CN115850962B - Halogen-free flame-retardant reinforced nylon material and preparation method and application thereof - Google Patents
Halogen-free flame-retardant reinforced nylon material and preparation method and application thereof Download PDFInfo
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- CN115850962B CN115850962B CN202310030410.XA CN202310030410A CN115850962B CN 115850962 B CN115850962 B CN 115850962B CN 202310030410 A CN202310030410 A CN 202310030410A CN 115850962 B CN115850962 B CN 115850962B
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 97
- 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 title claims abstract description 80
- 239000004677 Nylon Substances 0.000 title claims abstract description 73
- 229920001778 nylon Polymers 0.000 title claims abstract description 73
- 239000000463 material Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- -1 phosphorus-nitrogen modified silane Chemical class 0.000 claims abstract description 43
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003365 glass fiber Substances 0.000 claims abstract description 22
- 239000000314 lubricant Substances 0.000 claims abstract description 18
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 15
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 15
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 14
- 239000011777 magnesium Substances 0.000 claims abstract description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 13
- 239000011574 phosphorus Substances 0.000 claims abstract description 13
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 13
- 239000010703 silicon Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- REBHQKBZDKXDMN-UHFFFAOYSA-M [PH2]([O-])=O.C(C)[Al+]CC Chemical compound [PH2]([O-])=O.C(C)[Al+]CC REBHQKBZDKXDMN-UHFFFAOYSA-M 0.000 claims abstract description 11
- 238000012545 processing Methods 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 claims description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 7
- 230000009471 action Effects 0.000 claims description 7
- OLLFKUHHDPMQFR-UHFFFAOYSA-N dihydroxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](O)(O)C1=CC=CC=C1 OLLFKUHHDPMQFR-UHFFFAOYSA-N 0.000 claims description 7
- UBIJTWDKTYCPMQ-UHFFFAOYSA-N hexachlorophosphazene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 UBIJTWDKTYCPMQ-UHFFFAOYSA-N 0.000 claims description 7
- DZKXDEWNLDOXQH-UHFFFAOYSA-N 1,3,5,2,4,6-triazatriphosphinine Chemical compound N1=PN=PN=P1 DZKXDEWNLDOXQH-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000010008 shearing Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 8
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 abstract description 6
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 abstract description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000004952 Polyamide Substances 0.000 description 8
- 239000002131 composite material Substances 0.000 description 8
- 229920002647 polyamide Polymers 0.000 description 8
- 229920000877 Melamine resin Polymers 0.000 description 5
- 229920000388 Polyphosphate Polymers 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 5
- 239000001205 polyphosphate Substances 0.000 description 5
- 235000011176 polyphosphates Nutrition 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000012043 crude product Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 229920006122 polyamide resin Polymers 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- LXWPJAGZRHTAOO-UHFFFAOYSA-N [Sb].[Br] Chemical compound [Sb].[Br] LXWPJAGZRHTAOO-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 2
- PUAQLLVFLMYYJJ-UHFFFAOYSA-N 2-aminopropiophenone Chemical compound CC(N)C(=O)C1=CC=CC=C1 PUAQLLVFLMYYJJ-UHFFFAOYSA-N 0.000 description 1
- 239000004953 Aliphatic polyamide Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002262 Schiff base Chemical group 0.000 description 1
- 150000004753 Schiff bases Chemical group 0.000 description 1
- 239000004110 Zinc silicate Substances 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical group [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229920003231 aliphatic polyamide Polymers 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- ZIWYFFIJXBGVMZ-UHFFFAOYSA-N dioxotin hydrate Chemical compound O.O=[Sn]=O ZIWYFFIJXBGVMZ-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910001853 inorganic hydroxide Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000007974 melamines Chemical class 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
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical group CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229960001296 zinc oxide Drugs 0.000 description 1
- XSMMCTCMFDWXIX-UHFFFAOYSA-N zinc silicate Chemical compound [Zn+2].[O-][Si]([O-])=O XSMMCTCMFDWXIX-UHFFFAOYSA-N 0.000 description 1
- 235000019352 zinc silicate Nutrition 0.000 description 1
- BNEMLSQAJOPTGK-UHFFFAOYSA-N zinc;dioxido(oxo)tin Chemical compound [Zn+2].[O-][Sn]([O-])=O BNEMLSQAJOPTGK-UHFFFAOYSA-N 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a halogen-free flame-retardant reinforced nylon material, and a preparation method and application thereof. The halogen-free flame-retardant reinforced nylon material comprises the following raw materials: nylon, glass fiber, diethyl aluminum phosphinate, a flame retardant synergist, an antioxidant and a lubricant, wherein the flame retardant synergist comprises a mixture of phosphorus-nitrogen modified silane and stevensite. The halogen-free flame-retardant reinforced nylon material is prepared by a double-screw extruder. According to the halogen-free flame-retardant reinforced nylon material based on the synergy of phosphorus, nitrogen, silicon and magnesium, which is provided by the invention, the diethyl aluminum hypophosphite is adopted as a flame retardant, and the synthesized phosphorus-nitrogen modified silane and the stevensite are designed to serve as flame-retardant synergists to replace traditional MPP or zinc borate and the like, so that the obtained halogen-free flame-retardant reinforced nylon material has excellent mechanical property, flame retardant property and processability, and the material has good temperature resistance in the processing process and generates less mold scale.
Description
Technical Field
The invention relates to a nylon material, in particular to a halogen-free flame-retardant reinforced nylon material based on the synergism of phosphorus, nitrogen, silicon and magnesium, and a preparation method and application thereof, and belongs to the technical field of high polymer materials.
Background
As engineering plastics, the polyamide (nylon) material has higher mechanical property, impact property and higher heat resistance, is a material with excellent performance, and is widely applied in the fields of electronic appliances, LED illumination, automobile industry and the like. However, nylon is easy to burn, and cannot meet the high flame retardant performance requirements of the nylon in the fields of electronics and electricity, new energy automobiles, aerospace, buildings and the like. With the development of electronic and electric, household appliances and new energy automobile parts to the high-performance miniaturization, the requirements on nylon flame retardance are stricter, and meanwhile, green and environment-friendly products are also the future development trend. Therefore, the preparation of the nylon with high flame retardant property has practical significance for expanding the application of flame retardant nylon materials and promoting the development of the electronic and electric industry.
In order to improve the flame retardant property of nylon, a flame retardant is often required to be added into nylon resin to realize the fireproof function. In the prior art, a halogen or halogen-free flame retardant is usually added into nylon to realize flame retardance. Although the bromine-antimony flame retardant has excellent flame retardant effect, the bromine-antimony flame retardant system has high smoke density and has adverse effects on human bodies and the environment. Chinese patent CN114874616a discloses a halogen-free flame retardant polyamide composite material with anti-yellowing and low-modulus and its preparation method. The polyamide composite material comprises the following components: polyamide resin, compound halogen-free flame retardant, metal oxide, polyhydroxy component and other auxiliary agents; the compound halogen-free flame retardant comprises alkyl phosphinate, melamine polyphosphate and zinc borate; the ratio of the polyamide resin to the compound halogen-free flame retardant to the metal oxide to the polyhydroxy component is (40-60) to (15-25) to (0.2-1.5) in parts by weight. Chinese patent CN114456593a discloses an anti-tracking halogen-free flame retardant polyamide composite material, and preparation method and application thereof, comprising the following components in parts by weight: 10-60 parts of aliphatic polyamide, 5-50 parts of aromatic polyamide, 10-50 parts of glass fiber, 8-20 parts of hypophosphite, 0.3-1 part of melamine derivative and 2-10 parts of inorganic hydroxide. Chinese patent CN114181521a discloses a halogen-free flame retardant polyamide composite material and a preparation method thereof. The halogen-free flame-retardant polyamide composite material comprises, by weight, 35-88 parts of polyamide resin, 2-30 parts of filler, 10-30 parts of flame retardant composition and 0.5-5 parts of auxiliary materials, wherein the flame retardant composition consists of aluminum diethylphosphinate, an organosilicon compound and modified zinc borate. Chinese patent CN112662171a discloses a halogen-free flame retardant reinforced polyamide composite material, its preparation method and application. The halogen-free flame-retardant reinforced polyamide composite material comprises the following components: polyamide resins, organic hypophosphites, surface-coated melamine polyphosphate, corrosion inhibitors, silicone masterbatches and fibers; wherein the corrosion inhibitor comprises an esterified polyol and at least one of zinc borate, zinc stannate, boehmite, hydrotalcite, zinc oxide, zinc hydroxide, basic zinc silicate, or tin dioxide hydrate. The hypophosphite flame retardant is added into nylon, and the flame retardant such as melamine polyphosphate and zinc borate is cooperated to effectively improve the flame retardant property of the nylon, but the melamine polyphosphate has poor thermal stability, a large amount of acidic substances are easily generated in the processing process, the mechanical property of the material is influenced, the compatibility of zinc borate and nylon is poor, precipitation is easily generated after long-term use, and the quality of the material is influenced.
Disclosure of Invention
The invention aims to solve the defects of the technology and provides a halogen-free flame-retardant reinforced nylon material based on the cooperation of phosphorus, nitrogen, silicon and magnesium and a preparation method thereof.
The invention also aims at providing the application of the halogen-free flame-retardant reinforced nylon material.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
the embodiment of the invention provides a halogen-free flame-retardant reinforced nylon material, which comprises the following raw materials: nylon, glass fiber, diethyl aluminum phosphinate, a flame retardant synergist, an antioxidant and a lubricant, wherein the flame retardant synergist comprises a mixture of phosphorus-nitrogen modified silane and stevensite.
In some embodiments, the raw materials of the halogen-free flame retardant reinforced nylon material comprise the following components in parts by weight: 30-75 parts of nylon, 15-45 parts of glass fiber, 6-10 parts of diethyl aluminum phosphinate, 2-4 parts of flame retardant synergist, 0.1-0.5 part of antioxidant and 0.2-1.0 part of lubricant.
In some embodiments, the mass ratio of phosphorus-nitrogen modified silane to stevensite in the flame retardant synergist is 1:1 to 1:4.
the embodiment of the invention also provides a preparation method of the halogen-free flame-retardant reinforced nylon material, which comprises the following steps:
under the double screw conveying and shearing actions, the mixed system of nylon, diethyl aluminum phosphinate, phosphorus-nitrogen modified silane, stevensite, antioxidant and lubricant is fully melted and plasticized, and then bracing, cooling and granulating are carried out, so that the halogen-free flame-retardant reinforced nylon material based on the synergy of phosphorus, nitrogen, silicon and magnesium is prepared.
The embodiment of the invention also provides application of the halogen-free flame-retardant reinforced nylon material in preparing electronic and electric or new energy automobile connectors and the like.
Compared with the prior art, the invention has at least the following advantages:
according to the halogen-free flame-retardant reinforced nylon material based on the synergy of phosphorus, nitrogen, silicon and magnesium, which is provided by the invention, the diethyl aluminum hypophosphite is adopted as a flame retardant, and the synthesized phosphorus-nitrogen modified silane and the stevensite are designed to serve as flame-retardant synergists to replace traditional MPP or zinc borate and the like, so that the obtained halogen-free flame-retardant reinforced nylon material has excellent mechanical property, flame retardant property and processability, and the material has good temperature resistance in the processing process and generates less mold scale.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments described in the present invention, and other drawings may be obtained according to the drawings without inventive effort to those skilled in the art.
FIG. 1 is an infrared spectrum of a phosphorus-nitrogen modified silane in an exemplary embodiment of the present invention.
Detailed Description
In view of the defects existing in the prior art, the inventor of the present invention has long-term research and a great deal of practice, and has proposed the technical scheme of the present invention, mainly to provide a halogen-free flame-retardant reinforced nylon material based on the synergy of phosphorus, nitrogen, silicon and magnesium, and a preparation method thereof, wherein the material has excellent mechanical properties, flame retardant properties and processability. The technical scheme, the implementation process, the principle and the like are further explained as follows.
Specifically, as one aspect of the technical scheme of the invention, the halogen-free flame-retardant reinforced nylon material based on the synergy of phosphorus, nitrogen, silicon and magnesium comprises the following raw materials: nylon, glass fiber, diethyl aluminum phosphinate, a flame retardant synergist, an antioxidant and a lubricant, wherein the flame retardant synergist comprises a mixture of phosphorus-nitrogen modified silane and stevensite.
In some embodiments, the flame retardant synergist is a mixture of phosphorus-nitrogen modified silane and stevensite, and the mass part ratio of the phosphorus-nitrogen modified silane to the stevensite is 1:1 to 1:4.
according to the invention, the phosphorus-nitrogen modified silane and the stevensite are synthesized to serve as flame-retardant synergists, so that the flame-retardant reinforced high-temperature nylon material has excellent mechanical properties, flame retardant properties and processability, and is good in temperature resistance and less in mold scale in the processing process.
The protocol action mechanism of each component in the halogen-free flame-retardant reinforced nylon material based on the synergism of phosphorus, nitrogen, silicon and magnesium is as follows: the diethyl aluminum hypophosphite is used as a flame retardant, the synthesized phosphorus-nitrogen modified silane and the stevensite are designed to be used as flame retardant synergists to replace traditional MPP or zinc borate and the like, phosphazene, schiff base and benzene ring structures are introduced into the phosphorus-nitrogen modified silane, so that the carbon forming performance of nylon is effectively improved, and silane with a branched chain structure is introduced to effectively synergistically act with magnesium element, so that the flame retardant performance of the nylon material is further improved. In addition, the phosphorus-nitrogen modified silane is designed and introduced with an amino structure, so that the compatibility of the silane and a nylon matrix is greatly improved, and the dispersibility of the flame retardant in the nylon resin is facilitated, so that the excellent flame retardant performance is met under the condition of lower flame retardant addition.
In some embodiments, the halogen-free flame retardant reinforced nylon material comprises the following materials in parts by weight: 30-75 parts of nylon, 15-45 parts of glass fiber, 6-10 parts of diethyl aluminum phosphinate, 2-4 parts of flame retardant synergist, 0.1-0.5 part of antioxidant and 0.2-1.0 part of lubricant.
In some embodiments, the stevensite has a particle size of 1-10 μm, the stevensite has a silica content of 45wt% or more (45% or more) and a magnesia content of 30wt% or more (30% or more).
In some embodiments, the phosphazene modified silane is prepared by reacting 4-hydroxybenzaldehyde, hexachlorotriphosphazene, aminopropyl triethoxysilane, and diphenyldihydroxysilane in a molar ratio of 6:1:20:10 to 7:1:35:12.5.
Specifically, the preparation method of the phosphorus-nitrogen modified silane comprises the following steps:
dissolving 4-hydroxybenzaldehyde in tetrahydrofuran and triethylamine as an acid binding agent, and reacting with hexachloro-triphosphazene to obtain hexa (4-aldehyde phenoxy) cyclotriphosphazene;
and (3) enabling the hexa (4-aldehyde phenoxy) cyclotriphosphazene to react with aminopropyl triethoxysilane, and then adding diphenyl dihydroxysilane to continue to react to obtain phosphorus-nitrogen modified silane.
In some preferred embodiments, the method for preparing the phosphorus-nitrogen modified silane specifically comprises the steps of:
(1) Synthesis of hexa (4-aldehyde phenoxy) cyclotriphosphazene
1.4mol of 4-hydroxybenzaldehyde is dissolved in a sufficient amount of Tetrahydrofuran (THF) and 1.4mol of Triethylamine (TEA) as acid binding agents and added into a reaction kettle, and a magnetic stirring device, a condenser tube and a nitrogen protection device are arranged. 70g of Hexachlorotriphosphazene (HCCP) is dissolved in THF, and then dropwise added at room temperature, and after the dropwise addition, the temperature is raised to the reflux temperature (65-75 ℃) for continuous reaction for 24-48 h. Filtering twice after the reaction is finished to remove triethylamine hydrochloride, obtaining filtrate, removing solvent by rotary evaporation, then pouring the filtrate into a large amount of water for sedimentation, and obtaining a crude product after washing the obtained solid by water. The crude product was recrystallized from ethyl acetate to give the product.
(2) And (2) refluxing 1.5mol of the product obtained in the step (1) and 7mol of aminopropyl triethoxysilane in a large amount of ethyl acetate (80-90 ℃) for reaction for 6-10 hours, then adding 2.5mol of diphenyldihydroxysilane for continuous reaction for 8-12 hours, filtering to obtain a solid, and fully washing and drying to obtain the phosphorus-nitrogen modified silane.
In some embodiments, the nylon may include any one or a combination of two of PA6, PA66, and the like, but is not limited thereto.
Further, the glass fibers are chopped glass fibers, and the diameter of the glass fibers is 9-11 μm.
Further, the antioxidant may be an antioxidant 1098, but is not limited thereto.
Further, the lubricant may be a lubricant E wax, but is not limited thereto.
Another aspect of the embodiment of the present invention provides a method for preparing the halogen-free flame retardant reinforced nylon material, which includes:
under the double screw conveying and shearing actions, the mixed system of nylon, diethyl aluminum phosphinate, phosphorus-nitrogen modified silane, stevensite, antioxidant and lubricant is fully melted and plasticized, and then bracing, cooling and granulating are carried out, so that the halogen-free flame-retardant reinforced nylon material based on the synergy of phosphorus, nitrogen, silicon and magnesium is prepared.
In some preferred embodiments, the preparation method of the halogen-free flame-retardant reinforced nylon material based on the synergy of phosphorus, nitrogen, silicon and magnesium comprises the following steps:
the nylon base material, diethyl aluminum phosphinate, phosphorus nitrogen modified silane, stevensite, antioxidant and lubricant are fed through a main feeding port of a double-screw extruder, glass fibers are added through side feeding, and the obtained mixed system material is fully melted and plasticized under the double-screw conveying and shearing actions, and then is subjected to bracing, cooling and granulating to obtain the halogen-free flame-retardant reinforced nylon material. Wherein the rotating speed of the double-screw extruder is 300-500 rpm, and the processing temperature is 220-260 ℃.
The invention also provides an application of the halogen-free flame-retardant reinforced nylon material based on the synergism of phosphorus, nitrogen, silicon and magnesium in the fields of preparation of electronic and electrical connectors, new energy automobile connectors and the like.
By means of the technical scheme, the halogen-free flame-retardant reinforced nylon material based on the synergism of phosphorus, nitrogen, silicon and magnesium adopts diethyl aluminum hypophosphite as a flame retardant, and the synthetic phosphorus-nitrogen modified silane and the stevensite are designed to serve as flame-retardant synergists to replace traditional MPP or zinc borate and the like, so that the obtained halogen-free flame-retardant reinforced nylon material has excellent mechanical properties, flame retardant properties and processability, and is good in temperature resistance in the processing process, and few in mold scale are produced.
The invention will be explained in more detail below by means of a specific embodiment and the accompanying drawings. It should be understood, however, that the specific functional details disclosed in this specification are not to be interpreted as limiting, but merely as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the present invention in virtually any appropriately detailed embodiment. The test methods in the following examples, in which no specific conditions are noted, were all conducted under conventional conditions. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
The raw materials used in the following examples were: PA6 (new painting mada), PA66 (new material of Zhejiang new), chopped glass fiber (boulder, alkali-free chopped glass fiber, diameter of 9-12 μm, length of 3-4.5 mm), diethyl aluminum hypophosphite (clahn), lubricant E wax (commercially available), antioxidant 1098 (basf), 4-hydroxybenzaldehyde (albestic reagent), ethyl acetate (albestic reagent), hexachloro-triphosphazene (albestic reagent), aminopropyl triethoxysilane (albestic reagent), diphenyl dihydroxy silane (albestic reagent), stevensite (sushi, auspicious chemical technology, ltd), melamine polyphosphate (MPP, hangjieshi).
The procedure for examples 1-4 is as follows:
(1) Synthesis of hexa (4-aldehyde phenoxy) cyclotriphosphazene
1.4mol of 4-hydroxybenzaldehyde is dissolved in a sufficient amount of Tetrahydrofuran (THF) and 1.4mol of Triethylamine (TEA) as acid binding agents and added into a reaction kettle, and a magnetic stirring device, a condenser tube and a nitrogen protection device are arranged. 70g of Hexachlorotriphosphazene (HCCP) are dissolved in THF and then added dropwise at room temperature, after which the reaction is continued by heating to reflux temperature (70 ℃ C.). Filtering twice after the reaction is finished to remove triethylamine hydrochloride, obtaining filtrate, removing solvent by rotary evaporation, then pouring the filtrate into a large amount of water for sedimentation, and obtaining a crude product after washing the obtained solid by water. The crude product was recrystallized from ethyl acetate to give the product.
(2) And (3) heating and refluxing 1.5mol of the product obtained in the step (1) and 7mol of aminopropyl triethoxysilane in a large amount of ethyl acetate for 6-10 hours, then adding 2.5mol of diphenyldihydroxysilane, continuously stirring for reaction for 8 hours, filtering to obtain a solid, and fully washing and drying to obtain the phosphorus-nitrogen modified silane.
As shown in FIG. 1, according to the infrared spectrum (IR v/cm -1 ) Obtained, 1701cm -1 At the-C=O (carbonyl) peak, the characteristic peak of benzene ring C=C appears at 1600cm -1 And 1500cm -1 ，1175cm -1 The infrared characteristic peak at the position is attributed to P=N telescopic vibration, 959cm -1 The infrared characteristic peak is the stretching vibration peak of P-O-C, which shows that the phosphorus-nitrogen modified silane introduces the phosphorus-nitrogen and benzene ring structure.
Feeding nylon base material, diethyl aluminum phosphinate, phosphorus nitrogen modified silane, stevensite, antioxidant and lubricant through a main feeding port of a double-screw extruder, adding glass fiber through side feeding, fully melting and plasticizing the material under the double-screw conveying and shearing actions, bracing, cooling and granulating to obtain the nylon composite material. Wherein the rotating speed of the double-screw extruder is 300-500 rpm, and the processing temperature is 220-260 ℃.
The grain size of the stevensite adopted in the above example is 1-10 μm, the content of silicon dioxide in the stevensite is more than or equal to 45%, and the content of magnesium oxide is more than or equal to 30%. The glass fibers are chopped glass fibers, and the diameter of the glass fibers is 9-11 mu m.
Comparative examples 1 to 3
Comparative examples 1 to 3 differ from examples 1 to 4 in that: in the comparative examples, conventional zinc borate or MPP is adopted as a flame retardant synergist, and in examples 1-4, phosphorus-nitrogen modified silane and stevensite are adopted to synergistically prepare diethyl aluminum hypophosphite flame retardant modified nylon, so that a lower flame retardant adding proportion is realized, and better mechanical performance and flame retardant performance are obtained.
Comparative example 4
This comparative example differs from examples 1-4 in that: phosphorus-nitrogen modified silane was added but no stevensite was added.
Comparative example 5
This comparative example differs from examples 1-4 in that: stevensite was added, but no phosphazene modified silane was added.
Comparative example 6
This comparative example differs from examples 1-4 in that: the mass ratio of the phosphorus-nitrogen modified silane to the stevensite is greater than 1:4.
The material ratios of examples 1 to 4 and comparative examples 1 to 6 are shown in Table 1.
TABLE 1 Material ratios for examples 1-4 and comparative examples 1-3
The pellets obtained in each of the above examples and comparative examples were injection molded into respective bars according to ISO test standards, and then were subjected to a test after being left to stand for 24 hours at 23.+ -. 2 ℃ under an environment of 50.+ -. 5% relative humidity; tensile strength was measured according to ISO527 standard; flexural strength was measured according to ISO178 standard; the Charpy (Charpy impact test) notched impact strength was measured according to ISO179 standard. The results obtained from the test are shown in Table 2.
TABLE 2 pellet test results
The results show that the halogen-free flame-retardant reinforced nylon materials prepared in the examples 1-4 have excellent mechanical properties, flame retardant properties and processability, and the materials have good temperature resistance in the processing process and generate less mold deposit.
Further, the present inventors have conducted experiments with reference to the foregoing examples 1 to 4, with other raw materials, process operations, process conditions described in the present specification, for example, nylon was mixed at 75 parts, glass fiber was 45 parts, antioxidant was 0.1 parts and 0.5 parts, lubricant was 0.2 parts and 1.0 part, aluminum diethylphosphinate was 6 parts, and the like, as compared with examples 1 to 4, and all of the preferable results were obtained.
The foregoing is merely illustrative of specific embodiments of the present invention, but the design concept of the present invention is not limited thereto, and any insubstantial modification of the present invention by using the design concept shall fall within the scope of the present invention.
Claims (10)
1. The halogen-free flame-retardant reinforced nylon material is characterized by comprising the following raw materials in percentage by weight: 30-75 parts of nylon, 15-45 parts of glass fiber, 6-10 parts of diethyl phosphinic acid aluminum, 2-4 parts of flame retardant synergist, 0.1-0.5 part of antioxidant and 0.2-1.0 part of lubricant, wherein the flame retardant synergist is a mixture of phosphorus-nitrogen modified silane and stevensite, the mass ratio of the phosphorus-nitrogen modified silane to the stevensite is 1:1-1:4, and the phosphorus-nitrogen modified silane is prepared by reacting 4-hydroxybenzaldehyde, hexachlorotriphosphazene, aminopropyl triethoxysilane and diphenyl dihydroxysilane according to the mol ratio of 6:1:20:10-7:1:35:12.5.
2. The halogen-free flame retardant reinforced nylon material of claim 1, wherein: the grain diameter of the stevensite is 1-10 mu m, the content of silicon dioxide in the stevensite is more than 45wt%, and the content of magnesium oxide is more than 30 wt%.
3. The halogen-free flame retardant reinforced nylon material of claim 1, wherein: the nylon comprises any one or combination of two of PA6 and PA 66.
4. The halogen-free flame retardant reinforced nylon material of claim 1, wherein: the glass fiber comprises chopped glass fiber, and the diameter of the glass fiber is 9-11 mu m.
5. The halogen-free flame retardant reinforced nylon material of claim 1, wherein: the antioxidant comprises an antioxidant 1098; and/or, the lubricant comprises lubricant E wax.
6. The method for preparing a halogen-free flame retardant reinforced nylon material according to any one of claims 1 to 5, comprising:
under the double screw conveying and shearing actions, the mixed system of nylon, diethyl aluminum phosphinate, phosphorus-nitrogen modified silane, stevensite, antioxidant and lubricant is fully melted and plasticized, and then bracing, cooling and granulating are carried out, so that the halogen-free flame-retardant reinforced nylon material based on the synergy of phosphorus, nitrogen, silicon and magnesium is prepared.
7. The method of manufacturing according to claim 6, comprising:
the nylon base material, diethyl aluminum phosphinate, phosphorus nitrogen modified silane, stevensite, antioxidant and lubricant are fed through a main feeding port of a double-screw extruder, glass fibers are added through side feeding, the obtained mixed system is fully melted and plasticized under the double-screw conveying and shearing actions, and then the mixed system is bracing, cooled and granulated to obtain the halogen-free flame-retardant reinforced nylon material.
8. The method of manufacturing according to claim 7, wherein: the rotating speed of the double-screw extruder is 300-500 rpm, and the processing temperature is 220-260 ℃.
9. The method of manufacturing according to claim 6, comprising:
dissolving 4-hydroxybenzaldehyde in tetrahydrofuran and triethylamine as an acid binding agent, and reacting with hexachloro-triphosphazene to obtain hexa (4-aldehyde phenoxy) cyclotriphosphazene;
and (3) enabling the hexa (4-aldehyde phenoxy) cyclotriphosphazene to react with aminopropyl triethoxysilane, and then adding diphenyl dihydroxysilane to continue to react to obtain phosphorus-nitrogen modified silane.
10. Use of the halogen-free flame retardant reinforced nylon material of any one of claims 1-5 for the preparation of connectors for electrical and electronics or new energy automobiles.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002080715A (en) * | 2000-06-30 | 2002-03-19 | Mitsubishi Engineering Plastics Corp | Composition for magnet made of flame-retarded resin and magnet made of flame-retarded resin |
| JP2003292772A (en) * | 2002-03-29 | 2003-10-15 | Sakamoto Yakuhin Kogyo Co Ltd | Flame retardant polyamide resin composition |
| CN102257070A (en) * | 2008-12-17 | 2011-11-23 | 巴斯夫欧洲公司 | Layered silicate flame retardant compositions |
| CN110938294A (en) * | 2019-10-30 | 2020-03-31 | 南京聚隆科技股份有限公司 | Connector flame-retardant polyester material for new energy automobile and preparation method thereof |
| CN113260656A (en) * | 2019-01-07 | 2021-08-13 | 奥升德功能材料运营有限公司 | Non-halogenated flame retardant polyamide composition |
| CN115322441A (en) * | 2022-09-09 | 2022-11-11 | 江西福尔鑫医药化工有限公司 | Method for producing aluminum hypophosphite flame retardant by using sodium hypophosphite mother solution |
-
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002080715A (en) * | 2000-06-30 | 2002-03-19 | Mitsubishi Engineering Plastics Corp | Composition for magnet made of flame-retarded resin and magnet made of flame-retarded resin |
| JP2003292772A (en) * | 2002-03-29 | 2003-10-15 | Sakamoto Yakuhin Kogyo Co Ltd | Flame retardant polyamide resin composition |
| CN102257070A (en) * | 2008-12-17 | 2011-11-23 | 巴斯夫欧洲公司 | Layered silicate flame retardant compositions |
| CN113260656A (en) * | 2019-01-07 | 2021-08-13 | 奥升德功能材料运营有限公司 | Non-halogenated flame retardant polyamide composition |
| CN110938294A (en) * | 2019-10-30 | 2020-03-31 | 南京聚隆科技股份有限公司 | Connector flame-retardant polyester material for new energy automobile and preparation method thereof |
| CN115322441A (en) * | 2022-09-09 | 2022-11-11 | 江西福尔鑫医药化工有限公司 | Method for producing aluminum hypophosphite flame retardant by using sodium hypophosphite mother solution |
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