CN117106233B - Composite flame retardant containing aluminum phosphite and preparation method thereof - Google Patents
Composite flame retardant containing aluminum phosphite and preparation method thereof Download PDFInfo
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- CN117106233B CN117106233B CN202311377024.4A CN202311377024A CN117106233B CN 117106233 B CN117106233 B CN 117106233B CN 202311377024 A CN202311377024 A CN 202311377024A CN 117106233 B CN117106233 B CN 117106233B
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 46
- 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 41
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- HJJOHHHEKFECQI-UHFFFAOYSA-N aluminum;phosphite Chemical compound [Al+3].[O-]P([O-])[O-] HJJOHHHEKFECQI-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims description 20
- 239000010455 vermiculite Substances 0.000 claims abstract description 41
- 229910052902 vermiculite Inorganic materials 0.000 claims abstract description 41
- 235000019354 vermiculite Nutrition 0.000 claims abstract description 41
- 239000011521 glass Substances 0.000 claims abstract description 38
- 239000004005 microsphere Substances 0.000 claims abstract description 38
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 23
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 17
- 239000010445 mica Substances 0.000 claims abstract description 15
- 229910052618 mica group Inorganic materials 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 13
- 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 9
- ZJKCITHLCNCAHA-UHFFFAOYSA-K aluminum dioxidophosphanium Chemical compound [Al+3].[O-][PH2]=O.[O-][PH2]=O.[O-][PH2]=O ZJKCITHLCNCAHA-UHFFFAOYSA-K 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims description 28
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 15
- 239000000314 lubricant Substances 0.000 claims description 15
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 15
- -1 hexaphenoxy melamine Chemical compound 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 238000012216 screening Methods 0.000 claims description 8
- 229940098697 zinc laurate Drugs 0.000 claims description 8
- GPYYEEJOMCKTPR-UHFFFAOYSA-L zinc;dodecanoate Chemical compound [Zn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O GPYYEEJOMCKTPR-UHFFFAOYSA-L 0.000 claims description 8
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 7
- 229960001763 zinc sulfate Drugs 0.000 claims description 7
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- UWLXIENHSVDFSW-UHFFFAOYSA-N [diphenyl-[triphenyl-(phosphanylamino)-lambda5-phosphanyl]imino-lambda5-phosphanyl]benzene Chemical compound C1(=CC=CC=C1)P(N=P(C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1)(NP)(C1=CC=CC=C1)C1=CC=CC=C1 UWLXIENHSVDFSW-UHFFFAOYSA-N 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 5
- 238000011161 development Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 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
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000004246 zinc acetate Substances 0.000 description 2
- 229960000314 zinc acetate Drugs 0.000 description 2
- OGNSDRMLWYNUED-UHFFFAOYSA-N 1-cyclohexyl-4-[4-[4-(4-cyclohexylcyclohexyl)cyclohexyl]cyclohexyl]cyclohexane Chemical group C1CCCCC1C1CCC(C2CCC(CC2)C2CCC(CC2)C2CCC(CC2)C2CCCCC2)CC1 OGNSDRMLWYNUED-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/5399—Phosphorus bound to nitrogen
-
- 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
- C08K7/16—Solid spheres
- C08K7/18—Solid spheres inorganic
- C08K7/20—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
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- 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
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
-
- 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
Abstract
The invention provides a composite flame retardant containing aluminum phosphite, which is prepared from the following components in parts by weight: 56-74 parts of diethyl aluminum phosphinate, 22-31 parts of aluminum phosphinate, 14-23 parts of hexaphenyl triphosphazene, 5-9 parts of modified glass microspheres, 3-7 parts of mica, 1-5 parts of modified vermiculite, 1-3 parts of a silane coupling agent and 2-5 parts of a heat stabilizer; according to the invention, the aluminum phosphite, the modified glass microspheres, the mica, the modified vermiculite and other components are compounded, so that the prepared composite flame retardant has an excellent flame retardant effect, can remarkably improve the mechanical properties of the material, and has important significance in development and application of PVC materials.
Description
Technical Field
The invention belongs to the technical field of flame retardants, and particularly relates to a composite flame retardant containing aluminum phosphite and a preparation method thereof.
Background
The aluminum phosphite is a novel environment-friendly halogen-free inorganic phosphorus flame retardant, and has the characteristics of being slightly soluble in water, not easy to volatilize, high in phosphorus content, good in thermal stability and the like. Because the aluminum phosphite has high phosphorus content, the flame retardant has the advantages of good heat stability, small water solubility, large flame retardant efficiency and the like, and has better flame retardant effect when being used on PVC plastics. However, with the increase of the application field of the PVC material, the single use of the aluminum phosphite can not meet the market application requirement, and the situation that the mechanical property of the PVC material is easily reduced when the single addition of the aluminum phosphite is found to occur is studied.
Disclosure of Invention
The invention aims to provide a composite flame retardant containing aluminum phosphite and a preparation method thereof, wherein the aluminum phosphite and the rest components are compounded, so that the prepared composite flame retardant has excellent flame retardant effect and can improve the mechanical property of a material.
In order to achieve the above object, the present invention provides the following technical solutions:
the composite flame retardant containing the aluminum phosphite is prepared from the following components in parts by weight: 56-74 parts of diethyl aluminum phosphinate, 22-31 parts of aluminum phosphinate, 14-23 parts of hexaphenyl triphosphazene, 5-9 parts of modified glass microspheres, 3-7 parts of mica, 1-5 parts of modified vermiculite, 1-3 parts of a silane coupling agent and 2-5 parts of a heat stabilizer; the preparation method of the modified vermiculite comprises the following steps: crushing raw ore vermiculite to 50-100 meshes by a ball mill to obtain vermiculite powder; adding 10g of vermiculite powder into 300-400ml of hydrochloric acid aqueous solution with the concentration of 3-5mol/L, heating to 70-90 ℃, stirring for 4 hours, filtering, washing to neutrality, drying at 130 ℃ for 15-20 hours, and grinding to less than 100 meshes to obtain modified vermiculite;
the preparation method of the modified glass microsphere comprises the following steps: ablating the glass microspheres in a muffle furnace at 550 ℃ for 1-1.5h, immersing the ablated glass microspheres in an active lubricant for 4-5h, taking out, drying and sintering in the muffle furnace at 340 ℃ to obtain modified glass microspheres; wherein the active lubricant comprises the following components in percentage by mass: 50-53% of polytetrafluoroethylene with the grain diameter less than or equal to 12 mu m, 1-3% of lanthanum oxide, 0.5-2% of cerium oxide and the balance of ethanol.
The particle size is less than or equal to 12 mu m of polytetrafluoroethylene, which is purchased from merck, 430943.
Further, the glass microsphere has a diameter of 9-12 μm.
Further, the mica is 2000-3000 mesh.
Further, the silane coupling agent is one or more selected from silane coupling agent KH550, silane coupling agent KH560 and silane coupling agent KH 570.
Further, the heat stabilizer is one or more of zinc acetate, zinc laurate, zinc sulfate or cerium oxide.
Further, the heat stabilizer is zinc laurate, zinc sulfate and cerium oxide with the mass ratio of 1-3:1:1-3.
Further, the active lubricant comprises the following components in percentage by mass: 52% of polytetrafluoroethylene with the grain diameter less than or equal to 12 mu m, 2% of lanthanum oxide, 1% of cerium oxide and the balance of ethanol.
The invention also provides a preparation method of the composite flame retardant containing aluminum phosphite,
(1) Placing the components of the composite flame retardant into a variable frequency mixer for low-speed mixing and high-speed mixing two-stage uniform mixing;
(2) And conveying the uniformly mixed materials to a centrifugal vibration screening machine for screening to obtain the composite flame retardant.
Further, the stirring speed of low-speed mixing is 700-1000rpm/min, the mixing time is 5-10min, the temperature is not controlled, the stirring speed of high-speed mixing is 3000-4000rpm/min, the temperature is controlled at 60-70 ℃, and the mixing time is 30-40min.
Compared with the prior art, the invention has the advantages that:
the invention provides various aluminum phosphite-containing composite flame retardants and a preparation method thereof, and the aluminum phosphite and modified glass microspheres, mica, modified vermiculite and other components are compounded, so that the prepared composite flame retardants have excellent flame retardant effect, can remarkably improve the mechanical properties of materials, and have important significance in development and application of PVC materials.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The composite flame retardant containing the aluminum phosphite is prepared from the following components in parts by weight: 56-74 parts of diethyl aluminum phosphinate, 22-31 parts of aluminum phosphinate, 14-23 parts of hexaphenyl triphosphazene, 5-9 parts of modified glass microspheres, 3-7 parts of mica, 1-5 parts of modified vermiculite, 1-3 parts of a silane coupling agent and 2-5 parts of a heat stabilizer; the preparation method of the modified vermiculite comprises the following steps: crushing raw ore vermiculite to 50-100 meshes by a ball mill to obtain vermiculite powder; adding 10g of vermiculite powder into 300-400ml of hydrochloric acid aqueous solution with the concentration of 3-5mol/L, heating to 70-90 ℃, stirring for 4 hours, filtering, washing to neutrality, drying at 130 ℃ for 15-20 hours, and grinding to less than 100 meshes to obtain modified vermiculite;
the preparation method of the modified glass microsphere comprises the following steps: ablating the glass microspheres in a muffle furnace at 550 ℃ for 1-1.5h, immersing the ablated glass microspheres in an active lubricant for 4-5h, taking out, drying and sintering in the muffle furnace at 340 ℃ to obtain modified glass microspheres; wherein the active lubricant comprises the following components in percentage by mass: 50-53% of polytetrafluoroethylene with the grain diameter less than or equal to 12 mu m, 1-3% of lanthanum oxide, 0.5-2% of cerium oxide and the balance of ethanol.
The particle size is less than or equal to 12 mu m of polytetrafluoroethylene, which is purchased from merck, 430943.
The glass microspheres of this example have a diameter of 9-12. Mu.m.
The mica of this example is 2000-3000 mesh.
The silane coupling agent of the embodiment is one or more selected from silane coupling agent KH550, silane coupling agent KH560 and silane coupling agent KH 570.
The heat stabilizer of the embodiment is one or more of zinc acetate, zinc laurate, zinc sulfate or cerium oxide.
The heat stabilizer of the embodiment is zinc laurate, zinc sulfate and cerium oxide with the mass ratio of 1-3:1:1-3.
The active lubricant of the embodiment comprises the following components in percentage by mass: 52% of polytetrafluoroethylene with the grain diameter less than or equal to 12 mu m, 2% of lanthanum oxide, 1% of cerium oxide and the balance of ethanol.
The preparation method of the composite flame retardant containing the aluminum phosphite of the embodiment,
(1) Placing the components of the composite flame retardant into a variable frequency mixer for low-speed mixing and high-speed mixing two-stage uniform mixing;
(2) And conveying the uniformly mixed materials to a centrifugal vibration screening machine for screening to obtain the composite flame retardant.
The stirring speed of low-speed mixing in the embodiment is 700-1000rpm/min, the mixing time is 5-10min, the temperature is not controlled, the stirring speed of high-speed mixing is 3000-4000rpm/min, the temperature is controlled at 60-70 ℃, and the mixing time is 30-40min.
Example 1
The embodiment provides a composite flame retardant containing aluminum phosphite, which is prepared from the following components in parts by weight: 65 parts of diethyl aluminum phosphinate, 27 parts of aluminum phosphinate, 21 parts of hexaphenyl triphosphazene, 7 parts of modified glass microspheres, 5 parts of mica, 3 parts of modified vermiculite, 2 parts of a silane coupling agent and 3 parts of a heat stabilizer; the preparation method of the modified vermiculite comprises the following steps: crushing raw ore vermiculite to 80 meshes by a ball mill to obtain vermiculite powder; 10g of vermiculite powder is added into 350ml of hydrochloric acid aqueous solution with the concentration of 4mol/L, the temperature is raised to 85 ℃, the mixture is stirred for 4 hours, the mixture is filtered, washed to be neutral, dried for 17 hours at the temperature of 130 ℃, and ground to be less than 100 meshes, so that the modified vermiculite is obtained.
Aluminum diethylphosphinate, CAS:225789-38-8. Hexaphenyl triphosphazene, CAS 1110-78-7.
The preparation method of the modified glass microsphere comprises the following steps: ablating the glass microspheres in a muffle furnace at 550 ℃ for 1h, immersing the ablated glass microspheres in an active lubricant for 5h, taking out, drying and sintering in the muffle furnace at 340 ℃ to obtain modified glass microspheres; wherein the active lubricant comprises the following components in percentage by mass: 52% of polytetrafluoroethylene with the grain diameter less than or equal to 12 mu m, 2% of lanthanum oxide, 1% of cerium oxide and the balance of ethanol.
The polytetrafluoroethylene with the particle size less than or equal to 12 mu m is purchased from merck, 430943.
The diameter of the glass microsphere is 10 mu m.
The mica is 2500 mesh.
The silane coupling agent is a silane coupling agent KH550.
The heat stabilizer is composed of zinc laurate, zinc sulfate and cerium oxide in a mass ratio of 2:1:3.
The embodiment also provides a preparation method of the composite flame retardant containing aluminum phosphite,
(1) Placing the components of the composite flame retardant into a variable frequency mixer for low-speed mixing and high-speed mixing two-stage uniform mixing;
(2) And conveying the uniformly mixed materials to a centrifugal vibration screening machine for screening to obtain the composite flame retardant.
The stirring speed of low-speed mixing is 900rpm/min, the mixing time is 10min, the temperature is not controlled, the stirring speed of high-speed mixing is 3500rpm/min, the temperature is controlled at 65 ℃, and the mixing time is 35min.
Example 2
The differences between this embodiment and embodiment 1 are: the composite flame retardant containing the aluminum phosphite is prepared from the following components in parts by weight: 56 parts of diethyl aluminum phosphinate, 31 parts of aluminum phosphinate, 23 parts of hexaphenyl triphosphazene, 5 parts of modified glass microspheres, 3 parts of mica, 1 part of modified vermiculite, 2 parts of a silane coupling agent and 2 parts of a heat stabilizer.
Example 3
The differences between this embodiment and embodiment 1 are: the composite flame retardant containing the aluminum phosphite is prepared from the following components in parts by weight: 57 parts of diethyl aluminum phosphinate, 25 parts of aluminum phosphinate, 22 parts of hexaphenyl tripolyphosphazene, 8 parts of modified glass microspheres, 4 parts of mica, 2 parts of modified vermiculite, 3 parts of a silane coupling agent and 4 parts of a heat stabilizer.
Example 4
The differences between this embodiment and embodiment 1 are: the preparation method of the modified vermiculite comprises the following steps: crushing raw ore vermiculite to 60 meshes through a ball mill to obtain vermiculite powder; adding 10g of vermiculite powder into 400ml of hydrochloric acid aqueous solution with the concentration of 5mol/L, heating to 90 ℃, stirring for 4 hours, filtering, washing to neutrality, drying at 130 ℃ for 15 hours, and grinding to less than 100 meshes to obtain the modified vermiculite.
Example 5
The differences between this embodiment and embodiment 1 are: the preparation method of the modified glass microsphere comprises the following steps: ablating the glass microspheres in a muffle furnace at 550 ℃ for 1h, immersing the ablated glass microspheres in an active lubricant for 4h, taking out, drying and sintering in the muffle furnace at 340 ℃ to obtain modified glass microspheres; wherein the active lubricant comprises the following components in percentage by mass: 53% of polytetrafluoroethylene with the grain diameter less than or equal to 12 mu m, 1% of lanthanum oxide, 2% of cerium oxide and the balance of ethanol.
Example 6
The differences between this embodiment and embodiment 1 are: the heat stabilizer is zinc laurate, zinc sulfate and cerium oxide with the mass ratio of 3:1:1.
Comparative example 1
The difference between this comparative example and example 1 is: the composite flame retardant containing the aluminum phosphite is prepared from the following components in parts by weight: 50 parts of diethyl aluminum phosphinate, 35 parts of aluminum phosphinate, 12 parts of hexaphenyl triphosphazene, 4 parts of modified glass microspheres, 9 parts of mica, 2 parts of modified vermiculite, 2 parts of a silane coupling agent and 6 parts of a heat stabilizer.
Comparative example 2
The difference between this comparative example and example 1 is: the preparation method of the modified vermiculite comprises the following steps: crushing raw ore vermiculite to 150 meshes by a ball mill to obtain vermiculite powder; adding 10g of vermiculite powder into 500ml of hydrochloric acid aqueous solution with the concentration of 2mol/L, heating to 75 ℃, stirring for 4 hours, filtering, washing to neutrality, drying at 130 ℃ for 15 hours, and grinding to be less than 100 meshes to obtain the modified vermiculite.
Comparative example 3
The difference between this comparative example and example 1 is: the preparation method of the modified glass microsphere comprises the following steps: ablating the glass microspheres in a muffle furnace at 550 ℃ for 1h, immersing the ablated glass microspheres in an active lubricant for 4h, taking out, drying and sintering in the muffle furnace at 340 ℃ to obtain modified glass microspheres; wherein the active lubricant comprises the following components in percentage by mass: 55% of polytetrafluoroethylene with the grain diameter less than or equal to 12 mu m, 5% of lanthanum oxide and the balance of ethanol.
Comparative example 4
The difference between this comparative example and example 1 is: the heat stabilizer is zinc laurate, zinc oxide and lanthanum oxide with the mass ratio of 1:3:0.5.
Comparative example 5
The difference between this comparative example and example 1 is: the composite flame retardant containing the aluminum phosphite is prepared from the following components in parts by weight: 65 parts of diethyl aluminum phosphinate, 32 parts of aluminum phosphinate, 18 parts of hexaphenyl triphosphazene, 9 parts of mica, 3 parts of vermiculite, 2 parts of a silane coupling agent and 3 parts of a heat stabilizer.
Performance testing
The composite flame retardants prepared in examples and comparative examples were applied to conventional PVC materials, and the properties of the materials were tested according to the national standards, and the results of the performance tests are shown in table 1.
TABLE 1 Performance test results
As shown in examples 1-3 and comparative examples 1-5, the products of the invention have excellent flame retardant properties, and simultaneously the flame retardant properties and tensile strength properties can be improved in a coordinated manner, and as shown in comparative examples 1-5, the composite flame retardants prepared by different methods have a tendency to deteriorate the properties of the products, and the performance effects of the products are most remarkable only when the products are prepared by the methods of the invention.
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that various modifications and adaptations can be made without departing from the principles of the present invention, and such modifications and adaptations are intended to be comprehended within the scope of the present invention.
Claims (7)
1. The composite flame retardant containing the aluminum phosphite is characterized by being prepared from the following components in parts by weight: 56-64 parts of diethyl aluminum phosphinate, 22-31 parts of aluminum phosphinate, 14-23 parts of hexaphenoxy melamine, 5-9 parts of modified glass microspheres, 3-7 parts of mica, 1-5 parts of modified vermiculite, 1-3 parts of a silane coupling agent and 2-5 parts of a heat stabilizer; the preparation method of the modified vermiculite comprises the following steps: crushing raw ore vermiculite to 50-100 meshes by a ball mill to obtain vermiculite powder; adding 10g of vermiculite powder into 300-400ml of hydrochloric acid aqueous solution with the concentration of 3-5mol/L, heating to 70-90 ℃, stirring for 4 hours, filtering, washing to neutrality, drying at 130 ℃ for 15-20 hours, and grinding to less than 100 meshes to obtain modified vermiculite; the heat stabilizer is composed of zinc laurate, zinc sulfate and cerium oxide in a mass ratio of 1-3:1:1-3; the preparation method of the modified glass microsphere comprises the following steps: ablating the glass microspheres in a muffle furnace at 550 ℃ for 1-1.5h, then immersing the ablated glass microspheres in an active lubricant for 4-5h, taking out, drying and sintering in the muffle furnace at 340 ℃ to obtain modified glass microspheres; wherein the active lubricant comprises the following components in percentage by mass: 50-53% of polytetrafluoroethylene with the grain diameter less than or equal to 12 mu m, 1-3% of lanthanum oxide, 0.5-2% of cerium oxide and the balance of ethanol.
2. The aluminum phosphite containing composite flame retardant of claim 1, wherein the glass microspheres have a diameter of 9-12 μm.
3. The aluminum phosphite containing composite flame retardant of claim 1, wherein the mica is 2000-3000 mesh.
4. The aluminum phosphite containing composite flame retardant according to claim 1, wherein the silane coupling agent is selected from one or more of silane coupling agent KH550, silane coupling agent KH560, silane coupling agent KH 570.
5. The aluminum phosphite containing composite flame retardant of claim 1, wherein the reactive lubricant comprises the following components in mass percent: 52% of polytetrafluoroethylene with the grain diameter less than or equal to 12 mu m, 2% of lanthanum oxide, 1% of cerium oxide and the balance of ethanol.
6. The method for preparing the aluminum phosphite-containing composite flame retardant according to any one of claims 1-5, wherein,
(1) Placing the components of the composite flame retardant into a variable frequency mixer for low-speed mixing and high-speed mixing two-stage uniform mixing;
(2) And conveying the uniformly mixed materials to a centrifugal vibration screening machine for screening to obtain the composite flame retardant.
7. The method for preparing aluminum phosphite containing composite flame retardant according to claim 6, wherein the stirring speed of low speed mixing is 700-1000rpm, the mixing time is 5-10min, the temperature is not controlled, the stirring speed of high speed mixing is 3000-4000rpm, the temperature is controlled at 60-70 ℃, and the mixing time is 30-40min.
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| US3968297A (en) * | 1972-05-15 | 1976-07-06 | E. I. Du Pont De Nemours And Company | Polytetrafluoroethylene coatings for glass fabrics |
| KR20090030505A (en) * | 2007-09-20 | 2009-03-25 | 주식회사 엘지화학 | Flame retardant polyester composition with enhanced thermal resistance |
| WO2017097385A1 (en) * | 2015-12-07 | 2017-06-15 | Trovotech Gmbh | Complex halogen-free solid flame-retardant agent composition for polymer molding compounds, consisting of a reaction product of porous boron silicate glass particles which are produced by means of a high-temperature extrusion process and which melt at low temperatures, melamine, and ammonium nitrate, and method for producing same |
| CN109721768A (en) * | 2018-12-22 | 2019-05-07 | 广州市寅源新材料科技有限公司 | Bittern-free phosphorous-nitrogen composite flame-retardant agent and halogen-free combustion-proof thermoplastic polymer comprising it |
| CN115505172A (en) * | 2022-10-17 | 2022-12-23 | 广州市寅源新材料股份有限公司 | Halogen-free flame retardant and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102014001222A1 (en) * | 2014-01-29 | 2015-07-30 | Clariant lnternational Ltd | Halogen-free solid flame retardant mixture and its use |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3968297A (en) * | 1972-05-15 | 1976-07-06 | E. I. Du Pont De Nemours And Company | Polytetrafluoroethylene coatings for glass fabrics |
| KR20090030505A (en) * | 2007-09-20 | 2009-03-25 | 주식회사 엘지화학 | Flame retardant polyester composition with enhanced thermal resistance |
| WO2017097385A1 (en) * | 2015-12-07 | 2017-06-15 | Trovotech Gmbh | Complex halogen-free solid flame-retardant agent composition for polymer molding compounds, consisting of a reaction product of porous boron silicate glass particles which are produced by means of a high-temperature extrusion process and which melt at low temperatures, melamine, and ammonium nitrate, and method for producing same |
| CN109721768A (en) * | 2018-12-22 | 2019-05-07 | 广州市寅源新材料科技有限公司 | Bittern-free phosphorous-nitrogen composite flame-retardant agent and halogen-free combustion-proof thermoplastic polymer comprising it |
| CN115505172A (en) * | 2022-10-17 | 2022-12-23 | 广州市寅源新材料股份有限公司 | Halogen-free flame retardant and preparation method and application thereof |
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