CN116925534A - Nylon composition with adjustable dielectric constant and preparation method and application thereof - Google Patents
Nylon composition with adjustable dielectric constant and preparation method and application thereof Download PDFInfo
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- CN116925534A CN116925534A CN202210317466.9A CN202210317466A CN116925534A CN 116925534 A CN116925534 A CN 116925534A CN 202210317466 A CN202210317466 A CN 202210317466A CN 116925534 A CN116925534 A CN 116925534A
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- 239000004677 Nylon Substances 0.000 title claims abstract description 58
- 229920001778 nylon Polymers 0.000 title claims abstract description 58
- 239000000203 mixture Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000003063 flame retardant Substances 0.000 claims abstract description 14
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000012763 reinforcing filler Substances 0.000 claims abstract description 9
- 239000003607 modifier Substances 0.000 claims abstract description 6
- 229920006012 semi-aromatic polyamide Polymers 0.000 claims abstract description 6
- 239000006229 carbon black Substances 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000003963 antioxidant agent Substances 0.000 claims description 8
- 229910021645 metal ion Inorganic materials 0.000 claims description 8
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 claims description 6
- 230000003078 antioxidant effect Effects 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- 239000000314 lubricant Substances 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- YKIBJOMJPMLJTB-UHFFFAOYSA-M sodium;octacosanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O YKIBJOMJPMLJTB-UHFFFAOYSA-M 0.000 claims description 3
- 239000003381 stabilizer Substances 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- HGPXWXLYXNVULB-UHFFFAOYSA-M lithium stearate Chemical compound [Li+].CCCCCCCCCCCCCCCCCC([O-])=O HGPXWXLYXNVULB-UHFFFAOYSA-M 0.000 claims description 2
- 239000004209 oxidized polyethylene wax Substances 0.000 claims description 2
- 235000013873 oxidized polyethylene wax Nutrition 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 2
- 239000002671 adjuvant Substances 0.000 claims 1
- 239000012760 heat stabilizer Substances 0.000 claims 1
- 238000005187 foaming Methods 0.000 abstract description 8
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000463 material Substances 0.000 description 36
- 230000000052 comparative effect Effects 0.000 description 27
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 17
- 229910002113 barium titanate Inorganic materials 0.000 description 17
- 238000012360 testing method Methods 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 11
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 10
- 238000001746 injection moulding Methods 0.000 description 8
- 238000005452 bending Methods 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 239000002041 carbon nanotube Substances 0.000 description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 235000010215 titanium dioxide Nutrition 0.000 description 4
- -1 alkali metal montanate Chemical class 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- 239000005711 Benzoic acid Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- XSAOTYCWGCRGCP-UHFFFAOYSA-K aluminum;diethylphosphinate Chemical group [Al+3].CCP([O-])(=O)CC.CCP([O-])(=O)CC.CCP([O-])(=O)CC XSAOTYCWGCRGCP-UHFFFAOYSA-K 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229920006119 nylon 10T Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical group [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 description 1
- 240000007839 Kleinhovia hospita Species 0.000 description 1
- 229920006154 PA11T Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010892 electric spark Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012170 montan wax Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000001038 titanium pigment Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Abstract
The invention discloses a nylon composition with an adjustable dielectric constant, a preparation method and application thereof, wherein the nylon composition with the adjustable dielectric constant comprises the following components in parts by weight: 45-55 parts of semi-aromatic polyamide; 5-25 parts of halogen-free flame retardant; 12-30 parts of reinforcing filler; 0.3-5 parts of conductive carbon black; 0.1-1 part of flow modifier; 0.1-2.5 parts of flame retardant synergist. The nylon composition with adjustable dielectric constant provided by the invention has good dielectric constant adjustability, and meanwhile, the nylon composition has small loss of dielectric strength, mechanical strength, toughness, and the like, does not generate foaming phenomenon, and has very low scheme cost and good use value.
Description
Technical Field
The invention relates to the technical field of modified nylon materials, in particular to a nylon composition with an adjustable dielectric constant, a preparation method and application thereof.
Background
Recently, with the rapid development of 5G, the data transmission rate has been significantly increased, and the theoretical transmission rate of signal peaks can reach 10Gb per second, so that a new high-speed connector product has been created, which has a clear requirement for dielectric constant and dielectric loss due to the clear requirement for dielectric constant of the whole body, so that each structural member has a clear requirement for dielectric constant. Most of these products use LCP-based materials, which are used in a large amount in the industry due to their better dielectric constant tunability and lower dielectric loss characteristics. However, LCP materials have problems of poor bond line strength and poor toughness, and many locations of high-speed connectors are prone to cracking and have little strength. In order to improve and avoid the problem, a great deal of work is needed to be done on the die, even a waste structure is arranged to avoid the bonding line, and the position with poor toughness needs to be thickened, so that the design cost is obviously increased, but even so, the requirement of a customer is difficult to completely meet.
The high-temperature nylon material has excellent toughness, and among a plurality of materials which can be welded by wireless reflow, the high-temperature nylon material has the best toughness and bonding line strength, and meanwhile, the high-temperature nylon material can obtain very good fluidity by regulating and controlling a formula, so that the molding requirement of a high-speed connector can be met. Meanwhile, as the strength and the bonding line strength of the high-temperature nylon material are high, a plurality of lighter and thinner designs can be made, the interference to signals is reduced, the overall weight and the material consumption are reduced, and the purpose of saving the cost is achieved.
However, there are two significant disadvantages to the high temperature nylon materials that limit their use in high speed connectors:
1. the high-temperature nylon material has relatively large dielectric loss due to amide bonds, the dielectric loss of the LCP material with low dielectric loss can be about 0.01 percent, and the high-temperature nylon is usually about 0.1 to 0.2 percent;
2. the dielectric constant of the high-temperature nylon material is far different from that of the LCP material, the adjustability of the dielectric constant is poor, and meanwhile, the dielectric property of the high-temperature nylon material is influenced by a structure due to the structural design of clients and the like, so that the dielectric constant of the high-temperature nylon material must be ensured to be adjustable to a specific value required by the specification in the process of material development, and the span of the high-temperature nylon material is unequal from 3.3 to 6.0.
In the prior art, the dielectric constant is adjustable in the PA11T by doping the carbon nano tube, but the use of the carbon nano tube brings about remarkable reduction of the insulation performance, and the nylon material is characterized by high dielectric strength, so that the insulation safety of the scheme by doping the carbon nano tube cannot meet the requirement and is unacceptable, and meanwhile, the price of the carbon nano tube is extremely high, so that the cost is unacceptable for industrial mass production; it has also been proposed to use barium titanate and polyimide to prepare a high dielectric constant material, but the polyimide material itself has poor processability, cannot form complex parts, and barium titanate has great damage to the toughness of the system, which can cause significant risks of decrease in bond line strength and cracking, and has no obvious advantage compared with LCP schemes; it has also been proposed to use barium titanate to regulate the dielectric constant of LCP, but this solution suffers from all of the disadvantages described above, resulting in a poor customer processing experience.
Therefore, how to ensure the strength, toughness, foamability and other properties of the material on the premise of improving the adjustability of the dielectric constant of the material is a problem to be solved.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a nylon composition with adjustable dielectric constant, and a preparation method and application thereof. By adding a proper amount of conductive carbon black, the invention ensures that the losses of dielectric strength, foamability and other performances are small on the premise of adjustable dielectric constant, and the prepared material has low density, extremely low scheme cost and good use value.
The method is realized by the following technical proposal
The nylon composition with the adjustable dielectric constant comprises the following components in parts by weight:
preferably, the composition comprises the following components in parts by weight:
further, the conductive carbon black is CF conductive carbon black and/or acetylene carbon black. Conductive carbon black affects the penetration of electrical signals and thus the dielectric constant.
In the prior art, the efficiency of improving the dielectric constant of the carbon black is extremely low, more than 6% is needed to be added to obtain an obvious dielectric constant improving effect, and the mechanical property of the material is greatly influenced under the condition of the addition amount, so that the toughness is greatly reduced, the risk of cracking is easy to occur, meanwhile, the feeding difficulty and the potential safety hazard of explosion are easy to exist in the production due to the addition of the high-proportion carbon black, even if the difficulties are overcome, the dielectric loss is greatly improved due to the addition of a large amount of common carbon black, so that the dielectric constant adjustability of the nylon material is hardly improved by carbon black. However, the inventor researches that the ideal dielectric constant can be obtained by only adding 1.5-3 parts by weight of conductive carbon black in the nylon resin through regulating and controlling the formula, and meanwhile, the dielectric loss is not greatly changed, so that the density of the product is obviously reduced compared with the solution of adding barium titanate or titanium white or the solution of adopting LCP as a basic raw material, and the requirements of customers on cost reduction and weight reduction can be better met.
If barium titanate is used, the addition amount of the barium titanate needs to reach more than 15 percent to achieve a better dielectric constant optimization and adjustment effect, but after a large amount of barium titanate is added, the mechanical strength and the bubbling resistance of the material are seriously affected, so that the material cannot be used as a raw material of a product; the use of common carbon black can lead to obvious increase of dielectric loss of the material without meaning, but the use of conductive carbon black can freely regulate and control dielectric constant under lower addition amount, and has excellent mechanical strength and bubbling resistance, thereby having more use value;
in addition, the conductive carbon black has low price, and has obvious price and cost advantages compared with the proposal of large addition amount and high cost of POSS grafted polymer, conductive carbon nano tube, barium titanate and the like disclosed in the prior art.
Further, the free metal ion of the conductive carbon black is 100ppm or less. By limiting the concentration of free metal ions in the conductive carbon black, electrical breakdown caused by the overhigh concentration of the free metal ions can be avoided, the carbon black can be ensured to have improved dielectric constant, meanwhile, the phenomena of breakdown and electric spark are avoided, and the dielectric strength of the material is ensured.
Further, the semiaromatic polyamide is derived from the following repeat units: 50mol% of recurring units based on terephthalic acid and 50mol% of recurring units based on diamine.
In particular, the diamine-based repeating unit is selected from NH (C 2 H 4 NH 2 ) 2 、H 2 N[C 2 H 4 NH] 2 C 2 H 4 NH 2 、H 2 N[C 2 H 4 NH] 3 C 2 H 4 NH 2 、NH[(CH 2 ) 4 NH 2 ] 2 、NH[(CH 2 ) 5 NH 2 ] 2 、NH[(CH 2 ) 6 NH 2 ] 2 、NH[(CH 2 ) 7 NH 2 ] 2 、NH[(CH 2 ) 8 NH 2 ] 2 、NH[(CH 2 ) 9 NH 2 ] 2 、NH[(CH 2 ) 10 NH2] 2 、NH[(CH 2 ) 11 NH 2 ] 2 、N[(CH 2 ) 12 NH 2 ] 2 、NH[(CH 2 ) 13 NH 2 ] 2 、NH[(CH 2 ) 14 NH 2 ) 2 、NH[(CH 2 ) 15 NH 2 ] 2 、NH[(CH 2 ) 16 NH 2 ] 2 、NH[(CH 2 ) 17 NH 2 ] 2 、NH[(CH 2 ) 18 NH 2 ] 2 、H 2 N(H 2 C) 10 NH(CH 2 ) 5 NH 2 、H 2 N(H 2 C) 10 NH(CH 2 ) 6 NH 2 、H 2 N(H 2 C) 10 NH(CH 2 ) 7 NH 2 、H 2 N(H 2 C) 10 NH(CH 2 ) 8 NH 2 、H 2 N(H 2 C) 10 NH(CH 2 ) 9 NH 2 、H 2 N(H 2 C) 10 NH(CH 2 ) 11 NH 2 、H 2 N(H 2 C) 10 NH(CH 2 ) 12 NH 2 、H 2 N(H 2 C) 9 NH(CH 2 ) 6 CH(CH 3 )CH 2 NH 2 、H 2 N(H 2 C) 9 NHCH 2 CH(CH 3 )(CH 2 ) 6 NH 2 、NH[(CH 2 ) 6 CH(CH 3 )CH 2 NH 2 ] 2 、NH[CH 2 CH(CH 3 )(CH 2 ) 6 NH 2 ] 2 One or more of them.
Preferably, the semiaromatic polyamide is PA6T.
Further, the halogen-free flame retardant is preferably aluminum diethylphosphinate.
Further, the reinforcing filler is preferably glass fiber.
Further, the flow modifier is one or more of sodium montanate, lithium stearate, sodium stearate, oxidized polyethylene wax or oxidized propylene wax.
Further, the flame retardant synergist is preferably zinc borate.
Further, 0.1-2 parts of auxiliary agent is also included. The auxiliary agent is one or more of an antioxidant, a heat-resistant stabilizer, an impact stabilizer, other polymers or a lubricant.
The antioxidant is selected from one or more of hindered phenol antioxidants, hindered amine antioxidants, thioether antioxidants and phosphonite antioxidants.
The other polymer is selected from one or more of other kinds of polyamide, polyester, polysulfone or polyphenylene oxide.
The lubricant is selected from one or more of erucamide, alkali metal montanate, stearate, montan wax, polyethylene wax, polypropylene wax or hyperbranched flow modifier.
The invention also provides a preparation method of the nylon composition with adjustable dielectric constant, which comprises the following steps:
s1, weighing the components according to the proportion, and premixing the reinforcing filler and the components except the halogen-free flame retardant to obtain a premix;
s2: and (3) respectively putting the premix, the reinforcing filler and the halogen-free flame retardant in the step (S1) into an extruder, carrying out melt blending, extruding and granulating to obtain the nylon composition with the adjustable dielectric constant.
Further, the extruder is a double-screw extruder, the premix in the step S1 is put into a feed opening of the double-screw extruder, meanwhile, the reinforcing filler is added into a first side feed opening of the double-screw extruder, the halogen-free flame retardant is added into a second side feed opening, and the nylon composition with adjustable dielectric constant is obtained through melt blending, extrusion and granulation at the processing temperature of 290-330 ℃.
The invention also provides application of the nylon composition with the adjustable dielectric constant in preparation of electronic electrical parts, and the nylon composition is particularly suitable for the fields of 5G and high-speed data transmission.
Compared with the prior art, the invention has the beneficial effects that:
(1) The dielectric constant can be adjusted within a certain range by using the conductive carbon black, and compared with the use of barium titanate, common carbon black and the like, the conductive carbon black has lower dielectric loss;
(2) The prepared nylon composition can obtain fluidity close to that of LCP through scientifically adjusting the use of the flow modifier and the flame retardant synergist, so that the nylon composition is suitable for 5G high-speed connectors and other parts;
(3) Preferably, PA6T resin is used, and the dielectric constant can be optimally adjusted in a wider range.
In summary, the invention provides a nylon composition with adjustable dielectric constant, by adding a proper amount of conductive carbon black and designing a specific formula, on the premise of adjustable dielectric constant, the invention ensures that the dielectric strength, mechanical strength, toughness and other performance losses of the material are smaller, no foaming phenomenon occurs, and meanwhile, the scheme cost is extremely low, so that the nylon composition has good use value.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
< preparation of examples and comparative examples >
The raw materials used in the examples and comparative examples of the present invention are derived from commercial or homemade sources, but are not limited to these materials:
semi-aromatic polyamide a: PA10T, homemade, contains 50 mole% terephthalic acid, the remainder being decylenediamine of the diamines described previously, with a relative viscosity of 2.4, the specific homemade process being: adding decanediamine, terephthalic acid, a benzoic acid end-capping agent and deionized water into a reaction kettle with nitrogen atmosphere and pressure of 2-4Mpa according to the proportion, heating the reaction kettle to 160-220 ℃ and keeping the temperature for 0.5-1.5 hours, and heating to 230-240 ℃ and keeping the temperature for 10-15 hours to obtain PA10T;
semi-aromatic polyamide B: PA6T, homemade, 50mol% terephthalic acid, the remainder being hexamethylenediamine of the diamines mentioned above, with a relative viscosity of 2.4, the specific homemade process being: adding hexamethylenediamine, terephthalic acid, a benzoic acid end-capping agent and deionized water into a reaction kettle with nitrogen atmosphere and pressure of 2-4Mpa, heating the reaction kettle to 160-220 ℃ and keeping the temperature for 0.5-1.5 hours, and heating to 230-240 ℃ and keeping the temperature for 10-15 hours to obtain PA6T;
halogen-free flame retardant: aluminum diethylphosphinate is commercially available, and the same commercially available product is used in parallel experiments;
ordinary carbon black: the free metal ion concentration was 500ppm, trade name 50L, available from cabot, U.S.A.;
CF conductive carbon black with a free metal ion concentration of 100ppm, trade mark 7067, available from Bola carbon black;
acetylene black: the free metal ion concentration was 100ppm, grade Y-50A, available from Degussa;
carboter carbon black: the free metal ion concentration was 500ppm, trade name BP2000, available from cabot;
titanium white powder: brand R-2233, available from Germany Kang Nuosi;
barium titanate: the trademark BT-1, volume average particle size 0.1 μm, was obtained from Saka chemical Co., ltd;
flame retardant synergist: zinc borate, commercially available, was used in parallel experiments using the same commercially available product;
glass fiber: 3mm of chopped round glass fiber, with the trade mark of ECS301HP, 3mm of chopped round glass fiber, purchased from Qiangqing International composite material Co., ltd; the method comprises the steps of carrying out a first treatment on the surface of the
Flow modifier: sodium montanate, commercially available, was used in parallel experiments using the same commercially available product;
an antioxidant: hindered phenols, commercially available, were used in parallel experiments using the same commercially available product.
The preparation methods of the examples and comparative examples of the present invention are as follows:
s1, weighing the components according to the proportion of the table 1 and the table 3, and premixing the components except the reinforcing filler and the halogen-free flame retardant to obtain a premix;
s2: and (3) respectively putting the premix, the reinforcing filler and the halogen-free flame retardant in the step (S1) into a double-screw extruder, carrying out melt blending, extruding and granulating to obtain the nylon composition with the adjustable dielectric constant.
Wherein, the screw length-diameter ratio of the twin-screw extruder is 52:1, the barrel temperature of the twin-screw extruder is 320 ℃, the screw rotating speed of the twin-screw extruder is 200rpm, and the feeding speed is 350Kg/h.
In the present specification, "parts" means "parts by weight" unless specifically stated otherwise.
< test Standard >
The performance test criteria for each of the examples and comparative examples of the present invention are as follows:
tensile strength: heating and melting the nylon composition at 290-330 ℃ and performing injection molding to form a tensile sample, and performing tensile property test according to international standard ISO 527-2019 to obtain tensile strength;
flexural strength/flexural modulus: and (3) heating, melting and injection molding the nylon composition at 290-330 ℃ to prepare a tensile sample bending sample, and performing bending performance test according to international standard ISO 178-2010 to obtain bending strength and bending modulus.
Flowability test: performing 0.5mm strip injection molding under the condition of 310 ℃, and measuring the flowability and the thermal stability of the strip injection molding by testing the lengths of a fifth die, a tenth die and a fifteenth die;
foaming test: heating, melting and injection molding the nylon composition at 290-330 ℃ to prepare a square plate with the thickness of 60mm and 1mm, modulating for 168 hours at the humidity of 85 ℃/85%, and then carrying out SMT (surface Mount technology) testing at the temperature of 240-260-280-300 ℃ to observe the foaming condition;
dielectric property test: heating and melting nylon composition at 290-330 deg.C, performing heating and melting, injection molding to obtain 100mm×100mm×2mm flat test piece, and measuring dielectric loss and dielectric constant at frequency of 2.5GHz by using separation medium resonator method (SPDR method);
density testing: heating and melting nylon composition at 290-330 deg.c, injection molding to form small blocks of 10mm×10mm×4mm, and density testing with density tester;
dielectric strength test: heating and melting nylon composition at 290-330 deg.c, injection molding to produce square plate of 60mm x 1mm, and dielectric strength test with dielectric strength tester;
TABLE 1 examples 1-13 formulations (parts by weight)
TABLE 2 Performance test results for examples 1-13
Table 3. Comparative examples 1-9 formulations (parts by weight)
TABLE 4 Performance test results for comparative examples 1-9
Comparative example 10
The formation test was performed with LCP having a dielectric constant of 3.8, which is common in the market, and the results are shown below: the tensile strength is 93MPa, the bending strength is 145MPa, the bending modulus is 8103MPa, the fifth mode of the elongated strip is 39.68mm, the tenth mode of the elongated strip is 42.13mm, the fifteenth mode of the elongated strip is 45.07mm, the dielectric constant is 3.8, and the dielectric loss is 0.1X10 -2 Density of 1.80g/cm 3 . However, the tensile strength and the bending strength of LCP are poor, and serious cracking is very easy to occur in the transportation process and the vibration process of the product, so that the LCP is damaged in functionality and cannot be applied at all. And LCP is more difficult than high temperature nylon electroplating, and the metal of electroplating is easy to desorb simultaneously, in addition, because LCP density is higher, the wearability is poor, easily causes and contacts the violent wearing and tearing of metal.
Examples 1 to 4 and examples 7 to 8, the dielectric loss was only 1.0X10 with the gradual increase of the addition amount of the conductive carbon black from 0.3 parts by weight to 3.0 parts by weight -2 Up to 1.35×10 -2 Meanwhile, the tensile strength still can reach 135Mpa and above, the use strength is very good, the fluidity is kept good, and the sliding is only slight.
In examples 5-6, PA6T was used as the matrix, and the material achieved a more suitable dielectric constant while having extremely high mechanical strength and superior fluidity due to the increase in dielectric constant caused by the change in chemical structure of the resin.
Comparative example 1A material using non-conductive carbon black, while the dielectric constant of comparative example 1 was also improved correspondingly as compared with example 4, the dielectric loss thereof had been improved to 3.56X10 -2 The dielectric loss increases.
Comparative examples 2 to 6, using materials of barium titanate and titanium white, in the case of adding 9 parts by weight of barium titanate (comparative example 3), the dielectric constant was increased only to 3.67, and the conductive carbon black was added only by about 1.5 parts by weight (example 3), so that the value could be obtained; the addition of 3% inorganic barium titanate (comparative example 2) caused the tensile strength of the system to have been reduced to 117Mpa; with further increase of the addition amount of barium titanate, the addition amount reaches 40 parts by weight (comparative example 6), and the dielectric constant can reach 6.24, but at this time, the tensile strength of the nylon composition system has been reduced to only 69Mpa, the fluidity has been greatly deteriorated, and no use value has been found. Comparative example 7 the addition of titanium pigment was the same as that of the conductive carbon black of example 4, as compared with example 4, but the tensile strength and density of comparative example 7 had no practical significance.
Examples 7, 8, commonly found in and on the marketCompared with LCP (comparative example 10) with dielectric constant of 3.8, examples 7 and 8 show absolute dominant mechanical strength (tensile strength and flexural strength) at similar dielectric constants, and can fully meet the requirements of customers and the safety of products; at the same time, the density was measured, and the nylon composition (example 8) added with the conductive carbon black had a density of only 1.42g/cm at a similar dielectric constant 3 While LCP (comparative example 10) was 1.8g/cm 3 The nylon composition density was only 78.9% of the LCP, and the conductive carbon black added nylon composition also had a very low density compared to the barium titanate and titanium dioxide addition schemes (comparative examples 2-9).
In addition, the dielectric strength and foamability of some of the samples prepared from the compositions of examples and comparative examples were also tested, and the results are shown in tables 5 and 6.
TABLE 5 test of dielectric Strength of partial example samples and comparative example samples
| Example 8 | Comparative example 10 | Comparative example 3 | |
| Dry dielectric strength/KV | 40.59 | 30.18 | 39.74 |
| Wet dielectric strength/KV | 36.83 | 29.11 | 35.33 |
From the experimental results, the addition of the conductive carbon black does not bring about obvious reduction of insulation performance as reported in the literature by using the carbon nanotubes, and the dielectric strength of the conductive carbon black addition scheme is higher than that of the barium titanate scheme (comparative example 3) and the current common LCP scheme (comparative example 10) no matter in a dry state or a wet state, so that the conductive carbon black addition scheme has certain advantages, the voltage resistance is better, the safety of products can be ensured, and the nylon composition with the adjustable dielectric constant provided by the invention can be suitable for preparing electronic and electric parts, and is particularly suitable for the fields of 5G and high-speed data transmission.
TABLE 6 foaming comparison of part of the examples and comparative examples
| Foamability of foam | Example 8 | Comparative example 10 | Comparative example 3 |
| Probability of foaming | 0/100 | 30/100 | 100/100 |
From the experimental results, the use of barium titanate can significantly increase the foamability of the material, even achieve 100% of foamability probability, which is unacceptable on SMT products, and LCP introduces a lot of small molecules to cause partial air trapping and foaming due to the adjustment of dielectric constant, while the scheme of using conductive carbon black does not have any foaming problem, which is a significant advantage, and can further prove that the nylon composition with adjustable dielectric constant provided by the invention can be suitable for preparing electronic and electrical products, in particular for the fields of 5G and high-speed data transmission.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (10)
1. The nylon composition with the adjustable dielectric constant is characterized by comprising the following components in parts by weight:
2. the nylon composition with adjustable dielectric constant according to claim 1, which comprises the following components in parts by weight:
3. a nylon composition having an adjustable dielectric constant as claimed in claim 1 or 2, wherein the conductive carbon black is CF conductive carbon black and/or acetylene carbon black.
4. The nylon composition having an adjustable dielectric constant according to claim 1 or 2, wherein the free metal ion of the conductive carbon black is 100ppm or less.
5. The nylon composition of claim 1 or 2, wherein the semiaromatic polyamide is PA6T.
6. The nylon composition of claim 1 or 2, wherein the flow modifier is one or more of sodium montanate, lithium stearate, sodium stearate, oxidized polyethylene wax, or oxidized propylene wax.
7. The nylon composition of claim 1 or 2, further comprising 0.1 to 2 parts of an auxiliary agent.
8. The nylon composition of claim 7, wherein the adjuvant is one or more of an antioxidant, a heat stabilizer, an impact stabilizer, other polymers, or a lubricant.
9. A method for preparing a nylon composition having an adjustable dielectric constant according to any one of claims 1 to 8, comprising the steps of:
s1: weighing the components according to the proportion, and premixing the reinforcing filler and the components except the halogen-free flame retardant to obtain a premix;
s2: and (3) respectively putting the premix, the reinforcing filler and the halogen-free flame retardant in the step (S1) into an extruder, carrying out melt blending, extruding and granulating to obtain the nylon composition with the adjustable dielectric constant.
10. Use of a nylon composition with an adjustable dielectric constant according to any one of claims 1-8 for the preparation of electronic electrical articles.
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