CN116925541A - Halogen-free environment-friendly flame-retardant nylon with high glow wire - Google Patents
Halogen-free environment-friendly flame-retardant nylon with high glow wire Download PDFInfo
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- CN116925541A CN116925541A CN202310690834.9A CN202310690834A CN116925541A CN 116925541 A CN116925541 A CN 116925541A CN 202310690834 A CN202310690834 A CN 202310690834A CN 116925541 A CN116925541 A CN 116925541A
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- flame retardant
- graphene oxide
- zirconium phosphate
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 85
- 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 56
- 239000004677 Nylon Substances 0.000 title abstract description 13
- 229920001778 nylon Polymers 0.000 title abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 50
- 229920002302 Nylon 6,6 Polymers 0.000 claims abstract description 46
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims abstract description 39
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 claims abstract description 30
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims abstract description 29
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 239000006185 dispersion Substances 0.000 claims abstract description 11
- 239000004094 surface-active agent Substances 0.000 claims abstract description 11
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical group OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000003647 oxidation Effects 0.000 claims abstract description 8
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 7
- 239000002131 composite material Substances 0.000 claims abstract description 6
- 239000003365 glass fiber Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000003963 antioxidant agent Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 239000000314 lubricant Substances 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 229910006251 ZrOCl2.8H2O Inorganic materials 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 1
- 235000011007 phosphoric acid Nutrition 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 239000007789 gas Substances 0.000 abstract description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 2
- 238000010000 carbonizing Methods 0.000 abstract description 2
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 230000007246 mechanism Effects 0.000 abstract description 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 2
- 239000011574 phosphorus Substances 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 230000007704 transition Effects 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 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 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- JYVWZHOGCZHONC-UHFFFAOYSA-N aminomethyl(phenyl)phosphinic acid Chemical compound NCP(O)(=O)C1=CC=CC=C1 JYVWZHOGCZHONC-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000010954 inorganic particle 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
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000012899 standard injection Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000002604 ultrasonography 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/328—Phosphates of heavy metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- 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
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- 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 application relates to a high glowing filament halogen-free environment-friendly flame-retardant nylon 66, which is characterized in that a gas phase and condensed phase flame-retardant mechanism is jointly formed by introducing halogen-free flame retardants containing phosphorus and nitrogen components to achieve the aim of flame retardance, and flaky alpha-zirconium phosphate is loaded on the surface of graphene oxide, so that the thermal oxidation stability of the graphene oxide is improved, the alpha-zirconium phosphate can also play a role in catalyzing and carbonizing, and the thermal stability and flame retardance of a polymer composite material are improved synergistically: according to the application, the transition phase zirconium phosphate is converted into alpha-zirconium phosphate in a short time by gas and vapor generated by instantaneous microwave heating decomposition of ammonium nitrate, the zirconium phosphate can be uniformly dispersed on the surface of graphene oxide by combining the dispersion effect of the surfactant, the flame-retardant effect of the nylon material can be better promoted by a small amount of flame-retardant synergist, and the problems of complex preparation process and high energy consumption of the graphene-loaded zirconium phosphate composite material are solved.
Description
Technical Field
The application belongs to the technical field of high polymer materials, and particularly relates to a high glow wire halogen-free environment-friendly flame-retardant nylon.
Background
Nylon 66 is one of the earliest synthetic development and relatively cheap varieties in polyamide resin, has the characteristics of light weight, high mechanical strength and easy molding and processing, has excellent comprehensive properties such as wear resistance, oil resistance, self-lubricating property, corrosion resistance and the like, and occupies the first five major engineering plastics with excellent physical properties, but is easy to burn, has poor dimensional stability and the like, and limits the application fields. Therefore, flame retardant modification of nylon 66 is a common concern in the current academia and industry.
Chinese patent CN104746168B discloses a flame retardant nylon 66 fiber and a preparation method thereof, wherein the flame retardant nylon 66 fiber contains 0.5-15% by mass of flame retardant aminomethyl phenyl phosphinic acid, the addition amount of the flame retardant is small but the flame retardant effect is good; chinese patent CN104861645B discloses a heat-conducting flame-retardant nylon 66 and a preparation method thereof, wherein the added graphene is modified by aqueous titanate, and is subjected to magnetic field and ultrasonic treatment to achieve dispersion and stripping effects, no agglomeration is generated in nylon 66, and the heat-conducting flame-retardant nylon 66 with good graphene dispersion and good bonding can be prepared by the method; however, the single-component flame retardant has poor use effect, and the graphene is modified by the aqueous titanate, so that the graphene is also modified insufficiently to cause uneven dispersion, and further dispersion treatment by adopting a magnetic field and ultrasound is required; chinese patent CN112126224a discloses a high temperature resistant flame retardant nylon and a preparation method thereof, which adopts nano zirconium phosphate and the like as heat stabilizer and flame retardant to be used in combination, so as to have the characteristics of high temperature resistance, high flame retardance, high melting point and the like, but the problem of uneven dispersion due to easy agglomeration in plastic materials still exists due to small particle size and high surface energy of nano inorganic particles; chinese patent CN105694107B discloses a preparation method of nano alpha-zirconium phosphate loaded graphene oxide flame retardant, wherein zirconium phosphate is loaded on the surface of graphene oxide sheet in the form of nano particles, so that the thermal stability and flame retardant effect of the graphene oxide sheet in a high polymer material can be improved, but the preparation method is time-consuming, long in energy consumption, expensive in the used oxidation reagent, not suitable for large-scale mass production, and long in production period of the composite material.
Accordingly, the present application has been made to solve the above-mentioned problems occurring in the prior art.
Disclosure of Invention
Aiming at the prior art, the application provides a high glow wire halogen-free environment-friendly flame retardant nylon 66, which comprises 55-60% of PA66, 12-20% of halogen-free flame retardant, 25-30% of glass fiber, 3-5% of flame retardant synergist and 0-1% of other auxiliary agents by mass, wherein the flame retardant synergist is graphene oxide loaded with nano zirconium phosphate.
Preferably, the halogen-free flame retardant is commercially available halogen-free flame retardant FR-3300.
Preferably, the other auxiliary agents are antioxidants and/or lubricants.
Preferably, the specific preparation method of the graphene oxide loaded with the nano zirconium phosphate comprises the following steps:
step 1), preparing graphene oxide by adopting a Hummers oxidation expansion method;
step 2), zrOCl is added 2 ·8H 2 O, surfactant, graphene oxide and H 3 PO 4 Respectively dissolving in deionized water to obtainAnd (3) adding ammonium nitrate into the solution with a certain concentration under vacuum condition after uniformly dispersing, continuously stirring uniformly, carrying out microwave heating reaction for 30min at 80 ℃, and washing and drying to obtain the graphene oxide alpha-ZrP/rGO loaded with nano zirconium phosphate.
Preferably, the surfactant in step 2) is polyvinylpyrrolidone, sodium dodecylbenzene sulfonate or sodium fatty alcohol ether sulfate.
Preferably, zrOCl in step 2) 2 ·8H 2 O, surfactant, graphene oxide and H 3 PO 4 The mass ratio of the deionized water to the deionized water is 1: (5-20): (3-15): (10-25): (800-2000).
Preferably, in step 2) ammonium nitrate is combined with ZrOCl 2 ·8H 2 The mass ratio of O is (4-10): 1.
the application further aims to provide a preparation method of the high glow wire halogen-free environment-friendly flame-retardant nylon 66, which comprises the following steps:
55-60% by mass of PA66, 12-20% by mass of halogen-free flame retardant, 3-5% by mass of flame retardant synergist and 0-1% by weight of other auxiliary agents are put into a stirrer to be stirred for 10 minutes, and put into a preheated double-screw machine to be produced, wherein the main machine rotating speed is 430r/min, and 25-30% by mass of glass fibers are added from a glass fiber port, and modified PA66 particles are obtained through a double-screw granulator.
Compared with the prior art, the high glow wire halogen-free environment-friendly flame retardant nylon 66 disclosed by the application has the advantages that the halogen-free flame retardant containing phosphorus and nitrogen components is introduced to jointly form a gas phase and condensed phase flame retardant mechanism to achieve the flame retardant purpose, and the flaky alpha-zirconium phosphate is loaded on the surface of graphene oxide, so that the thermal oxidation stability of the graphene oxide is improved, the alpha-zirconium phosphate can also play a role in catalyzing and carbonizing, and the thermal stability and flame retardant performance of the polymer composite material are improved synergistically: according to the application, the transition phase zirconium phosphate phase is converted into alpha-zirconium phosphate by the vapor generated by the violent expansion of the gas and liquid water generated by the instantaneous microwave heating decomposition of ammonium nitrate, the zirconium phosphate can be uniformly dispersed on the surface of graphene oxide by combining the dispersion effect of the surfactant, the good dispersibility of the zirconium phosphate can enable the zirconium phosphate to better exert flame retardant performance in flame retardant effect, the consumption of the zirconium phosphate can be reduced, the large-scale mass production can be realized, and the problems of complex preparation process, long time consumption and high energy consumption of the graphene loaded zirconium phosphate composite material are solved.
Drawings
FIG. 1 is a TEM image of graphene oxide loaded with nano zirconium phosphate prepared in example 1;
FIG. 2 is a graph of the finished graphene oxide loaded with nano zirconium phosphate prepared in example 1;
FIG. 3 is a graph of modified nylon PA66 particles obtained in example 2;
FIG. 4 is a graph of modified nylon PA66 particles obtained in comparative example 1.
Detailed Description
The implementation of the technical solution of the present application and the advantages thereof will be described in detail by the following specific examples, but should not be construed as limiting the scope of the implementation of the present application.
Example 1
The high glow wire halogen-free environment-friendly flame retardant nylon 66 comprises, by mass, 60% of PA66, 19% of a halogen-free flame retardant, 27% of glass fibers and 3% of graphene oxide loaded with nano zirconium phosphate. Wherein the halogen-free flame retardant is commercially available halogen-free flame retardant FR-3300, produced by Zhejiang Xuesen.
The specific preparation method of the graphene oxide loaded with the nano zirconium phosphate comprises the following steps:
step 1), preparing graphene oxide by adopting a Hummers oxidation expansion method;
step 2), 1kg ZrOCl is added 2 ·8H 2 O, 15kg surfactant PVP, 10kg graphene oxide and 16kg H 3 PO 4 Respectively dissolving in 1200L deionized water to prepare a solution, adding 7kg ammonium nitrate under vacuum condition after dispersing uniformly, continuously stirring uniformly, injecting into a microwave reaction kettle, setting at 80deg.C for microwave heating reaction for 30min, washing and drying after the reaction is completed to obtain graphene oxide alpha-ZrP/rGO loaded with nano zirconium phosphate (see figure 1 and figure 2), wherein the monodisperse flaky alpha-ZrP is loaded on the surface of graphene oxide as can be seen from figure 1, and the graphene oxide alpha-ZrP loaded with nano zirconium phosphate is obtained in a shorter time as can be seen from figure 2The kilogram-level alpha-ZrP/rGO has good industrialized application foundation compared with the laboratory gram-level product in the prior art.
And (3) placing the weighed PA66, halogen-free flame retardant and flame retardant synergist into a stirrer to stir for 10 minutes, placing the mixture into a preheated double-screw machine to produce, adding 27% glass fiber by mass of a host machine with the rotating speed of 430r/min from a glass fiber port, and finally obtaining a corresponding modified PA66 product.
Example 2
The high glow wire halogen-free environment-friendly flame retardant nylon 66 comprises 58.3% of PA66, 12% of halogen-free flame retardant, 25% of glass fiber, 4% of graphene oxide loaded with nano zirconium phosphate, 0.3% of lubricant PETS,0.2% of antioxidant 1098,0.2% of auxiliary antioxidant 168 by mass. Wherein the halogen-free flame retardant is a commercial halogen-free flame retardant FR-3300, manufactured by Zhejiang Xuesen, the PETS manufacturer is Italian hair base, and the manufacturers of the antioxidants 1098 and 168 are Tianjin An Long.
The specific preparation method of the graphene oxide with the nanometer zirconium phosphate comprises the following steps:
step 1), preparing graphene oxide by adopting a Hummers oxidation expansion method;
step 2) 1kg ZrOCl2.8H2O, 5kg surfactant PVP, 15kg graphene oxide and 10kg H 3 PO 4 Respectively dissolving in 800L deionized water to prepare solutions, adding 4kg of ammonium nitrate under vacuum condition after uniform dispersion, continuously stirring uniformly, injecting into a microwave reaction kettle, setting at 100 ℃ for microwave heating reaction for 20min, washing and drying after the reaction is completed to prepare the graphene oxide alpha-ZrP/rGO loaded with nano zirconium phosphate.
The weighed PA66, the halogen-free flame retardant and the flame retardant synergist are placed into a stirrer to be stirred for 10 minutes, the mixture is placed into a preheated double-screw machine to be produced, the main machine rotating speed is 430r/min, 25% of glass fibers by mass are added from a glass fiber port, and a corresponding modified PA66 product (see figure 3) is finally obtained, and as can be seen from figure 3, the obtained product is black and uniform in color, and the graphene oxide modified by the hummers method has good compatibility and dispersion performance with nylon materials.
Example 3
The high glow wire halogen-free environment-friendly flame retardant nylon 66 comprises 55.6% of PA66, 12% of halogen-free flame retardant, 29% of glass fiber, 3% of graphene oxide loaded with nano zirconium phosphate and 0.4% of lubricant PETS by mass. Wherein the halogen-free flame retardant is a commercial halogen-free flame retardant FR-3300, manufactured by Zhejiang Xuesen, and the PETS manufacturer is Italian hair base.
The specific preparation method of the graphene oxide loaded with the nano zirconium phosphate comprises the following steps:
step 1), preparing graphene oxide by adopting a Hummers oxidation expansion method;
step 2) 1kg ZrOCl2.8H2O, 20kg surfactant PVP, 5kg graphene oxide and 20kg H 3 PO 4 Respectively dissolving in 1800 liters of deionized water to prepare solutions, adding 9kg of ammonium nitrate under vacuum condition after uniform dispersion, continuously stirring uniformly, injecting into a microwave reaction kettle, setting at 70 ℃ for microwave heating reaction for 40min, washing and drying after the reaction is finished to prepare the graphene oxide alpha-ZrP/rGO loaded with nano zirconium phosphate.
And (3) placing the weighed PA66, halogen-free flame retardant and flame retardant synergist into a stirrer to stir for 10 minutes, placing the mixture into a preheated double-screw machine to produce, adding 29% by mass of glass fibers from a glass fiber port at the rotating speed of a main machine of 430r/min, and finally obtaining a corresponding modified PA66 product.
Comparative example 1
A modified nylon 66 comprises 60.3% of PA66, 13% of halogen-free flame retardant, 26% of glass fiber and 0.3% of lubricant PETS,0.2% of antioxidant 1098,0.2% of auxiliary antioxidant 168 by mass, wherein the halogen-free flame retardant is commercially available halogen-free flame retardant FR-3300, manufactured by Zhejiang Xuesen, the PETS manufacturer is Italian hair base, and the manufacturers of antioxidants 1098 and 168 are Tianjin An Long.
The weighed PA66, halogen-free flame retardant and calcium stearate are placed into a stirrer to be stirred for 10 minutes, the mixture is placed into a preheated double-screw machine to be produced, the main machine rotating speed is 430r/min, 26% of glass fibers by mass are added from a glass fiber port, and a corresponding modified PA66 product (see figure 4) is finally obtained, and the obtained product is white as can be seen from figure 4.
Comparative example 2
A modified nylon 66, which comprises 58.3% of PA66, 12% of halogen-free flame retardant, 25% of glass fiber, 4% of alpha-zirconium phosphate, 0.3% of lubricant PETS,0.2% of antioxidant 1098,0.2% of auxiliary antioxidant 168 by mass. Wherein the halogen-free flame retardant is a commercial halogen-free flame retardant FR-3300, manufactured by Zhejiang Xuesen, the PETS manufacturer is Italian hair base, and the manufacturers of the antioxidants 1098 and 168 are Tianjin An Long.
And (3) placing the weighed PA66, halogen-free flame retardant, alpha-zirconium phosphate and calcium stearate into a stirrer to be stirred for 10 minutes, placing the mixture into a preheated double-screw machine to be produced, adding 25% glass fiber by mass of the mixture into the mixture from a glass fiber port at the host rotation speed of 430r/min, and finally obtaining a corresponding modified PA66 product.
Performance testing
The modified PA66 prepared in examples 1-3 and comparative examples 1-2 was subjected to a GB/T standard injection molding sample bar, and subjected to a 24-hour performance test at a temperature of 23+ -2deg.C and a temperature of 50+ -5%, wherein a glowing filament flame retardancy test temperature value was performed under the conditions of GWFI/2.0mm using GB/T5169, a vertical flame retardancy test was performed under the conditions of 1.6mm using UL 94 standard, and a gray scale test was performed at 575-625 deg.C according to the GB/T9345 standard, as follows.
From the test results, the flame retardant effect of the nylon material PA66 is V1 before the flame retardant synergist is not added, V0 is added, and the burning temperature of the glowing filament is greatly improved. The flame retardant effect of comparative example 2 is not significantly improved after the same amount of the flame retardant synergist monomer as in example 2 is added, and the flame retardant effect of the nylon material is improved after the flame retardant synergist monomer is added after the flame retardant synergist monomer is compounded with graphene oxide, which is related to the different structures of the flame retardant synergist monomer and the graphene oxide. The application has the advantages of cost advantage and low energy consumption, is simple in reaction, is more suitable for large-scale mass production, is different from incompatibility of inorganic material zirconium phosphate in nylon components, poor in dispersing effect in granulating process and easy to agglomerate, and affects the exertion of flame-retardant effect, and the application has good compatibility with nylon materials by modifying graphene oxide, so that the modified nylon PA66 has good high-heat, environment-friendly and flame-retardant effects, the burning test residual rate reaches 30%, and the European and American environmental-friendly index requirements are met.
Claims (6)
1. The halogen-free environment-friendly flame-retardant nylon 66 with high glow wires is characterized in that: the flame-retardant composite material comprises 55-60% of PA66, 12-20% of halogen-free flame retardant, 25-30% of glass fiber, 3-5% of flame-retardant synergist and 0-1% of other auxiliary agents by mass, wherein the flame-retardant synergist is graphene oxide loaded with nano zirconium phosphate, and the specific preparation method of the graphene oxide loaded with nano zirconium phosphate is as follows:
step 1), preparing graphene oxide by adopting a Hummers oxidation expansion method;
step 2), zrOCl is added 2 ·8H 2 O, surfactant, graphene oxide and H 3 PO 4 Respectively dissolving the materials in deionized water to prepare a solution with a certain concentration, adding ammonium nitrate under a vacuum condition after uniform dispersion, continuously stirring uniformly, carrying out microwave heating reaction for 20-40min at 70-100 ℃, and washing and drying to obtain the graphene oxide alpha-ZrP/rGO loaded with nano zirconium phosphate.
2. The high glow wire halogen-free environment-friendly flame retardant nylon 66 according to claim 1, wherein: the surfactant in the step 2) is polyvinylpyrrolidone, sodium dodecyl benzene sulfonate or sodium fatty alcohol ether sulfate.
3. The high glow wire halogen-free environment-friendly flame retardant nylon 66 according to claim 1, wherein: in the step 2), the mass ratio of ZrOCl2.8H2O, the surfactant, the graphene oxide and H3PO4 to deionized water is 1: (5-20): (3-15): (10-25): (800-2000).
4. The high glow wire halogen-free environment-friendly flame retardant nylon 66 according to claim 1, wherein: in the step 2), the mass ratio of the ammonium nitrate to ZrOCl2.8H2O is (4-10): 1.
5. the high glow wire halogen-free environment-friendly flame retardant nylon 66 according to claim 1, wherein: the halogen-free flame retardant is a commercial halogen-free flame retardant FR-3300.
6. The high glow wire halogen-free environment-friendly flame retardant nylon 66 according to claim 1, wherein: the other auxiliary agents are antioxidants and/or lubricants.
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| CN202210666576.6A CN114957984A (en) | 2022-06-13 | 2022-06-13 | High glow-wire halogen-free environment-friendly flame-retardant nylon |
| CN2022106665766 | 2022-06-13 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102424722A (en) * | 2011-11-25 | 2012-04-25 | 深圳市科聚新材料有限公司 | High glow-wire and fiber halogen-free flame-retardant nylon 66 material and preparation method thereof |
| CN105694107A (en) * | 2016-01-26 | 2016-06-22 | 同济大学 | Preparation method of nano alpha-zirconium phosphate loaded graphene oxide flame retardant |
| WO2017173979A1 (en) * | 2016-04-05 | 2017-10-12 | 中国科学院理化技术研究所 | Highly effective non-halogen composite flame retardant and preparation method therefor |
| CN111117222A (en) * | 2019-12-12 | 2020-05-08 | 中广核俊尔(浙江)新材料有限公司 | Glow-wire-resistant nonflammable polyamide composition and preparation method and application thereof |
| CN111808392A (en) * | 2020-07-20 | 2020-10-23 | 上海荣富新型材料有限公司 | Preparation of alpha-ZrP/GO flame retardant and application thereof in polyvinyl alcohol |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105440671A (en) * | 2015-11-19 | 2016-03-30 | 东莞市众一新材料科技有限公司 | High-glow-wire glass-fiber reinforced flame-retardant nylon composite material and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102424722A (en) * | 2011-11-25 | 2012-04-25 | 深圳市科聚新材料有限公司 | High glow-wire and fiber halogen-free flame-retardant nylon 66 material and preparation method thereof |
| CN105694107A (en) * | 2016-01-26 | 2016-06-22 | 同济大学 | Preparation method of nano alpha-zirconium phosphate loaded graphene oxide flame retardant |
| WO2017173979A1 (en) * | 2016-04-05 | 2017-10-12 | 中国科学院理化技术研究所 | Highly effective non-halogen composite flame retardant and preparation method therefor |
| CN111117222A (en) * | 2019-12-12 | 2020-05-08 | 中广核俊尔(浙江)新材料有限公司 | Glow-wire-resistant nonflammable polyamide composition and preparation method and application thereof |
| CN111808392A (en) * | 2020-07-20 | 2020-10-23 | 上海荣富新型材料有限公司 | Preparation of alpha-ZrP/GO flame retardant and application thereof in polyvinyl alcohol |
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