CN114350139B - Polyamide LDS composite material and synthesis method thereof - Google Patents
Polyamide LDS composite material and synthesis method thereof Download PDFInfo
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- 229920002647 polyamide Polymers 0.000 title claims abstract description 112
- 239000002131 composite material Substances 0.000 title claims abstract description 89
- 239000004952 Polyamide Substances 0.000 title claims abstract description 66
- 238000001308 synthesis method Methods 0.000 title claims abstract description 20
- 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 claims abstract description 64
- 239000003063 flame retardant Substances 0.000 claims abstract description 62
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims abstract description 54
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 48
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims abstract description 46
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 35
- 239000011574 phosphorus Substances 0.000 claims abstract description 35
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical class O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 34
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000010949 copper Substances 0.000 claims abstract description 31
- 229910052802 copper Inorganic materials 0.000 claims abstract description 31
- XZAXQWXHBDKYJI-UHFFFAOYSA-N 2-[(6-oxobenzo[c][2,1]benzoxaphosphinin-6-yl)methyl]butanedioic acid Chemical compound C1=CC=C2P(CC(CC(=O)O)C(O)=O)(=O)OC3=CC=CC=C3C2=C1 XZAXQWXHBDKYJI-UHFFFAOYSA-N 0.000 claims abstract description 28
- HEQBUZNAOJCRSL-UHFFFAOYSA-N iron(ii) chromite Chemical compound [O-2].[O-2].[O-2].[Cr+3].[Fe+3] HEQBUZNAOJCRSL-UHFFFAOYSA-N 0.000 claims abstract description 28
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 21
- YAXWOADCWUUUNX-UHFFFAOYSA-N 1,2,2,3-tetramethylpiperidine Chemical compound CC1CCCN(C)C1(C)C YAXWOADCWUUUNX-UHFFFAOYSA-N 0.000 claims abstract description 14
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006116 polymerization reaction Methods 0.000 claims description 106
- 238000003756 stirring Methods 0.000 claims description 97
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 62
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 31
- GXDVEXJTVGRLNW-UHFFFAOYSA-N [Cr].[Cu] Chemical compound [Cr].[Cu] GXDVEXJTVGRLNW-UHFFFAOYSA-N 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 22
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- -1 gamma-aminopropyl triethoxysilane modified montmorillonite Chemical class 0.000 claims description 11
- 230000002194 synthesizing effect Effects 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
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- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 abstract description 18
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- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical group [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
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- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a polyamide LDS composite material and a synthesis method thereof, wherein the polyamide LDS composite material is synthesized by the following raw materials: hexamethylenediamine, terephthalic acid, caprolactam, a reactive phosphorus flame retardant [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] succinic acid, copper chrome black coated by silica sol, organically modified montmorillonite and tetramethyl piperidine amine. The polyamide LDS composite material has excellent mechanical property, flame retardant property and direct laser formability, and can be applied to products such as RF antennas, sensors, connectors and the like.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to a polyamide LDS composite material and a synthesis method thereof.
Background
In recent years, with the explosive growth of the emerging fields of mobile interconnection, internet of things, unmanned automobiles and the like, particularly the popularization of mobile phone 4G high-frequency networks, the electronic industry has seized the opportunity for development, and has obtained unprecedented development. Electronic equipment for high-speed wireless communication is developed towards miniaturization, environmental protection and high performance, and meanwhile, the receiving and transmitting materials of electromagnetic wave signals are required to have controllable dielectric characteristics on one hand and can be precisely and efficiently produced in batches on the other hand. However, the conventional high-frequency signal receiving and transmitting device (radio frequency/microwave antenna, GPS antenna, beidou antenna, navigation antenna, mobile phone main antenna, RFID, etc.) generally adopts the conventional technologies of ceramic material or polymer material and metal patch, etc., and has the limitations of poor dimensional stability, difficult online 3D design and regulation, etc.
Laser Direct Structuring (LDS) was proposed in 1997 by germany Le Puke laser electronics, with which high resolution circuits can be created in complex three-dimensional molded interconnect devices (3D-MID), functionally enabling integration of a polymer housing and a circuit board. The process flow of laser direct forming firstly carries out injection molding on a high polymer material containing a laser sensitive additive, then uses a computer to control a laser scanning route, carries out laser activation on the surface of the high polymer material according to a pre-designed circuit pattern, and finally plating metal on an activation area through electroless plating. The principle of the laser direct structuring technology is realized: (1) The material is required to form a rough surface after laser etching, so that an acting point is provided for subsequent electroless copper plating; (2) One or more metal compounds sensitive to laser, namely LDS additives, are added into a polymer material matrix, and special metal substances in the polymer matrix are activated by laser irradiation, so that active metal seeds are released from the surface of the matrix, a catalytic activation center is provided for electroless plating, and metal ions in an electroless plating solution are promoted to be deposited in a laser region to form a conductive pattern.
Currently, some research is done in the prior art on LDS composites, such as: chinese patent CN 105694447a provides a polyamide resin composition for NMT with LDS function and a preparation method thereof. The polyamide resin composition for NMT mainly comprises the following raw materials in parts by mass: 30-90 parts of polyamide resin, 10-40 parts of glass fiber, 3-25 parts of inorganic whisker, 3-10 parts of LDS auxiliary agent, 0.3-5 parts of stabilizer, 3-15 parts of flexibilizer and 0.5-3 parts of lubricant, wherein the polyamide resin is PA66 resin and/or PA6 resin; chinese patent CN 105849197a provides a thermoplastic, flame retardant plastic molding compound with improved mechanical properties and better surface properties, especially for LDS applications. The thermoplastic molding materials consist of: (A) 30 to 84.9% by weight of a thermoplastic polymer mixture consisting of (A1) 50 to 90% by weight of a partially aromatic, partially crystalline polyamide or a mixture of such polyamides; (A2) 5% to 50% by weight of a polyphenylene ether or a mixture of such polyphenylene ethers; (A3) 0-40% by weight of a partially crystalline, aliphatic polyamide, wherein (A1) - (A3) total 100% by weight of component (A); (B) 15 wt% to 60 wt% glass fibers; (C) 0.1-10 wt% of an LDS additive or a mixture of LDS additives, wherein at least one LDS additive is composed entirely or partially of an inorganic compound of copper and/or tin; (D) 0-40% by weight of a particulate filler material other than (C); (E) 0-5% by weight of other different additives; wherein the sum of (A) - (E) totals 100 weight percent; chinese patent CN 107646047a provides a thermoplastic polymer composition comprising: A. polyamide, b. reinforcing agent, and c. Laser Direct Structuring (LDS) additive; wherein the polyamide comprises a blend of: - (a.1) semi-crystalline semi-aromatic polyamide, and- (a.2) amorphous semi-aromatic polyamide or aliphatic polyamide or mixtures thereof; or a blend of: - (a.3) semi-crystalline aliphatic polyamide, and- (a.4) amorphous semi-aromatic polyamide; metal (di) phosphinates. The invention further relates to articles made from the thermoplastic polymer composition, as well as articles made from the LDS process and methods of making the same.
As can be seen from the above patent, the polyamide-based LDS composite material is mainly obtained by blending an LDS auxiliary agent and a polyamide resin, and the LDS auxiliary agent and the polyamide resin have poor compatibility, resulting in poor mechanical properties. Meanwhile, with the increasing requirement on flame retardance of high polymer products, polyamide belongs to a flammable resin, and the oxygen indexes of common PA1010, PA66 and PA6 are respectively 25.5, 24.3 and 26.4. The values are low and flame retardant modifications must be made, especially for use in electrical related products. Semi-aromatic polyamides, although incorporating aromatic ring structures that are prone to carbonization, have improved flame retardancy, are still unable to self-extinguish and require modification.
Disclosure of Invention
Based on the above, one of the purposes of the present invention is to provide a polyamide LDS composite material, which has excellent mechanical properties and flame retardant properties, and can be applied to products such as RF antennas, sensors, connectors, etc.
The specific technical scheme for realizing the aim of the invention comprises the following steps:
the polyamide LDS composite material is prepared from the following raw materials in parts by weight:
the reactive phosphorus flame retardant is [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] succinic acid;
The coated copper-chromium black is copper-chromium black coated by silica sol; the silica sol comprises the following components in percentage by mass: 8-10: 0.11 to 0.13 of tetraethyl orthosilicate, deionized water and hydrochloric acid;
the organic modified montmorillonite is gamma-aminopropyl triethoxy silane modified montmorillonite.
In some embodiments, the polyamide-based LDS composite material is prepared from the following raw materials in parts by weight:
in some embodiments, the polyamide-based LDS composite material is prepared from the following raw materials in parts by weight:
in some embodiments, the preparation method of the coated copper-chromium black comprises the following steps: placing copper-chromium black into a reaction kettle filled with absolute ethyl alcohol, adding silicon dioxide sol with the mass of 8-14 wt% of the copper-chromium black, heating the reaction kettle to 90-100 ℃ and stirring for reaction for 2.5-4.5 hours, and obtaining the coated copper-chromium black after filtering, drying and crushing.
In some of these embodiments, the silica sol consists of a mass ratio of 1:8.5 to 9.5:0.115 to 0.125 of tetraethyl orthosilicate, deionized water and hydrochloric acid.
In some embodiments, the silica sol is added in an amount of 10 to 12wt% of the mass of the copper chromium black.
In some of these embodiments, the temperature of the reaction vessel is 94 ℃ to 96 ℃.
In some embodiments, the stirring speed of the stirring reaction is 35-45 r/min, and the stirring reaction time is 3-4 hours.
Another object of the present invention is to provide a method for synthesizing the polyamide-based LDS composite material.
The specific technical scheme for realizing the aim of the invention comprises the following steps:
the synthesis method of the polyamide LDS composite material comprises the following steps:
(1) Adding the hexamethylenediamine, the terephthalic acid and the caprolactam which are subjected to vacuum drying into a stirring type polymerization reactor, and simultaneously adding a reactive phosphorus flame retardant, coated copper-chromium black, organically modified montmorillonite, tetramethyl piperidine amine and a proper amount of water; then vacuumizing for 3-6 min, introducing nitrogen for 3-6 min, and circulating for 5-8 times, wherein the system pressure in the stirring type polymerization reactor is controlled to be 0.1-0.3 MPa;
(2) And regulating the stirring speed of the stirring type polymerization reactor to be 30-50 r/min, heating the stirring type polymerization reactor to 275-285 ℃ in a sealed and uniform manner within 2-4 hours, deflating to 2.55MPa when the temperature of the stirring type polymerization reactor reaches 230 ℃, maintaining the pressure at 2.55MPa, deflating to normal pressure after reacting for 1.5-2.5 hours (pre-polymerization), simultaneously heating to 295-315 ℃ and continuing to react for 1-2 hours (post-polymerization), continuously vacuumizing at constant temperature for 0.2-1.2 hours (adhesion reaction), and supplementing nitrogen when discharging to obtain the catalyst.
In some of these embodiments, the method of synthesizing a polyamide-based LDS composite material comprises the steps of:
(1) Adding the hexamethylenediamine, the terephthalic acid and the caprolactam which are subjected to vacuum drying into a stirring type polymerization reactor, and simultaneously adding a reactive phosphorus flame retardant, coated copper-chromium black, organically modified montmorillonite, tetramethyl piperidine amine and a proper amount of water; then vacuumizing for 4-6 min, introducing nitrogen for 4-6 min, and circulating for 5-7 times, wherein the system pressure in the stirring type polymerization reactor is controlled to be 0.15-0.25 MPa;
(2) And regulating the stirring speed of the stirring type polymerization reactor to be 35-45 r/min, heating the stirring type polymerization reactor to 278-282 ℃ at a constant speed in a sealing manner within 2.5-3.5 hours, discharging gas to 2.55MPa when the temperature of the stirring type polymerization reactor reaches 230 ℃, maintaining the pressure at 2.55MPa, discharging gas to normal pressure after reacting for 1.8-2.2 hours (pre-polymerization reaction), heating to 300-310 ℃ at the same time, continuously reacting for 1.3-1.7 hours (post-polymerization reaction) at 300-310 ℃, continuously vacuumizing at constant temperature for 0.5-0.9 hour (tackifying reaction), and supplementing nitrogen when discharging to obtain the catalyst.
The polyamide LDS composite material has the following functions:
the polar oxygen index of the polyamide is generally 24.3-26.4%, the flame retardant grade is UL-94V-2, the dripping phenomenon is serious in the combustion process, the flame retardant polyamide is obtained by adding flame retardant into the polyamide for blending modification, the process is mature, the operation is simple and convenient, but most of the flame retardant is small molecules, the compatibility difference exists between the flame retardant and polyamide high molecules, the agglomeration and precipitation of the flame retardant are easy to cause, the problem of uneven distribution of the flame retardant in a resin matrix is solved, the problem of performance reduction caused by the precipitation of the flame retardant is particularly prominent in miniature precision components in the electronic and electric industry, and the problem can be well avoided by the in-situ polymerization polyamide LDS composite material. According to the invention, a flame-retardant unit reactive phosphorus flame retardant [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] succinic acid is introduced in the polymerization process of hexamethylenediamine, terephthalic acid and caprolactam monomers, and the reaction mechanism is that a flame-retardant monomer with a reactive functional group is copolymerized into a main chain of polyamide in an in-situ polymerization mode, so that molecular-level flame-retardant modification is realized, and the polyamide has intrinsic flame-retardant performance. The reactive phosphorus flame retardant [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] butanedioic acid is a novel phosphate flame retardant monomer with higher reactivity on two sides of carboxyl, and can be copolymerized into a polyamide main chain.
Spinel type composite metal oxides are complex oxides formed by compositing two or more metal oxides, such as copper chromium black (CuCr 2 O 4 ). The copper-chromium black metal is positioned at the end point of the crystal, and the metal is easy to form seeds on the outer layer after being irradiated by laser, thereby being beneficial to the copper deposition process in the electroless plating. In addition, the reactive phosphorus flame retardant is beneficial to reducing the crystallinity of polyamide, and the organically modified montmorillonite is beneficial to improving the surface roughness of polyamide, so that the plating rate of the LDS process is improved, namely, a thicker metal layer is obtained in the same time or a certain layer thickness is realized under the condition of shorter time or less energy requirement.
Copper chrome black belongs to metal oxide, the dispersibility of the copper chrome black in polyamide resin is poor, the LDS chemical plating effect and mechanical property of a composite material are affected, in order to solve the defects, the copper chrome black is coated on the surface through a Si-O-Si network structure formed by hydrolysis of tetraethyl orthosilicate, the interfacial compatibility of the copper chrome black and polyamide is improved, the copper chrome black coated with silica sol is uniformly dispersed in the polyamide resin, and the char formation of the Si-O-Si network structure in the resin combustion process is utilized, so that the char quality is improved, and the condensed phase flame-retardant effect of melamine cyanurate is improved.
The main component of the organically modified montmorillonite is silicate clay which has a nano lamellar structure and good dispersibility, is often used as an additive of a high polymer material, can improve the strength, toughness, thermal stability and fatigue resistance of the material, and can improve the processability of the material, and is called as a universal material. The organic modified montmorillonite can produce synergistic effect with the reactive phosphorus flame retardant [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] succinic acid, so that the flame retardant property and the LDS chemical plating effect of the polyamide-based LDS composite material are effectively improved.
In preparing polyamide-based LDS composites, a high temperature, high pressure environment is typically required. Under the environment, the high polymer is easy to oxidize with oxygen in the air, the molecular chain structure is damaged, the conditions of yellowing of the product, performance reduction and the like occur, the use of the product is seriously affected, and excessive addition of inorganic antioxidants can cause the problems of precipitation of the antioxidants, electric breakdown and the like. Therefore, the invention adopts the end-capping agent tetramethyl piperidine amine with an antioxidant function, and under a high temperature state, the thermal oxidation can lead the main chain of the polyamide LDS composite material to be degraded and broken, while the main chain capped by tetramethyl piperidine amine is provided with a hindered amine functional group which has the capability of capturing free radicals and decomposing hydroperoxides and a regeneration function because the hindered piperidine group can be wound on a high molecular chain, so that the thermal oxidation stability of the high temperature resistant polyamide copolymer is improved, and the chain segment degradation and breaking are not easy to occur.
Compared with the prior art, the polyamide LDS composite material and the synthesis method thereof provided by the invention have the following beneficial effects:
1. aiming at the defect that the polyamide-based LDS composite material prepared by a blending method is poor in mechanical property and flame retardant property, the flame retardant unit reaction type phosphorus flame retardant [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] succinic acid, copper chrome black coated by silica sol and organically modified montmorillonite are introduced in the polymerization process of hexamethylenediamine, terephthalic acid and caprolactam monomers, so that the flame retardant property of the polyamide-based LDS composite material, the compatibility and interfacial adhesion of an LDS auxiliary agent and polyamide base material resin can be effectively improved, the LDS effect is improved, and the adhesive force of a metal coating is improved. The polyamide LDS composite material can be applied to products such as RF antennas, sensors, connectors and the like.
2. According to the synthesis method of the polyamide-based LDS composite 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, so that the low-molecular extractables generated in the polymerization reaction process are removed, the forward polymerization reaction is facilitated, the residual low-molecular extractables cannot influence the performance of the polyamide LDS composite material, and therefore, additional extraction equipment is not needed to separate the low-molecular extractables, and the time and energy can be saved; the synthesis 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.
Drawings
FIG. 1 is a flow chart of the synthesis process of the polyamide-based LDS 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 polyamide-based LDS composite material is as follows (the preparation process flow chart is shown in figure 1):
wherein a=3 to 6, b=50 to 150, c=30 to 70, r is [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] butanedioic acid.
Reaction mechanism
From the reaction formula, the (1) [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] succinic acid, hexamethylenediamine, terephthalic acid and caprolactam are polymerized in situ to obtain an intrinsic flame retardant polyamide-based LDS composite material; (2) The carboxyl end group of the polyamide LDS composite material reacts with the amino end group of the end capping agent tetramethyl piperidine amine, so that the hindered piperidine group is polymerized on the polyamide main chain, and the hindered amine functional group has the capability of capturing free radicals and decomposing hydroperoxides and has a regeneration function, so that the thermal oxygen stability of the polyamide LDS composite material is improved, and the chain segment degradation and fracture are not easy to occur.
The raw materials used in the examples and comparative examples of the present invention are as follows:
hexamethylenediamine, available from Shen Ma Nilong chemical industry Co., ltd.
Terephthalic acid, available from petrochemical company, limited.
Caprolactam, available from the chinese petrochemical company, balm.
[ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] butanedioic acid, available from Shanghai Di Wei Gao Kemao Co.
Copper chrome black, available from pigment company of us Xue Te.
Tetraethyl orthosilicate, available from national pharmaceutical systems and chemicals limited.
Deionized water, self-making.
Hydrochloric acid, available from national pharmaceutical group chemical company, inc.
Absolute ethanol, available from national pharmaceutical group chemical company, inc.
Organically modified montmorillonite, gamma-aminopropyl triethoxysilane modified montmorillonite, is purchased from Zhejiang Feng iridg New Material Co.
Tetramethyl piperidine amine, available from guangzhou chemical reagent plant.
The preparation method of the coated copper chrome black used in the following examples and comparative examples comprises the following steps: tetraethyl orthosilicate: deionized water: the mass ratio of the hydrochloric acid is 1:9:0.12 into a silica sol. 100g of copper-chromium black is placed in a reaction kettle filled with 800mL of absolute ethyl alcohol, then 11wt% (calculated according to the mass of the copper-chromium black) or 11g of silicon dioxide sol is added, the temperature of the reaction kettle is raised to 95 ℃ and stirred for 3.5 hours, and the copper-chromium black coated with the silicon dioxide sol is prepared after filtration, drying and crushing.
The present invention will be described in detail with reference to specific examples.
Example 1 Polyamide-based LDS composite material and method for synthesizing same
The polyamide LDS composite material of the embodiment is prepared from the following raw materials in parts by weight:
the synthesis method of the polyamide LDS composite material comprises the following steps:
(1) Adding the hexamethylenediamine, the terephthalic acid and the caprolactam which are subjected to vacuum drying into a stirring type polymerization reactor, and simultaneously adding a reactive phosphorus flame retardant [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] succinic acid, coated copper chrome black, organically modified montmorillonite, tetramethyl piperidinamine and 200mL of water; then vacuumizing for 3min, introducing nitrogen for 3min, circulating for 8 times, and controlling the system pressure in the stirring type polymerization reactor to be 0.1MPa;
(2) And regulating the stirring speed of the stirring type polymerization reactor to be 30r/min, heating the stirring type polymerization reactor to 285 ℃ at a constant speed in a closed manner within 4 hours, deflating to 2.55MPa when the temperature of the stirring type polymerization reactor reaches 230 ℃, maintaining the pressure at 2.55MPa, deflating to normal pressure after reacting for 1.5 hours (pre-polymerization reaction), heating to 315 ℃ at the same time, continuing to react for 1 hour (post-polymerization reaction), continuously vacuumizing at constant temperature for 1.2 hours (adhesion reaction), finishing the reaction, and supplementing nitrogen when discharging to obtain the catalyst.
Example 2 Polyamide-based LDS composite material and synthetic method thereof
The polyamide LDS composite material of the embodiment is prepared from the following raw materials in parts by weight:
the synthesis method of the polyamide LDS composite material comprises the following steps:
(1) Adding the hexamethylenediamine, the terephthalic acid and the caprolactam which are subjected to vacuum drying into a stirring type polymerization reactor, and simultaneously adding a reactive phosphorus flame retardant [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] succinic acid, coated copper chrome black, organically modified montmorillonite, tetramethyl piperidinamine and 200mL of water; then vacuumizing for 6min, introducing nitrogen for 6min, circulating for 5 times, and controlling the system pressure in the stirring type polymerization reactor to be 0.3MPa;
(2) And regulating the stirring speed of the stirring type polymerization reactor to be 50r/min, heating the stirring type polymerization reactor to 275 ℃ at a constant speed in a closed manner within 2 hours, deflating to 2.55MPa when the temperature of the stirring type polymerization reactor reaches 230 ℃, maintaining the pressure at 2.55MPa, deflating to normal pressure after reacting for 2.5 hours (pre-polymerization reaction), heating to 295 ℃ at the same time, continuing to react for 2 hours (post-polymerization reaction), continuously vacuumizing at constant temperature for 0.2 hour (adhesion reaction), finishing the reaction, and supplementing nitrogen when discharging to obtain the catalyst.
Example 3 Polyamide-based LDS composite material and method for synthesizing same
The polyamide LDS composite material of the embodiment is prepared from the following raw materials in parts by weight:
the synthesis method of the polyamide LDS composite material comprises the following steps:
(1) Adding the hexamethylenediamine, the terephthalic acid and the caprolactam which are subjected to vacuum drying into a stirring type polymerization reactor, and simultaneously adding a reactive phosphorus flame retardant [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] succinic acid, silica sol coated copper chrome black, organically modified montmorillonite, tetramethyl piperidinamine and 200mL of water; then vacuumizing for 4min, introducing nitrogen for 4min, circulating for 7 times, and controlling the system pressure in the stirring type polymerization reactor to be 0.15MPa;
(2) And regulating the stirring speed of the stirring type polymerization reactor to 35r/min, heating the stirring type polymerization reactor to 282 ℃ at a constant speed in a sealed manner within 3.5 hours, deflating to 2.55MPa when the temperature of the stirring type polymerization reactor reaches 230 ℃, maintaining the pressure at 2.55MPa, deflating to normal pressure after reacting for 1.8 hours (pre-polymerization reaction), heating to 310 ℃ at the same time, continuing to react for 1.3 hours (post-polymerization reaction), continuously vacuumizing at constant temperature for 0.9 hour (tackifying reaction), finishing the reaction, and supplementing nitrogen when discharging to obtain the catalyst.
Example 4 Polyamide-based LDS composite Material and method for synthesizing the same
The polyamide LDS composite material of the embodiment is prepared from the following raw materials in parts by weight:
the synthesis method of the polyamide LDS composite material comprises the following steps:
(1) Adding the hexamethylenediamine, the terephthalic acid and the caprolactam which are subjected to vacuum drying into a stirring type polymerization reactor, and simultaneously adding a reactive phosphorus flame retardant [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] succinic acid, coated copper chrome black, organically modified montmorillonite, tetramethyl piperidinamine and 200mL of water; then vacuumizing for 6min, introducing nitrogen for 6min, circulating for 5 times, and controlling the system pressure in the stirring type polymerization reactor to be 0.25MPa;
(2) And regulating the stirring speed of the stirring type polymerization reactor to 45r/min, heating the stirring type polymerization reactor to 278 ℃ at a constant speed in 2.5 hours in a sealing way, discharging gas to 2.55MPa when the temperature of the stirring type polymerization reactor reaches 230 ℃, maintaining the pressure at 2.55MPa, reacting for 2.2 hours (pre-polymerization reaction), discharging gas to normal pressure, simultaneously heating to 300 ℃, continuously reacting for 1.7 hours (post-polymerization reaction) at 300 ℃, continuously vacuumizing at constant temperature for 0.5 hour (tackifying reaction), finishing the reaction, and supplementing nitrogen when discharging.
Example 5 Polyamide-based LDS composite Material and method for synthesizing the same
The polyamide LDS composite material of the embodiment is prepared from the following raw materials in parts by weight:
the synthesis method of the polyamide LDS composite material comprises the following steps:
(1) Adding the hexamethylenediamine, the terephthalic acid and the caprolactam which are subjected to vacuum drying into a stirring type polymerization reactor, and simultaneously adding a reactive phosphorus flame retardant [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] succinic acid, coated copper chrome black, organically modified montmorillonite, tetramethyl piperidinamine and 200mL of water; then vacuumizing for 5min, introducing nitrogen for 5min, circulating for 6 times, and controlling the system pressure in the stirring type polymerization reactor to be 0.2MPa;
(2) And regulating the stirring speed of the stirring type polymerization reactor to 40r/min, heating the stirring type polymerization reactor to 280 ℃ at a constant speed in a sealed manner within 3 hours, deflating to 2.55MPa when the temperature of the stirring type polymerization reactor reaches 230 ℃, maintaining the pressure at 2.55MPa, deflating to normal pressure after reacting for 2 hours (pre-polymerization reaction), heating to 305 ℃ at the same time, continuing to react for 1.5 hours (post-polymerization reaction), continuously vacuumizing at constant temperature for 0.7 hour (adhesion reaction), finishing the reaction, and supplementing nitrogen when discharging to obtain the catalyst.
Example 6 Polyamide-based LDS composite Material and method for synthesizing the same
The polyamide LDS composite material of the embodiment is prepared from the following raw materials in parts by weight:
the synthesis method of the polyamide LDS composite material comprises the following steps:
(1) Adding the hexamethylenediamine, the terephthalic acid and the caprolactam which are subjected to vacuum drying into a stirring type polymerization reactor, and simultaneously adding a reactive phosphorus flame retardant [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] succinic acid, coated copper chrome black, organically modified montmorillonite, tetramethyl piperidinamine and 200mL of water; then vacuumizing for 5min, introducing nitrogen for 5min, circulating for 6 times, and controlling the system pressure in the stirring type polymerization reactor to be 0.2MPa;
(2) And regulating the stirring speed of the stirring type polymerization reactor to 40r/min, heating the stirring type polymerization reactor to 280 ℃ at a constant speed in a sealed manner within 3 hours, deflating to 2.55MPa when the temperature of the stirring type polymerization reactor reaches 230 ℃, maintaining the pressure at 2.55MPa, deflating to normal pressure after reacting for 2 hours (pre-polymerization reaction), heating to 305 ℃ at the same time, continuing to react for 1.5 hours (post-polymerization reaction), continuously vacuumizing at constant temperature for 0.7 hour (adhesion reaction), finishing the reaction, and supplementing nitrogen when discharging to obtain the catalyst.
Example 7 Polyamide-based LDS composite Material and method for synthesizing the same
The polyamide LDS composite material of the embodiment is prepared from the following raw materials in parts by weight:
the synthesis method of the polyamide LDS composite material comprises the following steps:
(1) Adding the hexamethylenediamine, the terephthalic acid and the caprolactam which are subjected to vacuum drying into a stirring type polymerization reactor, and simultaneously adding a reactive phosphorus flame retardant [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] succinic acid, coated copper chrome black, organically modified montmorillonite, tetramethyl piperidinamine and 200mL of water; then vacuumizing for 5min, introducing nitrogen for 5min, circulating for 6 times, and controlling the system pressure in the stirring type polymerization reactor to be 0.2MPa;
(2) And regulating the stirring speed of the stirring type polymerization reactor to 40r/min, heating the stirring type polymerization reactor to 280 ℃ at a constant speed in a sealed manner within 3 hours, deflating to 2.55MPa when the temperature of the stirring type polymerization reactor reaches 230 ℃, maintaining the pressure at 2.55MPa, deflating to normal pressure after reacting for 2 hours (pre-polymerization reaction), heating to 305 ℃ at the same time, continuing to react for 1.5 hours (post-polymerization reaction), continuously vacuumizing at constant temperature for 0.7 hour (adhesion reaction), finishing the reaction, and supplementing nitrogen when discharging to obtain the catalyst.
Comparative example 1
The polyamide LDS composite material is prepared from the following raw materials in parts by weight:
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the synthesis method of the polyamide LDS composite material comprises the following steps:
(1) Adding the hexamethylenediamine, the terephthalic acid and the caprolactam which are dried in vacuum into a stirring type polymerization reactor, and simultaneously adding ammonium polyphosphate, copper chrome black, organically modified montmorillonite, tetramethyl piperidylamine and 200mL of water; then vacuumizing for 5min, introducing nitrogen for 5min, circulating for 6 times, and controlling the system pressure in the stirring type polymerization reactor to be 0.2MPa;
(2) And regulating the stirring speed of the stirring type polymerization reactor to 40r/min, heating the stirring type polymerization reactor to 280 ℃ at a constant speed in a sealed manner within 3 hours, deflating to 2.55MPa when the temperature of the stirring type polymerization reactor reaches 230 ℃, maintaining the pressure at 2.55MPa, deflating to normal pressure after reacting for 2 hours (pre-polymerization reaction), heating to 305 ℃ at the same time, continuing to react for 1.5 hours (post-polymerization reaction), continuously vacuumizing at constant temperature for 0.7 hour (adhesion reaction), finishing the reaction, and supplementing nitrogen when discharging to obtain the catalyst.
Comparative example 2
The polyamide LDS composite material is prepared from the following raw materials in parts by weight:
The synthesis method of the polyamide LDS composite material comprises the following steps:
(1) Adding the hexamethylenediamine, the terephthalic acid and the caprolactam which are subjected to vacuum drying into a stirring type polymerization reactor, and simultaneously adding a reactive phosphorus flame retardant [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] succinic acid, coated copper-chromium black, tetramethyl piperidylamine and 200mL of water; then vacuumizing for 5min, introducing nitrogen for 5min, circulating for 6 times, and controlling the system pressure in the stirring type polymerization reactor to be 0.2MPa;
(2) And regulating the stirring speed of the stirring type polymerization reactor to 40r/min, heating the stirring type polymerization reactor to 280 ℃ at a constant speed in a sealed manner within 3 hours, deflating to 2.55MPa when the temperature of the stirring type polymerization reactor reaches 230 ℃, maintaining the pressure at 2.55MPa, deflating to normal pressure after reacting for 2 hours (pre-polymerization reaction), heating to 305 ℃ at the same time, continuing to react for 1.5 hours (post-polymerization reaction), continuously vacuumizing at constant temperature for 0.7 hour (adhesion reaction), finishing the reaction, and supplementing nitrogen when discharging to obtain the catalyst.
Comparative example 3
The polyamide LDS composite material is prepared from the following raw materials in parts by weight:
The synthesis method of the polyamide LDS composite material comprises the following steps:
(1) Adding the hexamethylenediamine, the terephthalic acid and the caprolactam which are subjected to vacuum drying into a stirring type polymerization reactor, and simultaneously adding a reactive phosphorus flame retardant [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] succinic acid, coated copper chrome black, organically modified montmorillonite and 200mL of water; then vacuumizing for 5min, introducing nitrogen for 5min, circulating for 6 times, and controlling the system pressure in the stirring type polymerization reactor to be 0.2MPa;
(2) And regulating the stirring speed of the stirring type polymerization reactor to 40r/min, heating the stirring type polymerization reactor to 280 ℃ at a constant speed in a sealed manner within 3 hours, deflating to 2.55MPa when the temperature of the stirring type polymerization reactor reaches 230 ℃, maintaining the pressure at 2.55MPa, deflating to normal pressure after reacting for 2 hours (pre-polymerization reaction), heating to 305 ℃ at the same time, continuing to react for 1.5 hours (post-polymerization reaction), continuously vacuumizing at constant temperature for 0.7 hour (adhesion reaction), finishing the reaction, and supplementing nitrogen when discharging to obtain the catalyst.
The following is a list of the raw material compositions of examples 1-7 and comparative examples 1-3.
Table 1 list of raw material compositions of examples 1 to 7 and comparative examples 1 to 3
Remarks: a, replacing a reactive phosphorus flame retardant [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] succinic acid with ammonium polyphosphate; b, replacing the coated copper-chromium black with copper-chromium black.
Examples 1 to 7 were polyamide-based LDS composites prepared by adjusting the addition amounts of caprolactam, reactive phosphorus flame retardant [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] succinic acid, coated copper chrome black, organically modified montmorillonite and tetramethylpiperidine amine, comparative example 1 was prepared by substituting ammonium polyphosphate for reactive phosphorus flame retardant [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] succinic acid, and coated copper chrome black for copper chrome black, and comparative example 2 was polyamide-based LDS composites prepared without adding organically modified montmorillonite, and comparative example 3 was polyamide-based LDS composites prepared without adding tetramethylpiperidine amine. The polyamide-based LDS composite materials prepared in the above examples and comparative examples were subjected to the following performance tests:
tensile strength: the stretching rate was 50mm/min according to GB/T1040-2006 standard.
Limiting oxygen index: the sample sizes were 80mm by 10mm by 4mm according to GB/T2406.2-2009 standard test.
Vertical combustion test: the sample sizes were 125mm by 13mm by 0.8mm according to the UL94 standard test.
Intrinsic viscosity: according to GB/T1632-2008 standard test, the solvent is concentrated sulfuric acid, and the test temperature is 25 ℃.
Adhesion test (hundred test) of metal plating on plastic part surface: according to ASTM D3359, specifically, under the conditions of room temperature of 23+/-2 ℃ and relative humidity of 50+/-5%, a sharp blade (the blade angle is 15-30 ℃) is used for scribing 10 multiplied by 10 small grids of 1mm multiplied by 1mm on the surface of a test sample, and each scribing line is deep and the bottom layer of a plating layer; brushing the test area clean by the hairbrush; firmly adhering the tested small grid by using a 3M 600 adhesive tape, and forcefully wiping the adhesive tape by using an eraser to enlarge the contact area and the strength between the adhesive tape and a tested area; the adhesive tape was held at one end by hand and the scotch tape was pulled off rapidly at an angle of 60 ° in the vertical direction and 2 identical tests were performed at the same position. And (3) result judgment: qualified when the adhesive force is required to be more than or equal to 4B; 5B, the scribing edge is smooth, and no paint is dropped off at the scribing edge and the crossing point; 4B-paint with small pieces falling off at the cross points of the scribing lines, and the total falling-off area is less than 5%; 3B-paint with small pieces at the edges and the crossing points of the scribing lines is dropped, and the total dropped area is between 5 and 15 percent; 2B-a piece of paint is dropped off at the edge and the crossing point of the scribing line, and the total dropping area is 15-35%; 1B-a piece of paint is dropped off at the edge and the crossing point of the scribing line, and the total dropping area is between 35 and 65 percent; 0B-there is a flaking of paint off at the edges and crossing points of the scribe, and the total area of off is greater than 65%.
Heat retention experiment: in the case of injection molding the tensile strength test pieces of example 7 and comparative example 3, the polyamide-based LDS composite material was left in the cylinder of an injection molding machine at 320 ℃ for 10 minutes, and then the tensile strength test pieces were injection molded, and the tensile strength thereof was tested.
The results of the performance test are shown in Table 2.
Table 2 Table of Properties of Polyamide-based LDS composites of examples 1-7 and comparative examples 1-3
As can be seen from table 2:
as the addition amount of caprolactam and tetramethylpiperidine amine increases, the tensile strength and the intrinsic viscosity of the polyamide-based LDS composite material show a decreasing trend of variation. This is because, on the one hand, the more the amount of caprolactam is added, the smaller the ratio of benzene ring structure in rigid terephthalic acid is, the smaller the steric hindrance of polymer molecular chains is, and in the process that the polyamide-based LDS composite material is stretched by external force, the relative sliding among polymer molecular chains is easy to occur, so that the tensile strength is reduced, on the other hand, the addition amount of the polymerization inhibitor tetramethylpiperidine amine is increased, the terminal amino group of the tetramethylpiperidine amine can react with the terminal carboxyl group of the polyamide, so that the effect of polymer molecular chain termination is achieved, the intrinsic viscosity of the polymer is reduced, the Van der Waals force is also reduced, and the relative sliding among polymer molecular chains is easy to occur in the process that the polyamide-based LDS composite material is stretched by external force, so that the tensile strength is reduced.
With the reduction of the addition amount of the reactive phosphorus flame retardant [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] succinic acid and the organically modified montmorillonite, the limiting oxygen index of the polyamide-based LDS composite material shows a gradually reduced change trend, and the vertical burning test (UL 940.8 mm) is V0 grade. This is because the reactive phosphorus flame retardant [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] butanedioic acid is a novel phosphate flame retardant monomer with high reactivity of carboxyl groups at two sides and can be copolymerized into a polyamide main chain, flame retardant is mainly carried out through a condensed phase, PO free radicals are generated by thermal decomposition in the flame retardant polyamide process, the free radicals further react to generate phosphoric acid, pyrophosphoric acid and the like, dehydration carbonization or crosslinking of the polyamide resin is promoted, heat and oxygen exchange are blocked, and in addition, the PO free radicals can capture HO free radicals and the like participating in the free radical chain reaction in the combustion process to terminate the combustion reaction. Meanwhile, the organic modified montmorillonite can produce synergistic effect with the reactive phosphorus flame retardant [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] succinic acid, so that the flame retardant property and the LDS chemical plating effect of the polyamide-based LDS composite material are effectively improved.
When the addition amount of the coated copper-chromium black is 24-36 parts, the metal coating adhesion of the polyamide LDS composite material is 5B. The metal of copper chrome black is positioned at the end point of the crystal, the metal is easy to form seeds on the outer layer after being irradiated by laser, a catalytic activation center is provided for subsequent chemical plating, metal ions in the chemical plating solution are promoted to be deposited in a laser area to form a conductive pattern, and meanwhile, the metal seeds also have the effect of increasing the bonding strength of a plating layer and a resin matrix. In addition, the reactive phosphorus flame retardant is beneficial to reducing the crystallinity of polyamide, and the organically modified montmorillonite is beneficial to improving the surface roughness of polyamide, so that the plating rate of the LDS process is improved, namely, a thicker metal layer is obtained in the same time or a certain layer thickness is realized under the condition of shorter time or less energy requirement.
In summary, the polyamide-based LDS composite material with excellent mechanical property and flame retardant property can be obtained by adjusting the addition amount of caprolactam, a reactive phosphorus flame retardant [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] succinic acid, coated copper chrome black, organically modified montmorillonite and tetramethyl piperidine amine under the synergistic cooperation of various auxiliary agents. Among them, the polyamide-based LDS composite material of example 7 has the best comprehensive performance.
Comparative example 1 in comparison with example 7, comparative example 1 replaced the reactive phosphorus flame retardant [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] succinic acid with ammonium polyphosphate and the coated copper chrome black with copper chrome black. Because ammonium particles of ammonium polyphosphate have poor reactivity with terminal carboxyl groups of polyamide and copper chrome black has poor dispersibility in polyamide resin, the tensile strength and the metal coating adhesion of the polyamide-based LDS composite material synthesized in comparative example 1 are lower than those of example 7.
Comparative example 2 compared with example 7, comparative example 2 was free of addition of organically modified montmorillonite, and the polyamide-based LDS composite material synthesized in comparative example 2 was lower in tensile strength and metal plating adhesion than example 7. The main component of the organically modified montmorillonite is silicate clay, has a nano lamellar structure, has good dispersibility, is often used as an additive for high polymer materials, can improve the strength, toughness, thermal stability and fatigue resistance of the materials, and can improve the processability of the materials, and is called as a universal material. The organic modified montmorillonite can produce synergistic effect with the reactive phosphorus flame retardant [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] succinic acid, so that the flame retardant property and the LDS chemical plating effect of the polyamide-based LDS composite material are effectively improved.
Comparative example 3 in comparison with example 7, comparative example 3 was free of tetramethylpiperidine amine. The intrinsic viscosity of comparative example 3 is much higher than that of example 7, and the processability of comparative example 3 is poor. Since a high temperature and high pressure environment is generally required in preparing the high temperature resistant polyamide copolymer. Under the environment, the high polymer is easy to oxidize with oxygen in the air, the molecular chain structure is destroyed, the yellowing of the product, the performance reduction and the like occur, and the use of the product is seriously influenced. Example 7 by using a blocking agent tetramethylpiperidine amine having an antioxidant function, thermal oxidation can cause degradation and chain scission of the main chain of the high temperature resistant polyamide copolymer at a high temperature, while the main chain blocked with tetramethylpiperidine amine has a hindered amine functional group having a capability of capturing free radicals and decomposing hydroperoxides and a regenerating function because the hindered piperidine group can be entangled on a polymer chain, and the thermal oxygen stability of the high temperature resistant polyamide copolymer is improved, and segment degradation and cleavage are not easily caused.
The polyamide-based LDS composite materials synthesized in example 7 and comparative example 3 were subjected to a heat retention test, and the results show that the tensile strength of example 7 was 98MPa, the tensile strength of comparative example 3 was 98MPa, and the tensile strength of comparative example 3 was 54MPa, which indicates that the thermal stability of example 7 was higher than that of comparative example 3.
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 (10)
1. The polyamide LDS composite material is characterized by being prepared from the following raw materials in parts by weight:
116.2 parts of hexamethylenediamine, which is added into the mixture,
166.1 parts of terephthalic acid, which is used as a catalyst,
39.8 to 73.8 parts of caprolactam,
20.8 to 31.1 parts of reactive phosphorus flame retardant,
24-36 parts of coated copper-chromium black,
3 to 12 parts of organic modified montmorillonite,
0.62 to 1.09 portions of tetramethyl piperidine amine;
the reactive phosphorus flame retardant is [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] succinic acid;
the coated copper-chromium black is copper-chromium black coated by silica sol; the silica sol comprises the following components in percentage by mass: 8-10: 0.11 to 0.13 of tetraethyl orthosilicate, deionized water and hydrochloric acid;
the organic modified montmorillonite is gamma-aminopropyl triethoxysilane modified montmorillonite;
the synthesis method of the polyamide LDS composite material comprises the following steps:
(1) Adding the hexamethylenediamine, the terephthalic acid and the caprolactam which are subjected to vacuum drying into a stirring type polymerization reactor, and simultaneously adding a reactive phosphorus flame retardant, coated copper-chromium black, organically modified montmorillonite, tetramethyl piperidine amine and a proper amount of water; then vacuumizing for 3-6 min, introducing nitrogen for 3-6 min, and circulating for 5-8 times, wherein the system pressure in the stirring type polymerization reactor is controlled to be 0.1-0.3 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 275-285 ℃ in a sealed and uniform manner within 2-4 hours, deflating to 2.55MPa when the temperature of the stirring type polymerization reactor reaches 230 ℃, maintaining the pressure at 2.55MPa, reacting for 1.5-2.5 hours, deflating to normal pressure, simultaneously heating to 295-315 ℃, continuously reacting for 1-2 hours at 295-315 ℃, continuously vacuumizing for 0.2-1.2 hours at constant temperature, ending the reaction, and supplementing nitrogen when discharging to obtain the catalyst.
2. The polyamide-based LDS composite material according to claim 1, which is characterized by being prepared from the following raw materials in parts by weight:
116.2 parts of hexamethylenediamine, which is added into the mixture,
166.1 parts of terephthalic acid, which is used as a catalyst,
51.1 to 62.5 parts of caprolactam,
22.5 to 29.4 parts of reactive phosphorus flame retardant,
27-33 parts of coated copper-chromium black,
6 to 9 portions of organic modified montmorillonite,
0.7 to 1.01 portion of tetramethyl piperidine amine.
3. The polyamide-based LDS composite material of claim 2, which is prepared from the following raw materials in parts by weight:
116.2 parts of hexamethylenediamine, which is added into the mixture,
166.1 parts of terephthalic acid, which is used as a catalyst,
54.5 to 59.1 parts of caprolactam,
24.2 to 27.7 parts of reactive phosphorus flame retardant,
28.5 to 31.5 portions of coated copper chrome black,
6.9 to 8.1 portions of organic modified montmorillonite,
0.78 to 0.94 portion of tetramethyl piperidine amine.
4. The polyamide-based LDS composite material according to any one of claims 1 to 3, characterized in that the preparation method of the coated copper chrome black comprises the following steps: placing copper-chromium black into a reaction kettle filled with absolute ethyl alcohol, then adding silicon dioxide sol with the mass of 8-14 and wt% of the copper-chromium black, heating the reaction kettle to 90-100 ℃, stirring and reacting for 2.5-4.5 hours, and obtaining the coated copper-chromium black after filtering, drying and crushing.
5. The polyamide-based LDS composite material of claim 4, wherein the silica sol consists of the following components in mass ratio of 1:8.5 to 9.5:0.115 to 0.125 of tetraethyl orthosilicate, deionized water and hydrochloric acid.
6. The polyamide-based LDS composite material according to claim 4, wherein the addition amount of the silica sol is 10-12 wt% of the mass of copper-chromium black.
7. The polyamide-based LDS composite material of claim 4, wherein the temperature of the reaction vessel is 94 ℃ to 96 ℃.
8. The polyamide-based LDS composite material of claim 4, wherein the stirring reaction is carried out at a stirring speed of 35 r/min to 45r/min for 3 hours to 4 hours.
9. The synthesis method of the polyamide-based LDS composite material as claimed in any one of claims 1 to 8, which is characterized by comprising the following steps:
(1) Adding the hexamethylenediamine, the terephthalic acid and the caprolactam which are subjected to vacuum drying into a stirring type polymerization reactor, and simultaneously adding a reactive phosphorus flame retardant, coated copper-chromium black, organically modified montmorillonite, tetramethyl piperidine amine and a proper amount of water; then vacuumizing for 3-6 min, introducing nitrogen for 3-6 min, and circulating for 5-8 times, wherein the system pressure in the stirring type polymerization reactor is controlled to be 0.1-0.3 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 275-285 ℃ in a sealed and uniform manner within 2-4 hours, deflating to 2.55MPa when the temperature of the stirring type polymerization reactor reaches 230 ℃, maintaining the pressure at 2.55MPa, reacting for 1.5-2.5 hours, deflating to normal pressure, simultaneously heating to 295-315 ℃, continuously reacting for 1-2 hours at 295-315 ℃, continuously vacuumizing for 0.2-1.2 hours at constant temperature, ending the reaction, and supplementing nitrogen when discharging to obtain the catalyst.
10. The method for synthesizing the polyamide-based LDS composite material according to claim 9, which comprises the following steps:
(1) Adding the hexamethylenediamine, the terephthalic acid and the caprolactam which are subjected to vacuum drying into a stirring type polymerization reactor, and simultaneously adding a reactive phosphorus flame retardant, coated copper-chromium black, organically modified montmorillonite, tetramethyl piperidine amine and a proper amount of water; then vacuumizing for 4-6 min, introducing nitrogen for 4-6 min, and circulating for 5-7 times, wherein the system pressure in the stirring type polymerization reactor is controlled to be 0.15-0.25 MPa;
(2) And regulating the stirring speed of the stirring type polymerization reactor to be 35-45 r/min, heating the stirring type polymerization reactor to 278-282 ℃ at a constant speed in a closed manner within 2.5-3.5 hours, discharging gas to 2.55MPa when the temperature of the stirring type polymerization reactor reaches 230 ℃, maintaining the pressure at 2.55MPa, discharging gas to normal pressure after reacting for 1.8-2.2 hours, simultaneously heating to 300-310 ℃, continuously reacting for 1.3-1.7 hours at 300-310 ℃, continuously vacuumizing at constant temperature for 0.5-0.9 hour, and supplementing nitrogen when discharging to obtain the catalyst.
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