CN117024957A - Migration-resistant modified halogen-free flame-retardant polyamide composition and preparation method thereof - Google Patents
Migration-resistant modified halogen-free flame-retardant polyamide composition and preparation method thereof Download PDFInfo
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- CN117024957A CN117024957A CN202311110915.3A CN202311110915A CN117024957A CN 117024957 A CN117024957 A CN 117024957A CN 202311110915 A CN202311110915 A CN 202311110915A CN 117024957 A CN117024957 A CN 117024957A
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 112
- 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 89
- 239000004952 Polyamide Substances 0.000 title claims abstract description 26
- 229920002647 polyamide Polymers 0.000 title claims abstract description 26
- 239000000203 mixture Substances 0.000 title claims abstract description 25
- 238000013508 migration Methods 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 230000005012 migration Effects 0.000 title claims description 10
- 239000000463 material Substances 0.000 claims abstract description 18
- 239000000945 filler Substances 0.000 claims abstract description 11
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 9
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 9
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 9
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000004595 color masterbatch Substances 0.000 claims abstract description 7
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical class [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims description 20
- 230000002195 synergetic effect Effects 0.000 claims description 13
- 239000002131 composite material Substances 0.000 claims description 11
- -1 PA56 Polymers 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 239000011574 phosphorus Substances 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 5
- 239000004917 carbon fiber Substances 0.000 claims description 5
- 239000012765 fibrous filler Substances 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing 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
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 3
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 229920002748 Basalt fiber Polymers 0.000 claims description 2
- 229920006153 PA4T Polymers 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 229920003235 aromatic polyamide Polymers 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 239000011521 glass Substances 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
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 229920006119 nylon 10T Polymers 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 229920006139 poly(hexamethylene adipamide-co-hexamethylene terephthalamide) Polymers 0.000 claims description 2
- 229920006128 poly(nonamethylene terephthalamide) Polymers 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000010456 wollastonite Substances 0.000 claims description 2
- 229910052882 wollastonite Inorganic materials 0.000 claims description 2
- 239000011324 bead Substances 0.000 claims 1
- 239000004677 Nylon Substances 0.000 abstract description 16
- 229920001778 nylon Polymers 0.000 abstract description 16
- 238000001556 precipitation Methods 0.000 abstract description 5
- 238000013461 design Methods 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 3
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 abstract description 2
- HIVGXUNKSAJJDN-UHFFFAOYSA-N [Si].[P] Chemical compound [Si].[P] HIVGXUNKSAJJDN-UHFFFAOYSA-N 0.000 abstract description 2
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 6
- 150000002367 halogens Chemical class 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000004594 Masterbatch (MB) Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000005543 nano-size silicon particle Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229920000734 polysilsesquioxane polymer Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000002210 silicon-based material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000004114 Ammonium polyphosphate Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229920001276 ammonium polyphosphate Polymers 0.000 description 2
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 2
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 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
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
Abstract
The invention discloses an anti-migration modified halogen-free flame-retardant polyamide composition and a preparation method thereof, wherein the composition comprises the following raw materials in parts by weight: 31-87% of polyamide resin, 10-30% of filler and flame retardant: 2-25% of modified flame retardant: 1-10 percent of antioxidant: 0-1%, processing aid: 0-2% of color master batch: 0-1%. According to the molecular structure characteristics of the nylon material, the flame retardant with a novel structure is introduced in the formula design, and contains a large number of amino active functional groups, so that the flame retardant is convenient to chemically graft with the nylon material, the precipitation risk of the flame retardant is reduced, and the service life of the flame retardant polymer is prolonged. Meanwhile, the POSS-cyclic phosphoramidate-triazine derivative type flame retardant is introduced, and the flame retardant can play a flame retardant role of phosphorus-nitrogen or phosphorus-silicon, so that the flame retardant efficiency is further improved.
Description
Technical Field
The invention relates to the field of thermoplastic high polymer materials, in particular to an anti-migration modified halogen-free flame-retardant polyamide composition and a preparation method thereof.
Background
Polyamide (nylon) is an important thermoplastic plastic and is widely applied to the fields of automobile parts, instrument instruments, household appliances, communication and the like due to its excellent mechanical properties, heat resistance, wear resistance and chemical corrosion resistance. However, unmodified nylon materials are flammable and are extremely prone to fire during use. Therefore, in order to widen the application field of nylon, flame retardant modification is required.
The early-stage additive flame retardant mainly comprises a halogen flame retardant, the halogen flame retardant has the advantages of high flame retardant efficiency, small consumption, wide adaptability and the like, chinese patent CN116376274A discloses a brominated flame-retardant reinforced nylon material and a preparation method thereof, and the specific zirconium hydroxide and hydrotalcite are compounded to solve the problem of acidic corrosive gas in the aspects of physics and chemistry, so that the stability of a brominated flame-retardant nylon resin system is improved, and the product has good high-temperature aging resistance. However, halogen flame retardants generate toxic gases and a large amount of smoke during combustion, which are serious to human body and environment, and thus, many fields are currently increasingly limiting the application of halogen flame retardants.
The traditional additive halogen-free flame retardant mainly comprises nitrogen flame retardants such as melamine and the like; phosphorus flame retardants such as ammonium polyphosphate (APP) and triphenyl phosphate (TPP); such as aluminum hydroxide, magnesium hydroxide, and the like. Chinese patent CN112409785A proposes a halogen-free flame retardant nylon material and a preparation method thereof, wherein MCA is used as a flame retardant, nano silicon dioxide is used as a synergistic combustion improver, and the addition of the nano silicon dioxide can produce synergistic effect with the MCA flame retardant, so that the carbonization speed of nylon is accelerated. Chinese patent CN112409785a proposes a continuous carbon fiber reinforced halogen-free flame retardant nylon composite material and a preparation method thereof. By adopting a mode of batch mixing the novel halogen-free flame retardant master batch and the continuous carbon fiber reinforced PA master batch, the composite material with different carbon fiber contents can be prepared, does not contain halogen flame retardants, reaches UL94V0 level flame retardant index, and has excellent mechanical property, electrical property and processability. However, various conventional additive halogen-free flame retardants have certain defects. The nitrogen flame retardant has poor dispersibility in resin materials and has strict requirements on granularity and granularity distribution; the phosphorus flame retardant has the defects of poor thermal stability and easiness in hydrolysis; the inorganic flame retardant has good flame retardant effect, but the addition amount is larger, and the mechanical property of the resin material can be obviously damaged while the flame retardant property of the resin material is improved.
The organic silicon is a semi-inorganic polymer material which takes an-Si-O-Si-bond as a molecular main chain and has a side group connected with an organic group, so that the formation of heat-insulating protective carbon can be promoted, and the generation of combustible gas products in a resin matrix can be reduced. The cage-shaped polyhedral oligomeric Polysilsesquioxane (POSS) has both a silicon dioxide rigid core and an external organic substituent group, and is used as a nano silicon material with a three-dimensional cage-shaped structure, so that the nano silicon material becomes a hot spot of current research. However, the conventional organic silicon material cannot promote the polymer matrix to form carbon during combustion, so that a relatively continuous and compact carbon layer is formed, and the effect is poor when the organic silicon material is singly used as a flame retardant additive, and the organic silicon material is mostly used as a flame retardant synergist. CN 105732987a relates to an organopolysiloxane compound containing isocyanate groups, which gives the corresponding organopolysiloxane compound containing isocyanate groups by an ene-thiol addition reaction of an organopolysiloxane compound having mercapto groups with an isocyanate compound having polymerizable groups.
In recent years, the disclosed patent focuses on researching a halogen-free flame-retardant nylon material composed of a phosphorus flame retardant, a phosphorus flame retardant and a synergist, and the system has the advantage of environmental protection compared with a halogen flame-retardant system, but most of the disclosed researches focus on simple compound blending modification of the existing halogen-free flame retardant, so that the research on molecular structural design of a novel halogen-free flame retardant is relatively less, and the application and development of the halogen-free flame-retardant nylon material are hindered.
Disclosure of Invention
The invention aims to overcome the defects and shortcomings in the prior art and provides an anti-migration modified halogen-free flame-retardant polyamide composition and a preparation method thereof. Through the molecular structure design of the flame retardant, the flame retardant efficiency is improved by introducing the phosphorus flame retardant with a brand new structure, the adding amount and precipitation risk of the flame retardant are reduced, and the adding amount of the flame retardant is further reduced by introducing the flame retardant with a brand new structure.
An anti-migration modified halogen-free flame retardant polyamide composition comprises the following raw materials in parts by weight: 31-87% of polyamide resin, 10-30% of filler and flame retardant: 0.1-25%, synergistic flame retardant: 0.1-15%, antioxidant: 0-1%, processing aid: 0-2% of color master batch: 0-1%.
The polyamide resin is one or more of PA46, PA56, PA6, PA66, PA4T, PA5T, PA T/6, PA6T/66/6 and PA9T, PA10T, PA T/66.
The filler can be fibrous or non-fibrous filler according to the form, the fibrous filler can be one or more of glass fiber, carbon fiber, basalt fiber and para-aramid fiber, and the non-fibrous filler can be one or more of glass microsphere, wollastonite, mica, kaolin, talcum powder and calcium carbonate.
The flame retardant is a diaminodiethyl phosphinic acid-ethyl aluminum phosphite composite salt. Phosphorus content: 24-28%, aluminum content: 7-8%; particle size (D50) 10-50 μm; the structural formula of the flame retardant is as follows:
the migration-resistant modified halogen-free flame-retardant polyamide composition is characterized in that: the synergistic flame retardant is a POSS-cyclic phosphoramidate-triazine derivative flame retardant with the following molecular structural formula:
r is the following structural formula:
R 1 the structural formula is as follows:
R 2 is at least one of the following structural formulas:
-CH 2 -CH 3
-CH 3
the preparation method of the migration-resistant modified halogen-free flame retardant polyamide composition comprises the following steps:
(1) Weighing the dried raw materials according to the formula proportion; uniformly stirring and mixing polyamide resin, a flame retardant, an antioxidant, a processing aid and color master batches by a high-speed stirrer for later use, and then weighing a filler according to the formula ratio for later use;
(2) The resin, the flame retardant, the antioxidant, the processing aid and the masterbatch are added through a main feeding port of a double-screw extruder, the filler is added through a side feeding port of the double-screw extruder, and the halogen-free flame retardant polyamide composition is obtained after the procedures of melt extrusion, granulation, drying and the like at 260 ℃.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention improves the flame retardance of the nylon composite material on the basis of guaranteeing the mechanical property of the matrix, and has the advantages of good flame retardance effect, wide application range and the like.
(2) The diamino diethyl phosphinic acid-ethyl aluminum phosphite composite salt flame retardant adopted by the invention contains a large number of amino active functional groups, is convenient for chemical grafting with nylon materials, further reduces the precipitation risk of the flame retardant and prolongs the service life of the flame retardant polymer.
(3) The POSS-cyclic phosphoramidate-triazine derivative flame retardant adopted by the invention designs three flame retardant elements of phosphorus, nitrogen and silicon into one molecule at the same time, the phosphorus can promote the formation of carbon, the POSS is heated to decompose to increase the stability of a carbon layer, the nitrogen can generate gas for diluting oxygen, and the three have synergistic flame retardant effects.
(4) The POSS-cyclic phosphoramidate-triazine derivative flame retardant adopted by the invention is applied to the modified nylon composite material, and nano particles are formed in a nylon matrix through self-assembly, so that the effect of enhancing mechanical properties is achieved.
(5) The diamino diethyl phosphinic acid-ethyl aluminum phosphite compound salt flame retardant and the POSS-cyclic phosphoramidate-triazine derivative flame retardant adopted by the invention can play the flame retardant effect of phosphorus-nitrogen or phosphorus-silicon, and further improve the flame retardant efficiency.
Detailed Description
In order to make the technical scheme of the present invention more clear and easy to understand, the present invention is further illustrated by the following specific examples, which are only illustrative of the technical scheme of the present invention, but are not limiting to the scope of the present invention.
The examples and comparative examples of the present invention use the following materials, but are not limited to:
nylon 66 resin, trade name EPR27, zephyr-mountain horse;
flame retardant, diethyl aluminum hypophosphite, a new material with the trade name of LFR-8003 and Jiangsu Li Saide;
flame retardants, trade name OP1314, CLARIANT;
flame retardant, diamino ethyl phosphinic acid-ethyl aluminium phosphite composite salt, commercially available; a synergistic flame retardant, a POSS-cyclic phosphoramidate-triazine derivative, commercially available;
synergistic flame retardant, trade name TPP, zhejiang Wansheng Co., ltd;
glass fiber, trade name ECS301HP-3, chongqing International composite;
processing aids, commercially available under the trade name silicone powder;
antioxidant 1098, a hindered phenolic antioxidant, commercially available; antioxidant 168, phosphite antioxidant, commercially available;
black master batch, PA6-2015, commercially available;
the preparation methods of examples 1-10 and comparative examples 1-5: preparation of flame retardant polyamide composition:
weighing the dried raw materials according to the formula proportion; uniformly mixing polyamide resin, a flame retardant, a molecular sieve, an acid absorber, a synergistic flame retardant, an antioxidant, a processing aid and color master batches by a high-speed stirrer for later use, and weighing a filler according to a ratio for later use; the resin and the auxiliary agent mixed raw materials are added through a main feeding port of a double-screw extruder, the filler is added from a side feeding port of the double-screw extruder, and the flame-retardant polyamide composition is obtained after the procedures of melt extrusion, granulation, drying treatment and the like at 260 ℃.
Preparation of flame retardant polyamide composition test bars: the above materials were dried in a forced air drying oven at 120 ℃ for 4 hours and then injection molded into standard bars at an injection molding temperature of 280-300 ℃. The injection molded mechanical property sample bars are subjected to state adjustment for 24 hours in a laboratory standard environment (23 ℃ and 50% RH).
The testing method of each performance index comprises the following steps:
tensile properties: spline size according to ISO 527 method: 170 x 10 x 4mm, test speed 5mm/min.
Notched impact properties: spline size according to ISO 179 method: 80 x 10 x 4mm.
Flame retardant properties: spline size according to UL94 method: 127 x 12.7 x 1.6mm.
Precipitation resistance: a template of 150 x 100 x 3.2mm was placed in an environmental chamber, the conditioning of which was set to: temperature: the state of the surface precipitate was visually evaluated at 85℃with a humidity of 85% RH for 250 hours.
Table 1: examples 1-11 and comparative examples 1-5 halogen-free flame retardant polyamide compositions composition and properties:
table 2: comparative examples 1-5 halogen-free flame retardant polyamide composition and properties:
as can be seen from tables 1 and 2, the diamino ethyl phosphinic acid-ethyl aluminum phosphate composite salt/POSS-cyclic phosphoramidate-triazine derivative composite flame-retardant system can effectively reduce the addition amount of the flame retardant compared with other similar products commercialized in the market, has high flame-retardant efficiency, achieves UL94V0 flame retardance without precipitation, has small influence on mechanical properties, and the prepared halogen-free flame-retardant polyamide has the characteristic of high strength. The invention content of the patent can promote the market competitiveness of halogen-free flame-retardant polyamide materials and expand the application potential of the halogen-free flame-retardant polyamide composition in the fields of energy automobiles, electronic appliances, connectors and the like.
Claims (7)
1. An anti-migration modified halogen-free flame retardant polyamide composition, which is characterized in that: the material comprises the following raw materials in parts by weight: 31-87% of polyamide resin, 10-30% of filler and flame retardant: 0.1-25%, synergistic flame retardant: 0.1-15%, antioxidant: 0-1%, processing aid: 0-2% of color master batch: 0-1%.
2. The migration resistant modified halogen-free flame retardant polyamide composition according to claim 1, wherein: the polyamide resin is selected from one or more of PA46, PA56, PA6, PA66, PA4T, PA5T, PA T/6, PA6T/66/6 and PA9T, PA10T, PA T/66.
3. The migration resistant modified halogen-free flame retardant polyamide composition according to claim 1, wherein: the filler is fibrous or non-fibrous according to the form, and the fibrous filler can be one or more of glass fiber, carbon fiber, basalt fiber and para-aramid fiber.
4. A migration resistant modified halogen free flame retardant polyamide composition according to claim 3, wherein: the non-fibrous filler is selected from one or more of glass beads, wollastonite, mica, kaolin, talcum powder and calcium carbonate.
5. The migration resistant modified halogen-free flame retardant polyamide composition according to claim 1, wherein: the flame retardant is selected from diamino diethyl phosphinic acid-ethyl aluminum phosphite composite salt, wherein the phosphorus content is as follows: 24-28%, aluminum content: 7-8%; particle size (D50) 10-50 μm; the structural formula of the flame retardant is as follows:
6. the migration resistant modified halogen-free flame retardant polyamide composition according to claim 1, wherein: the synergistic flame retardant is a POSS-cyclic phosphoramidate-triazine derivative flame retardant, and the molecular structural formula of the synergistic flame retardant is as follows:
r is the following structural formula:
R 1 the structural formula is as follows:
R 2 is at least one of the following structural formulas:
-CH 2 -CH 3
-CH 3。
7. a process for the preparation of an migration resistant modified halogen free flame retardant polyamide composition according to any one of claims 1 to 6, characterized in that it comprises the steps of:
(1) Weighing the dried raw materials according to the formula proportion; uniformly stirring and mixing polyamide resin, a flame retardant, a synergistic flame retardant, an antioxidant, a processing aid and color master batches by a high-speed stirrer for later use, and then weighing a filler according to the formula ratio for later use;
(2) The mixed raw materials of the resin, the flame retardant, the synergistic flame retardant, the antioxidant, the processing aid and the color master batch are added through a main feeding port of a double-screw extruder, the filler is added from a side feeding port of the double-screw extruder, and the halogen-free flame retardant polyamide composition is obtained after the procedures of melt extrusion, granulation, drying and the like at 260 ℃.
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