CN114656785A - Polyamide composite material with high weld mark strength and preparation method and application thereof - Google Patents
Polyamide composite material with high weld mark strength and preparation method and application thereof Download PDFInfo
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- CN114656785A CN114656785A CN202210324077.9A CN202210324077A CN114656785A CN 114656785 A CN114656785 A CN 114656785A CN 202210324077 A CN202210324077 A CN 202210324077A CN 114656785 A CN114656785 A CN 114656785A
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- Prior art keywords
- composite material
- weld mark
- polyamide composite
- acid
- high weld
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- 239000004952 Polyamide Substances 0.000 title claims abstract description 37
- 229920002647 polyamide Polymers 0.000 title claims abstract description 37
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- 239000003063 flame retardant Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 14
- 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 13
- 229920005989 resin Polymers 0.000 claims abstract description 11
- 239000011347 resin Substances 0.000 claims abstract description 11
- 229920006012 semi-aromatic polyamide Polymers 0.000 claims abstract description 11
- 239000012779 reinforcing material Substances 0.000 claims abstract description 10
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 12
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 10
- 239000003365 glass fiber Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 239000000835 fiber Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000004427 diamine group Chemical group 0.000 claims description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 4
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 4
- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical compound OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 0.000 claims description 4
- 239000010456 wollastonite Substances 0.000 claims description 4
- 229910052882 wollastonite Inorganic materials 0.000 claims description 4
- -1 aromatic ring compound Chemical class 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 claims description 2
- DPQHRXRAZHNGRU-UHFFFAOYSA-N 2,4,4-trimethylhexane-1,6-diamine Chemical compound NCC(C)CC(C)(C)CCN DPQHRXRAZHNGRU-UHFFFAOYSA-N 0.000 claims description 2
- KSQSUDDRZLCKSW-UHFFFAOYSA-N 2,4-dimethylhexane-1,6-diamine Chemical compound NCC(C)CC(C)CCN KSQSUDDRZLCKSW-UHFFFAOYSA-N 0.000 claims description 2
- LMOSYFZLPBHEOW-UHFFFAOYSA-N 2,5-dichloroterephthalic acid Chemical compound OC(=O)C1=CC(Cl)=C(C(O)=O)C=C1Cl LMOSYFZLPBHEOW-UHFFFAOYSA-N 0.000 claims description 2
- GAGWMWLBYJPFDD-UHFFFAOYSA-N 2-methyloctane-1,8-diamine Chemical compound NCC(C)CCCCCCN GAGWMWLBYJPFDD-UHFFFAOYSA-N 0.000 claims description 2
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 claims description 2
- UFMBOFGKHIXOTA-UHFFFAOYSA-N 2-methylterephthalic acid Chemical compound CC1=CC(C(O)=O)=CC=C1C(O)=O UFMBOFGKHIXOTA-UHFFFAOYSA-N 0.000 claims description 2
- WTKWFNIIIXNTDO-UHFFFAOYSA-N 3-isocyanato-5-methyl-2-(trifluoromethyl)furan Chemical compound CC1=CC(N=C=O)=C(C(F)(F)F)O1 WTKWFNIIIXNTDO-UHFFFAOYSA-N 0.000 claims description 2
- FJSUFIIJYXMJQO-UHFFFAOYSA-N 3-methylpentane-1,5-diamine Chemical compound NCCC(C)CCN FJSUFIIJYXMJQO-UHFFFAOYSA-N 0.000 claims description 2
- MBRGOFWKNLPACT-UHFFFAOYSA-N 5-methylnonane-1,9-diamine Chemical compound NCCCCC(C)CCCCN MBRGOFWKNLPACT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 claims description 2
- 239000010425 asbestos Substances 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 claims description 2
- GWZCCUDJHOGOSO-UHFFFAOYSA-N diphenic acid Chemical compound OC(=O)C1=CC=CC=C1C1=CC=CC=C1C(O)=O GWZCCUDJHOGOSO-UHFFFAOYSA-N 0.000 claims description 2
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 claims description 2
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 239000010440 gypsum Substances 0.000 claims description 2
- 229910052602 gypsum Inorganic materials 0.000 claims description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N n-Dodecanedioic acid Natural products OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 claims description 2
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 claims description 2
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 claims description 2
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 claims description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 2
- 229910052895 riebeckite Inorganic materials 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Natural products OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- KLNPWTHGTVSSEU-UHFFFAOYSA-N undecane-1,11-diamine Chemical compound NCCCCCCCCCCCN KLNPWTHGTVSSEU-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 239000005909 Kieselgur Substances 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 238000005187 foaming Methods 0.000 abstract description 10
- 238000005516 engineering process Methods 0.000 abstract description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 4
- 238000004132 cross linking Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 17
- 238000012360 testing method Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- 229920006119 nylon 10T Polymers 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 6
- 238000005476 soldering Methods 0.000 description 6
- 239000000314 lubricant Substances 0.000 description 5
- 238000009864 tensile test Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 229920006351 engineering plastic Polymers 0.000 description 3
- 229920006139 poly(hexamethylene adipamide-co-hexamethylene terephthalamide) Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000012925 biological evaluation Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229930003827 cannabinoid Natural products 0.000 description 2
- 239000003557 cannabinoid Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- XSAOTYCWGCRGCP-UHFFFAOYSA-K aluminum;diethylphosphinate Chemical compound [Al+3].CCP([O-])(=O)CC.CCP([O-])(=O)CC.CCP([O-])(=O)CC XSAOTYCWGCRGCP-UHFFFAOYSA-K 0.000 description 1
- 229920006020 amorphous polyamide Polymers 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- MRNZSTMRDWRNNR-UHFFFAOYSA-N bis(hexamethylene)triamine Chemical compound NCCCCCCNCCCCCCN MRNZSTMRDWRNNR-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920006375 polyphtalamide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000010998 test method Methods 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
- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The polyamide composite material with high weld mark strength comprises the following components in parts by weight: 60 parts of semi-aromatic polyamide resin; 10-30 parts of a flame retardant; 0-60 parts of a reinforcing material; 0.01-1 part of triamine compound. According to the invention, a certain amount of triamine compounds are added to react with the terminal carboxyl groups of the semi-aromatic polyamide resin to form a micro-crosslinking system, so that the weld mark of the polyamide composite material is effectively wound, the aim of improving the strength of the weld mark is achieved, the foaming resistance is improved, and the polyamide composite material is especially suitable for an SMT (surface mounting technology) assembly process.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a high-solvent-strength polyamide composite material and a preparation method and application thereof.
Background
In recent years, with the high density of electronic products and the miniaturization of products, lead-free Surface Mount Technology (SMT) has become an important way of assembly. The application of the high-temperature resistant engineering plastic requires that components can bear the high temperature of 250-280 ℃, the traditional engineering plastics such as PA66 and PBT can not meet the requirement at all, and the high-temperature resistant engineering plastics can be produced at the same time. Semi-aromatic polyamide (PPA) has high melting point, high heat distortion temperature, high strength, and the like, and is widely used in the field of connectors.
The connector product has the characteristics of high fluidity, quick forming and high weld mark strength due to the fact that the material is determined by the multi-PIN structure; different from the traditional connector, the SMT assembly mode requires that the material must pass through 250-280 ℃, which is equivalent to rapid aging of the thin-walled material, and all properties of the material are reduced, especially the strength of the welding marks of the product is reduced, and the sliding is obvious.
Generally, the common methods for improving the weld marks of the materials in the prior art are as follows:
first, the product structure or the mold structure is improved, the convergence angle of the product weld mark is improved, or the weld mark is designed to be in an unstressed position, such as application number 202022094118 (mold structure for solving the weld mark on the surface of the product). However, this puts high demands on the product structure and the mold structure design, and the versatility is not strong, which also increases the design and product cost.
Secondly, the weld mark strength of the material is improved by the design from the formula. For example, patent application 200810218925 discloses a high weld mark strength reinforced polypropylene material and a preparation method thereof, wherein the welding mark strength of the material is improved by adding a coupling agent to improve the combination of a reinforcing material and resin; patent application 201510900503 discloses a polyamide material with high weld mark strength, a preparation method and application thereof, which reduces the crystallinity behavior of the material and simultaneously improves the fluidity of the material by adding a low-viscosity amorphous polyamide compound. The two schemes can improve the weld mark strength of the material, but are not suitable for SMT specification products injected by high-temperature nylon. The reason is that: the coupling agent sold in the market at present is mainly a liquid silane coupling agent, is easy to volatilize, is difficult to apply to high-temperature nylon processing, and is easy to cause the material to contain a large amount of micromolecule residues, so that the material is easy to foam when reflow soldering is carried out; and the introduction of the low-viscosity amorphous compound can destroy the crystalline behavior of the compound, reduce the cooling rate of the material, and cause the defects of burrs and the like easily existing during injection molding of thin-walled products.
Meanwhile, due to the introduction of the halogen-free flame retardant in the flame-retardant polyamide system, more gas is generated in the extrusion and processing of the material, and the injection-molded product is easier to foam in an SMT (surface mount technology) assembly mode, so that the functional problem and the appearance of the product are influenced.
Disclosure of Invention
The object of the invention is to provide a polyamide composite material with high weld line strength and improved blistering resistance.
Another object of the present invention is to provide a method for preparing the polyamide composite material having high weld mark strength.
The invention is realized by the following technical scheme:
the polyamide composite material with high weld mark strength comprises the following components in parts by weight:
60 parts of semi-aromatic polyamide resin;
10-30 parts of a flame retardant;
0-60 parts of a reinforcing material;
0.01-1 part of triamine compound.
The semi-aromatic polyamide resin is derived from diacid units and diamine units; the diacid units are derived from 45 to 100mol percent of aromatic dicarboxylic acid and 0 to 55mol percent of aliphatic dicarboxylic acid, the aromatic dicarboxylic acid is at least one of terephthalic acid, isophthalic acid, 2-methyl terephthalic acid, 2, 5-dichloro terephthalic acid, 2, 6-naphthalene dicarboxylic acid, 1, 4-naphthalene dicarboxylic acid, 4 '-biphenyl dicarboxylic acid and 2, 2' -biphenyl dicarboxylic acid, and the number of carbon atoms of the aliphatic dicarboxylic acid is 4 to 12; the diamine unit is derived from at least one of 1, 4-butanediamine, 1, 6-hexanediamine, 1, 8-octanediamine, 1, 9-nonanediamine, 1, 10-decanediamine, 1, 11-undecanediamine, 1, 12-dodecanediamine, 2-methyl-1, 5-pentanediamine, 3-methyl-1, 5-pentanediamine, 2, 4-dimethyl-1, 6-hexanediamine, 2, 4-trimethyl-1, 6-hexanediamine, 2,4, 4-trimethyl-1, 6-hexanediamine, 2-methyl-1, 8-octanediamine, 5-methyl-1, 9-nonanediamine.
The aliphatic dicarboxylic acid is at least one selected from 1, 4-succinic acid, 1, 6-adipic acid, 1, 8-suberic acid, 1, 9-azelaic acid, 1, 10-sebacic acid, 1, 11-undecanedioic acid and 1, 12-dodecanedioic acid.
The semi-aromatic polyamide resin used in the embodiment of the invention is a self-made raw material, and the method comprises the following steps:
the measured materials are added into a 20L pressure kettle, and 2 thousandths (mass of the total substance) of the 1098 antioxidant and 1 thousandth (mass of the total substance) of the sodium hypophosphite catalyst are fixedly added. In the preparation of the semi-aromatic polyamide resin, benzoic acid was used as an end-capping agent in an amount of 0.02 times the molar amount of the aromatic dicarboxylic acid unit and in an amine to carboxyl ratio (molar ratio) of 0.995 in order to make the carboxyl group in excess for reaction with the triamine compound during extrusion. After the completion of the addition, the mixture was evacuated, filled with nitrogen gas to replace the gas, and heated to a predetermined temperature of 230 ℃ to 240 ℃ and a constant pressure of 2.9 to 3.1MPa was maintained by removing the formed water. After the reaction is finished, releasing the pressure to normal pressure to obtain the prepolymer. The prepolymer is tackified in a solid phase at 240-250 ℃ in a rotary drum, and the semi-aromatic polyamide resin can be obtained after tackification for 1-3 hours.
The flame retardant is selected from at least one of phosphinate flame retardants or dialkylphosphinate flame retardants.
The reinforcing material is at least one selected from glass fiber, carbon fiber, asbestos fiber, wollastonite fiber, ceramic fiber, potassium titanate whisker, basic magnesium sulfate whisker, silicon carbide whisker, aluminum borate whisker, silicon dioxide, aluminum silicate, silicon oxide, calcium carbonate, titanium dioxide, talc, wollastonite, diatomite, clay, kaolin, spherical glass, mica and gypsum.
The triamine compound has a structure shown in the formula, wherein R1、R2、R3Is hydrogen or alkyl chain compound containing terminal amino with 1-12 carbon atoms,
specifically, wherein, n in the structural formula 11Any integer of 1 to 12, m1Any integer of 1 to 12, n1And m1May be the same or different values; n in the formula 22Any integer of 1 to 12, m2Any integer of =1-12, L = any integer of 1-12, n2、m2L may be the same or different values;
preferably, the structure of the triamine compound is shown in a structural formula 1.
Preferably, the triamine compound is contained in an amount of 0.20 to 0.75 parts by weight.
0-2 parts of auxiliary agent can be added according to actual needs, and the auxiliary agent is at least one of lubricant and oxidant.
The preparation method of the polyamide composite material with high weld mark strength comprises the following steps: according to the proportion, the components except the reinforcing material are uniformly mixed, and then are extruded and granulated by a double-screw extruder, and after the components are melted and blended at the temperature of 250-350 ℃, the polyamide composite material with high weld mark strength is obtained by cooling and granulation.
The polyamide composite material with high weld mark strength is applied to SMT manufacturing processes, such as a lamp strip bracket and an LED reflection bracket; the method is also used in the fields of high-voltage connector products, low-voltage electrical appliance products, relays, 5G communication connectors and the like.
The invention has the following beneficial effects:
according to the invention, a certain amount of triamine compounds are added to react with the terminal carboxyl groups of the semi-aromatic polyamide resin to form a micro-crosslinking system, so that the weld mark of the polyamide composite material is effectively wound, the aim of improving the strength of the weld mark is achieved, the foaming resistance is improved, and the polyamide composite material is especially suitable for an SMT (surface mounting technology) assembly process.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will aid those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any manner. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the concept of the invention. All falling within the scope of the present invention.
The raw material sources used in the examples and comparative examples are as follows:
PA10T, self-made;
PA5T/56, wherein terephthalic acid accounts for 70mol% of total acid, and is prepared by self;
PA6T/66, wherein terephthalic acid accounts for 60mol% of total acid, and is prepared by a self-made method;
PA10T/1010, wherein terephthalic acid accounts for 85mol% of total acid, and is prepared by self;
PA10T/10I, wherein terephthalic acid accounts for 90mol% of total acid, and is prepared by a self-made method.
Flame retardant A: aluminum diethylphosphinate, OP1230, clariant corporation;
and (3) a flame retardant B: zinc diethylphosphinate, PFR1210, chemical ltd, hong yu, york city;
glass fiber: commercially available, parallel tests were run with the same glass fiber;
triamine compound A-1: structural formula 1 (n)1=6，m1= 6), bis (hexamethylene) triamine, shanghai alatin biochem technology ltd;
triamine compound A-2: structure of the productFormula 1 (n)1=9，m1= 9) prepared according to the "Synthesis and Biological Evaluation of double Ligands for the Cannabinoid 1 Receptor" method (J. Med. chem. 2010, 53, 7048-;
triamine compound A-3: structural formula 1 (n)2=11，m2= 11), prepared according to the "Synthesis and Biological Evaluation of double Ligands for the Cannabinoid 1 Receptor" literature (J. Med. chem. 2010, 53, 7048-;
triamine compound B-1: structural formula 2 (n)3=5，m3=5, L = 5), prepared according to the method of international patent "a method for preparing alkylated amines", international patent number WO 2021/174523 Al;
triamine compound B-2: structural formula 2 (n)3=7，m3=7, L = 7), prepared according to the method of international patent "a method for preparing alkylated amines", international patent number WO 2021/174523 Al;
lubricant: commercially available, parallel tests used the same lubricant.
Examples and comparative examples preparation methods of polyamide composite materials: according to the proportion, the components except the reinforcing material are uniformly mixed, and then are extruded and granulated through a double-screw extruder, the reinforcing material is fed laterally, and after the components are melted and blended at the temperature of 250-350 ℃, the components are cooled and granulated to obtain the polyamide composite material with high weld mark strength.
The test methods are as follows:
(1) tensile strength: feeding the polyamide composition from a single side, and injection molding into ISO tensile test sample strips; the test bars were tested for tensile strength according to ISO-527-2:2012 standard after conditioning for 24h at 23 ℃ in a 50% RH laboratory standard environment.
(2) Weld mark strength before reflow: feeding the polyamide composition from two sides simultaneously, and performing injection molding to obtain an ISO tensile test sample strip, wherein the fusion line converging position is in the middle of the tensile test sample strip; test bars were tested for weld mark strength according to ISO-527-2:2012 standard after conditioning for 24 hours at 23 ℃ in a 50% RH laboratory standard environment.
(3) Strength of a welding mark after reflow soldering: feeding the polyamide composition from two sides simultaneously, and performing injection molding to obtain an ISO tensile test sample strip, wherein the fusion line converging position is in the middle of the tensile test sample strip; placing the sample strip in SER-710A equipment of Ziguangdong science and technology (Shenzhen) Limited, heating from room temperature to 150 ℃ within 45 seconds in air, heating from 150 ℃ to 200 ℃ within 135 seconds, heating to 260 ℃ at the maximum temperature rise rate of 3 ℃/s, wherein the time of above 255 ℃ is 20-40 seconds, and cooling to room temperature at the maximum temperature drop rate of 6 ℃/s; finally, testing the weld mark strength according to the ISO-527-2:2012 standard after adjusting the test sample bar in a laboratory standard environment with 50% RH at 23 ℃ for 24 h.
(4) Foaming temperature resistance: the polyamide composite materials of the examples or comparative examples were dried at 120 ℃ for 4h and then injection molded into 60 x 1mm square plaques, and tested after soaking in water at 23 ℃ for 24 h. Placing the test piece in SER-710A equipment of Ziguangdong science and technology (Shenzhen) Limited, heating from room temperature to 150 ℃ within 45 seconds in air, heating from 150 ℃ to 200 ℃ within 135 seconds, heating to the peak temperature at the maximum temperature rise rate of 3 ℃/s, cooling to room temperature at the maximum temperature drop rate of 6 ℃/s, taking out the test piece, and observing whether the test piece has a foaming phenomenon; wherein the peak temperature is gradually increased by taking 250 ℃ as a starting point and 5 ℃ as a step, and the peak temperature-5 ℃ corresponding to the foaming of the test piece is the foaming-resistant temperature.
Table 1: examples 1-6 high weld mark polyamide composite Material content (parts by weight) and test results
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | |
| PA10T | 60 | 60 | 60 | 60 | 60 | 60 |
| Flame retardant A | 20 | 20 | 20 | 20 | 20 | 20 |
| Glass fiber | 30 | 30 | 30 | 30 | 30 | 30 |
| Triamine compound A-1 | 0.3 | 0.3 | ||||
| Triamine compound A-2 | 0.3 | |||||
| Triamine compound A-3 | 0.3 | |||||
| Triamine compound B-1 | 0.3 | |||||
| Triamine compound B-2 | 0.3 | |||||
| Lubricant agent | 0.2 | |||||
| Tensile strength, MPa | 140 | 138 | 137 | 135 | 132 | 140 |
| Weld mark strength before reflow, MPa | 57 | 54 | 53 | 52 | 50 | 58 |
| Weld mark strength after reflow, MPa | 54 | 50 | 47 | 47 | 45 | 54 |
| Resistance to foaming temperature,. degree.C | 275 | 275 | 275 | 275 | 275 | 270 |
As is clear from examples 1 to 5, the triamine compound of the formula 1 is preferable, and the weld mark strength is more excellent.
It is understood from example 1/6 that the addition of a lubricant increases the weld line strength to some extent, but also affects the blister temperature resistance.
Table 2: examples 7-13 high weld mark polyamide composite Material content (parts by weight) and test results
| Example 7 | Example 8 | Example 9 | Example 10 | Example 11 | Example 12 | Example 13 | |
| PA10T | 60 | 60 | 60 | ||||
| PA5T/56 | 60 | ||||||
| PA6T/66 | 60 | ||||||
| PA10T/1010 | 60 | ||||||
| PA10T/10I | 60 | ||||||
| Flame retardant A | 10 | 20 | 20 | 20 | 20 | 20 | |
| Flame retardant B | 30 | ||||||
| Glass fiber | 10 | 40 | 60 | 30 | 30 | 30 | 30 |
| Triamine compound A-1 | 0.01 | 0.6 | 1.0 | 0.3 | 0.3 | 0.3 | 0.3 |
| Tensile strength, MPa | 100 | 145 | 170 | 150 | 148 | 142 | 140 |
| Weld mark strength before reflow, MPa | 54 | 53 | 57 | 55 | 54 | 50 | 48 |
| Weld mark strength after reflow soldering, MPa | 51 | 48 | 53 | 49 | 48 | 45 | 44 |
| Resistance to foaming temperature,. degree.C | 270 | 270 | 280 | 260 | 260 | 275 | 275 |
As is clear from examples 7 to 13 and comparative examples, the object of the present invention can be achieved within the scope of the present invention.
Table 3: examples 14-17 high weld mark polyamide composite Material content (parts by weight) and test results
| Example 14 | Example 15 | Example 16 | Example 17 | |
| PA10T | 60 | 60 | 60 | 60 |
| Flame retardant A | 20 | 20 | 20 | 20 |
| Glass fiber | 30 | 30 | 30 | 30 |
| Triamine compound A-1 | 0.01 | 0.2 | 0.75 | 1.0 |
| Tensile strength, MPa | 140 | 140 | 140 | 138 |
| Weld mark strength before reflow, MPa | 55 | 56 | 53 | 51 |
| Weld mark strength after reflow soldering, MPa | 48 | 51 | 50 | 48 |
| Resistance to foaming temperature,. degree.C | 270 | 275 | 280 | 280 |
As is clear from examples 1/14 to 17, the total performance is better when the content of the triamine compound is preferably 0.20 to 0.75 part by weight.
Table 4: comparative example high weld mark polyamide composite Material content (parts by weight) and test results
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| PA10T | 60 | 60 | ||
| PA6T/66 | 60 | |||
| PA5T/56 | 60 | |||
| Flame retardant A | 20 | 20 | 20 | 20 |
| Glass fiber | 30 | 30 | 30 | 30 |
| Triamine compound A-1 | 1.2 | |||
| Tensile strength, MPa | 138 | 140 | 145 | 142 |
| Weld mark strength before reflow, MPa | 45 | 53 | 51 | 48 |
| Weld mark strength after reflow soldering, MPa | 42 | 40 | 38 | 36 |
| Resistance to foaming temperature,. degree.C | 280 | 265 | 250 | 250 |
Comparative example 1 shows that the addition amount of the triamine compound is too high, which in turn causes a decrease in weld mark strength.
As is clear from comparative examples 2 to 4, when no triamine compound was added, the weld mark strength after reflow soldering was very low and the blister temperature was low.
Claims (10)
1. The polyamide composite material with high weld mark strength is characterized by comprising the following components in parts by weight:
60 parts of semi-aromatic polyamide resin;
10-30 parts of a flame retardant;
0-60 parts of reinforcing materials;
0.01-1 part of triamine compound.
2. The high weld mark strength polyamide composite material according to claim 1, wherein the semi-aromatic polyamide resin is derived from diacid units and diamine units; the diacid unit is derived from 45 to 100mol percent of aromatic dicarboxylic acid and 0 to 55mol percent of aliphatic dicarboxylic acid, the aromatic dicarboxylic acid is at least one of terephthalic acid, isophthalic acid, 2-methyl terephthalic acid, 2, 5-dichloro terephthalic acid, 2, 6-naphthalene dicarboxylic acid, 1, 4-naphthalene dicarboxylic acid, 4 '-biphenyl dicarboxylic acid and 2, 2' -biphenyl dicarboxylic acid, and the carbon number of the aliphatic dicarboxylic acid is 4 to 12; the diamine unit is derived from at least one of 1, 4-butanediamine, 1, 6-hexanediamine, 1, 8-octanediamine, 1, 9-nonanediamine, 1, 10-decanediamine, 1, 11-undecanediamine, 1, 12-dodecanediamine, 2-methyl-1, 5-pentanediamine, 3-methyl-1, 5-pentanediamine, 2, 4-dimethyl-1, 6-hexanediamine, 2, 4-trimethyl-1, 6-hexanediamine, 2,4, 4-trimethyl-1, 6-hexanediamine, 2-methyl-1, 8-octanediamine, 5-methyl-1, 9-nonanediamine.
3. The high weld mark strength polyamide composite material as claimed in claim 2, wherein the aliphatic dicarboxylic acid is at least one selected from 1, 4-succinic acid, 1, 6-adipic acid, 1, 8-suberic acid, 1, 9-azelaic acid, 1, 10-sebacic acid, 1, 11-undecanedioic acid, and 1, 12-dodecanedioic acid.
4. A high weld mark strength polyamide composite material as claimed in claim 1, wherein the flame retardant is selected from at least one of phosphinate flame retardants or dialkylphosphinate flame retardants.
5. The polyamide composite material with high weld mark strength as claimed in claim 1, wherein the reinforcing material is at least one selected from the group consisting of glass fiber, carbon fiber, asbestos fiber, wollastonite fiber, ceramic fiber, potassium titanate whisker, basic magnesium sulfate whisker, silicon carbide whisker, aluminum borate whisker, silica, aluminum silicate, calcium carbonate, titanium dioxide, talc, wollastonite, diatomaceous earth, clay, kaolin, spherical glass, mica, and gypsum.
6. A high weld mark strength polyamide composite material as claimed in claim 1, wherein the triamine compound has the following formula, wherein R is1、R2、R3Is hydrogen, or alkyl chain containing terminal amino with 1-12 carbon atoms, or aromatic ring compound containing terminal amino,
the triamine compound is selected from at least one of the following structural formulas;
wherein n in the structural formula 11Any integer of 1 to 12, m1Any integer of 1-12; n in the formula 22Any integer of 1 to 12, m2Any integer of 1-12, L = any integer of 1-12;
7. a high weld mark strength polyamide composite material according to claim 1, characterized in that the triamine compound is contained in an amount of 0.20 to 0.75 parts by weight.
8. A high weld mark strength polyamide composite material as claimed in claim 1, wherein the triamine compound is selected from formula 1.
9. A method for preparing a high weld mark strength polyamide composite material as claimed in any one of claims 1 to 8, characterized by comprising the steps of: according to the proportion, the components except the reinforcing material are uniformly mixed, and then are extruded and granulated by a double-screw extruder, and after the components are melted and blended at the temperature of 250-350 ℃, the polyamide composite material with high weld mark strength is obtained by cooling and granulation.
10. Use of a high weld mark strength polyamide composite material according to any one of claims 1 to 8, characterised in that it is used in an SMT manufacturing process.
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| CN112677612A (en) * | 2020-12-21 | 2021-04-20 | 珠海万通特种工程塑料有限公司 | Laser-weldable high-temperature-resistant polyamide composite material and preparation method and application thereof |
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