 were respectively tested according to the corresponding standards, and the results are shown in table 1.
TABLE 1 Low-k glass fiber reinforced nylon composite Performance index
Figure BDA0002601040740000121
Figure BDA0002601040740000131
As can be seen from Table 1, the low dielectric constant glass fiber reinforced nylon composite materials prepared in examples 1-6 have lower dielectric constants than those of the low dielectric constant glass fiber reinforced nylon composite materials prepared in comparative examples 1-3. Compared with the dielectric constant and dielectric loss difference of the comparative example, the low-dielectric-constant glass fiber reinforced nylon composite material prepared by the embodiment of the invention adopts the novel material PA 66/recycled PA66 blended resin, the alkali-free glass fiber with the surface specially treated and the functionalized POSS as raw materials, so that the dielectric constant and the dielectric loss of the composite material can be obviously reduced. The products prepared in the embodiments 1 to 6 are suitable for the requirements of materials in the field of high-frequency communication.
The above-mentioned embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (10)

1. The low-dielectric-constant glass fiber reinforced nylon composite material is characterized by being prepared from the following components in parts by weight:
PA 6680-120 shares;
20-40 parts of glass fiber;
1-5 parts of functionalized POSS;
0.1-0.5 part of flow modifier;
0.2-3 parts of antioxidant;
0.5-2 parts of light stabilizer;
0.3-1 part of lubricant.
2. The low dielectric constant glass fiber reinforced nylon composite of claim 1, wherein PA66 is comprised of virgin PA66 and recycled PA 66;
the new material PA 6660-80 weight parts, the recovery PA 6620-40 weight parts.
3. The low dielectric constant glass fiber reinforced nylon composite of claim 1, wherein the antioxidant comprises: antioxidant A and antioxidant B;
the antioxidant A is one or more than two of antioxidant 1098, antioxidant 1010, antioxidant 1076, antioxidant 1024, antioxidant 264, antioxidant 3125, antioxidant 3114 and antioxidant KY-586;
the antioxidant B is bis (3, 5-di-tert-butylphenyl) pentaerythritol diphosphite, tris (2, 4-di-tert-butylphenyl) phosphite, ethyl 2-methyl-4, 6- (1,1 '-dimethylethyl) phenol ] phosphate, tetrakis (2, 4-di-tert-butyloctaalkoxy-4, 4-biphenyl) phosphate, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, (2,4, 6-tri-tert-butylphenyl, 2-butyl-2-ethyl) -1, 3-propanediol phosphite, bis (2, 4-di-p-isopropylphenyl) pentaerythritol diphosphite, 2' -ethylenebis (4, 6-di-tert-butylphenyl) fluorophosphite and tetrakis (2, 4-di-tert-butylphenyl-4, 4-biphenylyl) bisphosphate.
4. The low dielectric constant glass fiber reinforced nylon composite of claim 1, wherein the glass fibers are alkali-free glass fibers;
the preparation method of the alkali-free glass fiber comprises the following steps:
and (3) placing the glass fiber in a silane coupling agent solution for hydrolysis condensation reaction to obtain the alkali-free glass fiber.
5. The low dielectric constant glass fiber reinforced nylon composite of claim 2, wherein the melt index of the virgin P66 is 230 ℃ 2.16kg load 25-65g/10min, the recycled PA 66: 2 to 10 percent of ash content and 5 to 30g/10min of 2.16kg load with the melt index of 230 ℃.
6. The low-dielectric-constant glass-fiber-reinforced nylon composite material of claim 3, wherein the mass ratio of the antioxidant A to the antioxidant B is (1-10): 1.
7. The low-dielectric-constant glass fiber reinforced nylon composite material and the preparation method thereof as claimed in claim 1, wherein the functionalized POSS is one or more than two of amino POSS monomer, carboxylic POSS monomer, epoxy POSS monomer and hydroxyl POSS monomer.
8. The low dielectric constant glass fiber reinforced nylon composite of claim 7, wherein the number of functional group substitutions in the functionalized POSS is from 2 to 8.
9. The low dielectric constant glass fiber reinforced nylon composite material and the preparation method thereof of claim 1, wherein the light stabilizer is tris (1,2,2,6, 6-pentamethyl-4-hydroxypiperidine) phosphite, benzoic acid (2,2,6, 6-tetramethyl-4-hydroxypiperidine) ester, N-bis (2,2,6, 6-tetramethyl-4-piperidinyl) -1, 6-hexanediamine, N-allyltetramethylpiperidinol, bis (1-octyloxy-2, 2,6, 6-tetramethyl-4-piperidinyl) sebacate, and 1,5,8, 12-tetrakis [4, 6-bis (N-butyl-N-1, 2,2,6, 6-pentamethyl-4-piperidinylamino) -1, one or more than two of 3, 5-triazine-2-yl ] -1,5,8, 12-tetraazadodecane;
the lubricant is a silicone lubricant;
the flow modifier is the flow modifier CYD 701C.
10. The method for preparing a low dielectric constant glass fiber reinforced nylon composite material according to any one of claims 1 to 9, comprising the steps of:
and melting and blending nylon, glass fiber, functionalized POSS, a flow modifier, an antioxidant, a light stabilizer and a lubricant, and extruding to obtain the low-dielectric-constant glass fiber reinforced nylon composite material.
CN202010724060.3A 2020-07-24 2020-07-24 Low-dielectric-constant glass fiber reinforced nylon composite material and preparation method thereof Pending CN111675900A (en)

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Application publication date: 20200918